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Food Chemistry IB Chemistry Option F

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Food Chemistry. IB Chemistry Option F. Nutrients. A food is any substance we deliberately ingest for nourishment, ideally containing one or more nutrients A nutrient is a component of food used by the body to provide energy or to grow and repair tissue Carbohydrates (sugars) - PowerPoint PPT Presentation

TRANSCRIPT

Page 1: Food Chemistry

Food Chemistry

IB Chemistry Option F

Nutrients A food is any substance we deliberately ingest

for nourishment ideally containing one or more nutrients

A nutrient is a component of food used by the body to provide energy or to grow and repair tissue

Carbohydrates (sugars) Lipids (fatsoils) Proteins Water Vitamins and minerals

Lack of nutrients leads to malnourishment

Food Groups 5 Main food groups

Grains ndash complex carbohydrates (polysaccharides) vitamins and minerals

Fruit ndash simple carbohydrates (mono and disaccharides) vitamins and minerals

Vegetables ndash simple and complex carbohydrates vitamins and minerals

MeatBeansFishPoultry ndash proteins vitamins and minerals fats and oils

Dairy ndash simple carbohydrates proteins fats and oils

Nutrients (carbohydrates)

Monosaccharides (ONE sugar) One carbonyl group (C=O) At least two hydroxyl groups (-OH) Empirical formula of CH2O

(carbo C and hydrate H2O) Ex Glucose C6H12O6 Ex Fructose C6H12O6

glucose

fructose

Nutrients (carbohydrates) Disaccharides (TWO

sugars) form when two monosaccharides come together releasing a water molecule (condensation reaction)

ldquoNew bondrdquo is called a glycosidic linkage between the two original monosaccharides

Polysaccharides (MANY sugars aka complex carbohydrates) are the combination of many simple sugars through glycosidic linkages

+ H2O

Nutrients (fats and oils)

Fats and oils are both classified as triglycerides Glycerol (CH2OHCHOHCH2OH) combines

with three fatty acid molecules (fatty = long nonpolar hydrocarbon chain and acid = carboxylic acid)

Also called triesters because of the formation of an ester group when an alcohol group (from glycerol) combines with a carboxylic acid group (from fatty acid)

Nutrients (fats and oils)

Formation of a triglyceride

Nutrients (proteins)

Proteins are polymers of amino acids 20 different amino acid ldquomonomersrdquo

form long chains of near infinite combinations

Typical protein is approximately 300 amino acids but can be made from less or more

Peptide bond (aka amide linkage) bonds amino acids together

+ H2O

Nutrients (water and vitaminsminerals)

Do not provide energy Water is used for transport and

various metabolic processes Vitamins and minerals are also

important in metabolic processes and as enzyme cofactors

Fats and Oils

Properties of a fat (chiefly melting point and chemical stability) are related to The degree of unsaturation ( of double bonds in

the hydrocarbon chains) More double bonds = lower melting point and more

reactive Length of the hydrocarbon chains

Shorter chains = lower melting point Whether the chain is cis or trans isomerized

around double bonds cis = lower melting point

Fats and Oils Saturated ndash all C-C single bonds

Fatty acid has a regular zig-zag shape due to geometry around sp3 hybridized carbon atoms

Monounsaturated ndash one C=C double bond Can be cis or trans isomerized

cis means hydrogen atoms are on same side of double bond trans means hydogen atoms are on opposite sides of the

double bond Polyunsaturated ndash multiple C=C double bonds

Can be either cis or trans isomerized A ldquofatrdquo is a tryglyceride that is solid at room

temperature Usually saturated monounsaturated or trans unsaturated

An oil is a triglyceride that is liquid at room temperature Usually polyunsaturated

Fats and Oils Fats with longer hydrocarbon chains are able to make

more van der Waals forces between each other making molecules harder to separate Higher melting point

Saturated fats have ldquostraightrdquo chains that pack closely and allow for lots of contact between molecules making molecules harder to separate Higher melting point

Trans-unsaturated fats have straight chains just as saturated fats do Higher melting point

Cis-unsaturated fats have irregularly-shaped less ldquostraightrdquo chains Do not pack as closely molecules are easier to separate Lower melting point

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 2: Food Chemistry

Nutrients A food is any substance we deliberately ingest

for nourishment ideally containing one or more nutrients

A nutrient is a component of food used by the body to provide energy or to grow and repair tissue

Carbohydrates (sugars) Lipids (fatsoils) Proteins Water Vitamins and minerals

Lack of nutrients leads to malnourishment

Food Groups 5 Main food groups

Grains ndash complex carbohydrates (polysaccharides) vitamins and minerals

Fruit ndash simple carbohydrates (mono and disaccharides) vitamins and minerals

Vegetables ndash simple and complex carbohydrates vitamins and minerals

MeatBeansFishPoultry ndash proteins vitamins and minerals fats and oils

Dairy ndash simple carbohydrates proteins fats and oils

Nutrients (carbohydrates)

Monosaccharides (ONE sugar) One carbonyl group (C=O) At least two hydroxyl groups (-OH) Empirical formula of CH2O

(carbo C and hydrate H2O) Ex Glucose C6H12O6 Ex Fructose C6H12O6

glucose

fructose

Nutrients (carbohydrates) Disaccharides (TWO

sugars) form when two monosaccharides come together releasing a water molecule (condensation reaction)

ldquoNew bondrdquo is called a glycosidic linkage between the two original monosaccharides

Polysaccharides (MANY sugars aka complex carbohydrates) are the combination of many simple sugars through glycosidic linkages

+ H2O

Nutrients (fats and oils)

Fats and oils are both classified as triglycerides Glycerol (CH2OHCHOHCH2OH) combines

with three fatty acid molecules (fatty = long nonpolar hydrocarbon chain and acid = carboxylic acid)

Also called triesters because of the formation of an ester group when an alcohol group (from glycerol) combines with a carboxylic acid group (from fatty acid)

Nutrients (fats and oils)

Formation of a triglyceride

Nutrients (proteins)

Proteins are polymers of amino acids 20 different amino acid ldquomonomersrdquo

form long chains of near infinite combinations

Typical protein is approximately 300 amino acids but can be made from less or more

Peptide bond (aka amide linkage) bonds amino acids together

+ H2O

Nutrients (water and vitaminsminerals)

Do not provide energy Water is used for transport and

various metabolic processes Vitamins and minerals are also

important in metabolic processes and as enzyme cofactors

Fats and Oils

Properties of a fat (chiefly melting point and chemical stability) are related to The degree of unsaturation ( of double bonds in

the hydrocarbon chains) More double bonds = lower melting point and more

reactive Length of the hydrocarbon chains

Shorter chains = lower melting point Whether the chain is cis or trans isomerized

around double bonds cis = lower melting point

Fats and Oils Saturated ndash all C-C single bonds

Fatty acid has a regular zig-zag shape due to geometry around sp3 hybridized carbon atoms

Monounsaturated ndash one C=C double bond Can be cis or trans isomerized

cis means hydrogen atoms are on same side of double bond trans means hydogen atoms are on opposite sides of the

double bond Polyunsaturated ndash multiple C=C double bonds

Can be either cis or trans isomerized A ldquofatrdquo is a tryglyceride that is solid at room

temperature Usually saturated monounsaturated or trans unsaturated

An oil is a triglyceride that is liquid at room temperature Usually polyunsaturated

Fats and Oils Fats with longer hydrocarbon chains are able to make

more van der Waals forces between each other making molecules harder to separate Higher melting point

Saturated fats have ldquostraightrdquo chains that pack closely and allow for lots of contact between molecules making molecules harder to separate Higher melting point

Trans-unsaturated fats have straight chains just as saturated fats do Higher melting point

Cis-unsaturated fats have irregularly-shaped less ldquostraightrdquo chains Do not pack as closely molecules are easier to separate Lower melting point

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 3: Food Chemistry

Food Groups 5 Main food groups

Grains ndash complex carbohydrates (polysaccharides) vitamins and minerals

Fruit ndash simple carbohydrates (mono and disaccharides) vitamins and minerals

Vegetables ndash simple and complex carbohydrates vitamins and minerals

MeatBeansFishPoultry ndash proteins vitamins and minerals fats and oils

Dairy ndash simple carbohydrates proteins fats and oils

Nutrients (carbohydrates)

Monosaccharides (ONE sugar) One carbonyl group (C=O) At least two hydroxyl groups (-OH) Empirical formula of CH2O

(carbo C and hydrate H2O) Ex Glucose C6H12O6 Ex Fructose C6H12O6

glucose

fructose

Nutrients (carbohydrates) Disaccharides (TWO

sugars) form when two monosaccharides come together releasing a water molecule (condensation reaction)

ldquoNew bondrdquo is called a glycosidic linkage between the two original monosaccharides

Polysaccharides (MANY sugars aka complex carbohydrates) are the combination of many simple sugars through glycosidic linkages

+ H2O

Nutrients (fats and oils)

Fats and oils are both classified as triglycerides Glycerol (CH2OHCHOHCH2OH) combines

with three fatty acid molecules (fatty = long nonpolar hydrocarbon chain and acid = carboxylic acid)

Also called triesters because of the formation of an ester group when an alcohol group (from glycerol) combines with a carboxylic acid group (from fatty acid)

Nutrients (fats and oils)

Formation of a triglyceride

Nutrients (proteins)

Proteins are polymers of amino acids 20 different amino acid ldquomonomersrdquo

form long chains of near infinite combinations

Typical protein is approximately 300 amino acids but can be made from less or more

Peptide bond (aka amide linkage) bonds amino acids together

+ H2O

Nutrients (water and vitaminsminerals)

Do not provide energy Water is used for transport and

various metabolic processes Vitamins and minerals are also

important in metabolic processes and as enzyme cofactors

Fats and Oils

Properties of a fat (chiefly melting point and chemical stability) are related to The degree of unsaturation ( of double bonds in

the hydrocarbon chains) More double bonds = lower melting point and more

reactive Length of the hydrocarbon chains

Shorter chains = lower melting point Whether the chain is cis or trans isomerized

around double bonds cis = lower melting point

Fats and Oils Saturated ndash all C-C single bonds

Fatty acid has a regular zig-zag shape due to geometry around sp3 hybridized carbon atoms

Monounsaturated ndash one C=C double bond Can be cis or trans isomerized

cis means hydrogen atoms are on same side of double bond trans means hydogen atoms are on opposite sides of the

double bond Polyunsaturated ndash multiple C=C double bonds

Can be either cis or trans isomerized A ldquofatrdquo is a tryglyceride that is solid at room

temperature Usually saturated monounsaturated or trans unsaturated

An oil is a triglyceride that is liquid at room temperature Usually polyunsaturated

Fats and Oils Fats with longer hydrocarbon chains are able to make

more van der Waals forces between each other making molecules harder to separate Higher melting point

Saturated fats have ldquostraightrdquo chains that pack closely and allow for lots of contact between molecules making molecules harder to separate Higher melting point

Trans-unsaturated fats have straight chains just as saturated fats do Higher melting point

Cis-unsaturated fats have irregularly-shaped less ldquostraightrdquo chains Do not pack as closely molecules are easier to separate Lower melting point

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 4: Food Chemistry

Nutrients (carbohydrates)

Monosaccharides (ONE sugar) One carbonyl group (C=O) At least two hydroxyl groups (-OH) Empirical formula of CH2O

(carbo C and hydrate H2O) Ex Glucose C6H12O6 Ex Fructose C6H12O6

glucose

fructose

Nutrients (carbohydrates) Disaccharides (TWO

sugars) form when two monosaccharides come together releasing a water molecule (condensation reaction)

ldquoNew bondrdquo is called a glycosidic linkage between the two original monosaccharides

Polysaccharides (MANY sugars aka complex carbohydrates) are the combination of many simple sugars through glycosidic linkages

+ H2O

Nutrients (fats and oils)

Fats and oils are both classified as triglycerides Glycerol (CH2OHCHOHCH2OH) combines

with three fatty acid molecules (fatty = long nonpolar hydrocarbon chain and acid = carboxylic acid)

Also called triesters because of the formation of an ester group when an alcohol group (from glycerol) combines with a carboxylic acid group (from fatty acid)

Nutrients (fats and oils)

Formation of a triglyceride

Nutrients (proteins)

Proteins are polymers of amino acids 20 different amino acid ldquomonomersrdquo

form long chains of near infinite combinations

Typical protein is approximately 300 amino acids but can be made from less or more

Peptide bond (aka amide linkage) bonds amino acids together

+ H2O

Nutrients (water and vitaminsminerals)

Do not provide energy Water is used for transport and

various metabolic processes Vitamins and minerals are also

important in metabolic processes and as enzyme cofactors

Fats and Oils

Properties of a fat (chiefly melting point and chemical stability) are related to The degree of unsaturation ( of double bonds in

the hydrocarbon chains) More double bonds = lower melting point and more

reactive Length of the hydrocarbon chains

Shorter chains = lower melting point Whether the chain is cis or trans isomerized

around double bonds cis = lower melting point

Fats and Oils Saturated ndash all C-C single bonds

Fatty acid has a regular zig-zag shape due to geometry around sp3 hybridized carbon atoms

Monounsaturated ndash one C=C double bond Can be cis or trans isomerized

cis means hydrogen atoms are on same side of double bond trans means hydogen atoms are on opposite sides of the

double bond Polyunsaturated ndash multiple C=C double bonds

Can be either cis or trans isomerized A ldquofatrdquo is a tryglyceride that is solid at room

temperature Usually saturated monounsaturated or trans unsaturated

An oil is a triglyceride that is liquid at room temperature Usually polyunsaturated

Fats and Oils Fats with longer hydrocarbon chains are able to make

more van der Waals forces between each other making molecules harder to separate Higher melting point

Saturated fats have ldquostraightrdquo chains that pack closely and allow for lots of contact between molecules making molecules harder to separate Higher melting point

Trans-unsaturated fats have straight chains just as saturated fats do Higher melting point

Cis-unsaturated fats have irregularly-shaped less ldquostraightrdquo chains Do not pack as closely molecules are easier to separate Lower melting point

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 5: Food Chemistry

Nutrients (carbohydrates) Disaccharides (TWO

sugars) form when two monosaccharides come together releasing a water molecule (condensation reaction)

ldquoNew bondrdquo is called a glycosidic linkage between the two original monosaccharides

Polysaccharides (MANY sugars aka complex carbohydrates) are the combination of many simple sugars through glycosidic linkages

+ H2O

Nutrients (fats and oils)

Fats and oils are both classified as triglycerides Glycerol (CH2OHCHOHCH2OH) combines

with three fatty acid molecules (fatty = long nonpolar hydrocarbon chain and acid = carboxylic acid)

Also called triesters because of the formation of an ester group when an alcohol group (from glycerol) combines with a carboxylic acid group (from fatty acid)

Nutrients (fats and oils)

Formation of a triglyceride

Nutrients (proteins)

Proteins are polymers of amino acids 20 different amino acid ldquomonomersrdquo

form long chains of near infinite combinations

Typical protein is approximately 300 amino acids but can be made from less or more

Peptide bond (aka amide linkage) bonds amino acids together

+ H2O

Nutrients (water and vitaminsminerals)

Do not provide energy Water is used for transport and

various metabolic processes Vitamins and minerals are also

important in metabolic processes and as enzyme cofactors

Fats and Oils

Properties of a fat (chiefly melting point and chemical stability) are related to The degree of unsaturation ( of double bonds in

the hydrocarbon chains) More double bonds = lower melting point and more

reactive Length of the hydrocarbon chains

Shorter chains = lower melting point Whether the chain is cis or trans isomerized

around double bonds cis = lower melting point

Fats and Oils Saturated ndash all C-C single bonds

Fatty acid has a regular zig-zag shape due to geometry around sp3 hybridized carbon atoms

Monounsaturated ndash one C=C double bond Can be cis or trans isomerized

cis means hydrogen atoms are on same side of double bond trans means hydogen atoms are on opposite sides of the

double bond Polyunsaturated ndash multiple C=C double bonds

Can be either cis or trans isomerized A ldquofatrdquo is a tryglyceride that is solid at room

temperature Usually saturated monounsaturated or trans unsaturated

An oil is a triglyceride that is liquid at room temperature Usually polyunsaturated

Fats and Oils Fats with longer hydrocarbon chains are able to make

more van der Waals forces between each other making molecules harder to separate Higher melting point

Saturated fats have ldquostraightrdquo chains that pack closely and allow for lots of contact between molecules making molecules harder to separate Higher melting point

Trans-unsaturated fats have straight chains just as saturated fats do Higher melting point

Cis-unsaturated fats have irregularly-shaped less ldquostraightrdquo chains Do not pack as closely molecules are easier to separate Lower melting point

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 6: Food Chemistry

Nutrients (fats and oils)

Fats and oils are both classified as triglycerides Glycerol (CH2OHCHOHCH2OH) combines

with three fatty acid molecules (fatty = long nonpolar hydrocarbon chain and acid = carboxylic acid)

Also called triesters because of the formation of an ester group when an alcohol group (from glycerol) combines with a carboxylic acid group (from fatty acid)

Nutrients (fats and oils)

Formation of a triglyceride

Nutrients (proteins)

Proteins are polymers of amino acids 20 different amino acid ldquomonomersrdquo

form long chains of near infinite combinations

Typical protein is approximately 300 amino acids but can be made from less or more

Peptide bond (aka amide linkage) bonds amino acids together

+ H2O

Nutrients (water and vitaminsminerals)

Do not provide energy Water is used for transport and

various metabolic processes Vitamins and minerals are also

important in metabolic processes and as enzyme cofactors

Fats and Oils

Properties of a fat (chiefly melting point and chemical stability) are related to The degree of unsaturation ( of double bonds in

the hydrocarbon chains) More double bonds = lower melting point and more

reactive Length of the hydrocarbon chains

Shorter chains = lower melting point Whether the chain is cis or trans isomerized

around double bonds cis = lower melting point

Fats and Oils Saturated ndash all C-C single bonds

Fatty acid has a regular zig-zag shape due to geometry around sp3 hybridized carbon atoms

Monounsaturated ndash one C=C double bond Can be cis or trans isomerized

cis means hydrogen atoms are on same side of double bond trans means hydogen atoms are on opposite sides of the

double bond Polyunsaturated ndash multiple C=C double bonds

Can be either cis or trans isomerized A ldquofatrdquo is a tryglyceride that is solid at room

temperature Usually saturated monounsaturated or trans unsaturated

An oil is a triglyceride that is liquid at room temperature Usually polyunsaturated

Fats and Oils Fats with longer hydrocarbon chains are able to make

more van der Waals forces between each other making molecules harder to separate Higher melting point

Saturated fats have ldquostraightrdquo chains that pack closely and allow for lots of contact between molecules making molecules harder to separate Higher melting point

Trans-unsaturated fats have straight chains just as saturated fats do Higher melting point

Cis-unsaturated fats have irregularly-shaped less ldquostraightrdquo chains Do not pack as closely molecules are easier to separate Lower melting point

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 7: Food Chemistry

Nutrients (fats and oils)

Formation of a triglyceride

Nutrients (proteins)

Proteins are polymers of amino acids 20 different amino acid ldquomonomersrdquo

form long chains of near infinite combinations

Typical protein is approximately 300 amino acids but can be made from less or more

Peptide bond (aka amide linkage) bonds amino acids together

+ H2O

Nutrients (water and vitaminsminerals)

Do not provide energy Water is used for transport and

various metabolic processes Vitamins and minerals are also

important in metabolic processes and as enzyme cofactors

Fats and Oils

Properties of a fat (chiefly melting point and chemical stability) are related to The degree of unsaturation ( of double bonds in

the hydrocarbon chains) More double bonds = lower melting point and more

reactive Length of the hydrocarbon chains

Shorter chains = lower melting point Whether the chain is cis or trans isomerized

around double bonds cis = lower melting point

Fats and Oils Saturated ndash all C-C single bonds

Fatty acid has a regular zig-zag shape due to geometry around sp3 hybridized carbon atoms

Monounsaturated ndash one C=C double bond Can be cis or trans isomerized

cis means hydrogen atoms are on same side of double bond trans means hydogen atoms are on opposite sides of the

double bond Polyunsaturated ndash multiple C=C double bonds

Can be either cis or trans isomerized A ldquofatrdquo is a tryglyceride that is solid at room

temperature Usually saturated monounsaturated or trans unsaturated

An oil is a triglyceride that is liquid at room temperature Usually polyunsaturated

Fats and Oils Fats with longer hydrocarbon chains are able to make

more van der Waals forces between each other making molecules harder to separate Higher melting point

Saturated fats have ldquostraightrdquo chains that pack closely and allow for lots of contact between molecules making molecules harder to separate Higher melting point

Trans-unsaturated fats have straight chains just as saturated fats do Higher melting point

Cis-unsaturated fats have irregularly-shaped less ldquostraightrdquo chains Do not pack as closely molecules are easier to separate Lower melting point

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 8: Food Chemistry

Nutrients (proteins)

Proteins are polymers of amino acids 20 different amino acid ldquomonomersrdquo

form long chains of near infinite combinations

Typical protein is approximately 300 amino acids but can be made from less or more

Peptide bond (aka amide linkage) bonds amino acids together

+ H2O

Nutrients (water and vitaminsminerals)

Do not provide energy Water is used for transport and

various metabolic processes Vitamins and minerals are also

important in metabolic processes and as enzyme cofactors

Fats and Oils

Properties of a fat (chiefly melting point and chemical stability) are related to The degree of unsaturation ( of double bonds in

the hydrocarbon chains) More double bonds = lower melting point and more

reactive Length of the hydrocarbon chains

Shorter chains = lower melting point Whether the chain is cis or trans isomerized

around double bonds cis = lower melting point

Fats and Oils Saturated ndash all C-C single bonds

Fatty acid has a regular zig-zag shape due to geometry around sp3 hybridized carbon atoms

Monounsaturated ndash one C=C double bond Can be cis or trans isomerized

cis means hydrogen atoms are on same side of double bond trans means hydogen atoms are on opposite sides of the

double bond Polyunsaturated ndash multiple C=C double bonds

Can be either cis or trans isomerized A ldquofatrdquo is a tryglyceride that is solid at room

temperature Usually saturated monounsaturated or trans unsaturated

An oil is a triglyceride that is liquid at room temperature Usually polyunsaturated

Fats and Oils Fats with longer hydrocarbon chains are able to make

more van der Waals forces between each other making molecules harder to separate Higher melting point

Saturated fats have ldquostraightrdquo chains that pack closely and allow for lots of contact between molecules making molecules harder to separate Higher melting point

Trans-unsaturated fats have straight chains just as saturated fats do Higher melting point

Cis-unsaturated fats have irregularly-shaped less ldquostraightrdquo chains Do not pack as closely molecules are easier to separate Lower melting point

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 9: Food Chemistry

Nutrients (water and vitaminsminerals)

Do not provide energy Water is used for transport and

various metabolic processes Vitamins and minerals are also

important in metabolic processes and as enzyme cofactors

Fats and Oils

Properties of a fat (chiefly melting point and chemical stability) are related to The degree of unsaturation ( of double bonds in

the hydrocarbon chains) More double bonds = lower melting point and more

reactive Length of the hydrocarbon chains

Shorter chains = lower melting point Whether the chain is cis or trans isomerized

around double bonds cis = lower melting point

Fats and Oils Saturated ndash all C-C single bonds

Fatty acid has a regular zig-zag shape due to geometry around sp3 hybridized carbon atoms

Monounsaturated ndash one C=C double bond Can be cis or trans isomerized

cis means hydrogen atoms are on same side of double bond trans means hydogen atoms are on opposite sides of the

double bond Polyunsaturated ndash multiple C=C double bonds

Can be either cis or trans isomerized A ldquofatrdquo is a tryglyceride that is solid at room

temperature Usually saturated monounsaturated or trans unsaturated

An oil is a triglyceride that is liquid at room temperature Usually polyunsaturated

Fats and Oils Fats with longer hydrocarbon chains are able to make

more van der Waals forces between each other making molecules harder to separate Higher melting point

Saturated fats have ldquostraightrdquo chains that pack closely and allow for lots of contact between molecules making molecules harder to separate Higher melting point

Trans-unsaturated fats have straight chains just as saturated fats do Higher melting point

Cis-unsaturated fats have irregularly-shaped less ldquostraightrdquo chains Do not pack as closely molecules are easier to separate Lower melting point

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 10: Food Chemistry

Fats and Oils

Properties of a fat (chiefly melting point and chemical stability) are related to The degree of unsaturation ( of double bonds in

the hydrocarbon chains) More double bonds = lower melting point and more

reactive Length of the hydrocarbon chains

Shorter chains = lower melting point Whether the chain is cis or trans isomerized

around double bonds cis = lower melting point

Fats and Oils Saturated ndash all C-C single bonds

Fatty acid has a regular zig-zag shape due to geometry around sp3 hybridized carbon atoms

Monounsaturated ndash one C=C double bond Can be cis or trans isomerized

cis means hydrogen atoms are on same side of double bond trans means hydogen atoms are on opposite sides of the

double bond Polyunsaturated ndash multiple C=C double bonds

Can be either cis or trans isomerized A ldquofatrdquo is a tryglyceride that is solid at room

temperature Usually saturated monounsaturated or trans unsaturated

An oil is a triglyceride that is liquid at room temperature Usually polyunsaturated

Fats and Oils Fats with longer hydrocarbon chains are able to make

more van der Waals forces between each other making molecules harder to separate Higher melting point

Saturated fats have ldquostraightrdquo chains that pack closely and allow for lots of contact between molecules making molecules harder to separate Higher melting point

Trans-unsaturated fats have straight chains just as saturated fats do Higher melting point

Cis-unsaturated fats have irregularly-shaped less ldquostraightrdquo chains Do not pack as closely molecules are easier to separate Lower melting point

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 11: Food Chemistry

Fats and Oils Saturated ndash all C-C single bonds

Fatty acid has a regular zig-zag shape due to geometry around sp3 hybridized carbon atoms

Monounsaturated ndash one C=C double bond Can be cis or trans isomerized

cis means hydrogen atoms are on same side of double bond trans means hydogen atoms are on opposite sides of the

double bond Polyunsaturated ndash multiple C=C double bonds

Can be either cis or trans isomerized A ldquofatrdquo is a tryglyceride that is solid at room

temperature Usually saturated monounsaturated or trans unsaturated

An oil is a triglyceride that is liquid at room temperature Usually polyunsaturated

Fats and Oils Fats with longer hydrocarbon chains are able to make

more van der Waals forces between each other making molecules harder to separate Higher melting point

Saturated fats have ldquostraightrdquo chains that pack closely and allow for lots of contact between molecules making molecules harder to separate Higher melting point

Trans-unsaturated fats have straight chains just as saturated fats do Higher melting point

Cis-unsaturated fats have irregularly-shaped less ldquostraightrdquo chains Do not pack as closely molecules are easier to separate Lower melting point

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 12: Food Chemistry

Fats and Oils Fats with longer hydrocarbon chains are able to make

more van der Waals forces between each other making molecules harder to separate Higher melting point

Saturated fats have ldquostraightrdquo chains that pack closely and allow for lots of contact between molecules making molecules harder to separate Higher melting point

Trans-unsaturated fats have straight chains just as saturated fats do Higher melting point

Cis-unsaturated fats have irregularly-shaped less ldquostraightrdquo chains Do not pack as closely molecules are easier to separate Lower melting point

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 13: Food Chemistry

Fats and Oils

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 14: Food Chemistry

Fats and Oils ldquoDegree of Crystallizationrdquo is

related to the melting point of a fat Higher melting point means a higher

degree of crystallization (fat is more likely to be solid at room temperature)

Increases with Increasing degree of saturation Increasing amount of trans-unsaturation Higher molecular mass

Naturally-occuring triglycerides most commonly tend to be cis-unsaturated

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 15: Food Chemistry

Fats and Oils cis-unsaturated fats are typically the

healthiest Lower melting point allows for less

buildup of plaque in the arteries that can cause stroke or heart attack

trans-unsaturated fats are less healthy do not commonly occur naturally are harder to metabolize and buildup in fatty tissue Cause an increase in LDL cholesterol

(Low Density Lipoprotein or ldquobadrdquo cholesterol

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 16: Food Chemistry

Fats and Oils Unsaturated oils are more reactive due to the

possibility of addition reactions across the double bonds Are thus less stable and keep less well than saturated

fats Prone to auto-oxidation in the presence of light

(photo-oxidation) which is a reaction of the fats with atmospheric oxygen

Also more prone to hydrogenation (addition of hydrogen) hydrolysis (breaking of the fat back into glycerol and fatty acids) and microbial degradation

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 17: Food Chemistry

Fats and Oils Unsaturated fats are often artificially

hydrogenatedpartially hydrogenated Increases degree of saturation

Allows for control of texture because melting point is affected

Improves stability and shelf life as reactivity is decreased Improves cooking technique where more solid fats are

needed Hydrogen gas is added over a solid nickel catalyst

Double bonds converted to single bonds and degree of saturation increases

Drawback - decreases the health value as fats are healthier when mono- or poly-unsaturated

Ni(s)

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 18: Food Chemistry

Shelf Life Foods gradually become unfit for consumption

due to Spoilage (growth of organisms) Changes in texture smell flavor or appearance

Undesirable processes caused by Change in water content Chemical reactions Exposure to light Changes in temperature

Shelf life is the length of time a product can be stored without these undesirable changes occurring

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 19: Food Chemistry

Shelf Life Change in water content

Causes texture change Loss of water increases exposure to air and thus oxidation

Causes rancidity and discoloration Increase in water encourages microbial growth and

spoilage Chemical reactionstemperature change

Increased temperature increases rates of ldquoharmful reactionsrdquo

Changes in pH or temperature affect the amount of water in a food

Souring with decrease in pH Changes color Can decrease nutritional value

Light provides energy for ldquoharmfulrdquo chemical reactions

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 20: Food Chemistry

Shelf Life Rancidity is a common type of food

degradation Unpleasant textures smells and flavors of fats

and oils

Two types of rancidity Hydrolytic rancidity ndash ester bond in fat is broken

yielding free fatty acids (reverse of formation of a fat) Oxidative rancidity ndash oxygen reacts near the C=C

double bonds in unsaturated fats

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 21: Food Chemistry

Shelf Life Hydrolytic rancidity of fats and oils

reverse of fat formation uses water (hydro lysis = ldquowaterrdquo ldquosplittingrdquo) to split triglycerides back into glycerol and fatty acids

Encouraged by Lipase ndash an enzyme produced by microorganisms Deep frying ndash encourages reaction of fats with moisture in

food Releases free fatty acids

4 ndash 8 carbon fatty acids have a powerfully pungent aromaflavor

palmitic stearic oleic lauric acids give a soapy fatty feel to foods

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 22: Food Chemistry

Shelf Life Oxidative rancidity of fats and oils

Reaction of atmospheric oxygen with fats and oils initiates complex process producing highly reactive free radicals

Products include unpleasant smellingtasting byproducts

More of an issue with increasing degree of unsaturation (more C=C double bonds to react with)

Encouraged by the presence of light (photo-oxidation) Enzymes produced by microorganisms

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 23: Food Chemistry

Shelf Life Oxidative rancidity of fats and oils occurs in 3

steps Initiation by exposure to light ndash produces highly

reactive hydrocarbon radicals (species with an unpaired electron)

R-H R + H Propagation ndash radicals produce other radicals

R + O2 R-O-O ROO + R-H R-O-O-H + R

Termination ndash radicals encounter one another and end the reaction

R + R R-R R-O-O + R-O-O R-O-O-O-O-R R + R-O-O R-O-O-R

(R-H = unsaturated fat or oil R = hydrocarbon radical images on next slide)

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 24: Food Chemistry

Shelf Life Initiation

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 25: Food Chemistry

Shelf Life Propagation

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 26: Food Chemistry

Shelf Life Termination

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 27: Food Chemistry

Shelf Life Shelf life is prolonged by hindering spoilage

processes Packaging

Opaque or darkened packages block light Can be gas impermeable to limit exposure to oxygen and water Can be filled with inert gases or vacuum packed (no gases)

Storage Low temperatures slow harmful reactions Smoking or drying foods removes water and hinder microbial

growth Additives

Salt or sugar added to remove water and hinder microbial growth

KNO3 or NaNO3 salts are reducing agents and can prevent harmful oxidation reactions

Anti-microbial agents Pickling - Organic acids and their salts (ex benzoic acid and

benzoate salts) make pH unfavorable for microbial growth Fermentation ndash production of alcohol hinders microbial growth

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 28: Food Chemistry

Shelf Life Antioxidants delay oxidative degradation

processes by reacting with oxygen to contain free radical formation Can occur naturally

Vitamin C (ascorbic acid) ndash citrus and green vegetables Vitamin E (tocopherol) ndash nuts seeds grains canola oil Beta-carotene ndash carrots broccoli tomatoes peaches Selenium ndash shellfish meat eggs grains Foods high in natural antioxidants green tea blueberries

cranberries dark chocolate turmeric oregano Can be synthetic additives but may have harmful

side effects BHA BHT PG THBP TBHQ

these are all based around a phenol

groupwhich is not

necessarily found in natural

antioxidants

(Full structures in

data booklet)

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 29: Food Chemistry

Shelf Life Types of antioxidants

Free radical quenchers React with radicals to produce less reactive radicals (HA =

quencher)R-O-O + HA R-O-O-H + A

Chelating agents Form very stable complex ions with transition metals (which

can produce radicals) Found naturally in rosemary tea and mustard Salts of the organic acid EDTA are added as artificial chelating

agents Reducing agents

React with oxygen or hydroperoxides Vitamin C or carotenoids are natural reducing agents

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 30: Food Chemistry

Color Foods are colored by either pigments or dyes

Pigments occur naturally Dyes are added artificially and must be tested for

safety Dyes or pigments will absorb a range of light

frequencies and reflect others The color we see in a dye or pigment is the result of

the colors of light reflected not absorbed Ex chlorophyll in green leaf vegetables absorbs red

and blue light reflecting green Molecular structures all involve extensive

delocalized pi bonding (shown on next slide) This system of delocalized pi bonding (conjugated

system) is responsible for the color we see

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 31: Food Chemistry

Color Some of the most common natural pigment

groups are Anthocyanins

Ex Cyanidin Carotenoids

Ex Beta-carotene Chlorophyll

Ex Chlorophyll-A Heme

Ex Heme B group

heme B groupchlorophyll-A

cyanidin

β-carotene

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 32: Food Chemistry

Color Anthocyanins

Responsible for reds pinks blues in berries beets flowers (Flavonones which give color to red grapes and berries are closely related to anthocyanins)

3-ring structures with varying numbers of OH groups in varying positions

Structure and therefore color is related to pH

predominantly red at low pH (acidic) blue at high pH (basic) and colorlesspale yellow at neutral pH

Temperature May break down at high temperatures and cause browning

Exposure to metal Form complexes with iron and aluminum and can change color

Color also affected when anthocyanins bond to sugars

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 33: Food Chemistry

Color Color of anthocyanins is pH dependent (they are

acidbase indicators)

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 34: Food Chemistry

Color Carotenes

Responsible for orange yellow and red colors in foods like carrots bananas tomatoes and saffron

Characterized by long hydrocarbon chains that often have carbon rings on the ends

Have nutritional value precursors to vitamin A (important in vision) act as antioxidants

Relatively stable during food processing but presence of C=C double bonds in hydrocarbon chain opens them up to oxidative degradation as seen in fats

Causes discoloration Prevents carotenoids from being able to be converted to

vitamin A

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 35: Food Chemistry

Color

β-carotene

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 36: Food Chemistry

Color Astaxanthin is a red pigment similar to

carotenoids found in lobster crab and salmon Bonds to proteins in the live animal and gives a

bluegreen color When heated bond to protein is broken which modifies

the structure and frequency of light absorbed appears bright red

Also an antioxidant

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 37: Food Chemistry

Color Chlorophyll

Green pigment responsible for plant photosynthesis Found in green vegetables Structure is centered around a porphyrin ring ndash a

planar ring system with 4 nitrogen atoms surrounding a central metal atom (magnesium in the case of chlorophyll)

Two forms chlorophyll A and chlorophyll B In chlorophyll B an aldehyde side chain replaces a

methyl side chain When cooked plant cells release acids

Causes an H+ ion to replace magnesium atom in center of structure causing a color change to an olivebrown

Opens the possibility for photodegradation (breakdown by light)

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 38: Food Chemistry

Color

chlorophyll A

(replaced with an aldehyde in chlorophyll B)

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 39: Food Chemistry

Color Heme

Pigment found in red blood cells Structure is similar to chlorophyll but there is an iron

atom in the center of the porphyrin ring Found in the protein myoglobin responsible for

oxygen transport Bright red when bound to oxygen but slow process

of autoxidation converts iron from +2 to +3 changing color to brown (less desirable) (myoglobin metmyoglobin)

Color change can be prevented by vacuum packing or packing with an inert gas like CO2

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 40: Food Chemistry

Color

heme groupin myoglobin

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 41: Food Chemistry

Color Color in foods is a result of the structures seen in

anthocyanins carotenoids chlorophylls and hemes All of these structures include an extensive network of

delocalized pi-bonds Alternating single and double bonds is called a conjugated

system The greater the extent of pi bond delocalization the closer

together in energy bonding and antibonding orbitals become All molecules absorb light energy as it promotes e-s between

molecular orbitals (bonding and antibonding orbitals) ndash energy required is proportional to distance between orbitals (less distance = less energy)

As orbitals are close together in a conjugated system low energy light (in the visible region) is absorbed for e- promotion

Color in these groups is the product of visible light absorption - color we see is complementary to the color(s) absorbed

Molecules without an extensive delocalized pi bond network (conjugated system) lack color as orbitals are further apart and only higher energy light promotes e-s (ex the anthocyanin carbinol)

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 42: Food Chemistry

Color Some pigments are water soluble because the

structures contain a large amount of -OH groups (H-bonding) Anthocyanins

Some pigments are fat soluble (ie not water soluble) because their structures contain little or no -OH groups (no H-bonding) carotenoids

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 43: Food Chemistry

Color

Many synthetic dyes are biochemically active and could be potentially harmful

Short-term toxicity easy to test and categorize but long-term effects are more difficult to study

Use of dyes in foods must be regulated but regulations are not standardized internationally posing issues in trade

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 44: Food Chemistry

Color Cooking foods often leads to browning

Two processes responsible Maillard reactions ndash combination of sugars and

proteins Caramelization ndash dehydration of sugar

Both involve removal of water molecule(s)

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 45: Food Chemistry

Color Maillard reactions

Sugars and proteins within the food combine in a condensation reaction

Aldehyde group in sugar (O atom) combines with amino group in protein (2 H atoms)

Initial condensation products polymerize to form brown-colored melanoidins

Maillard reactions only happen gt 140deg C Rate depends on amino acid present (ex lysine

reacts faster than cysteine)

initialcondensationproduct

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 46: Food Chemistry

Color Caramelization

Happens in foods high in carbohydrates Sugars dehydrate (lose H2O) at high temperatures

leaving behind C (dark brown color)

Browning intensifies the longer food is cooked eventually burning it (pure carbon is black)

Rate depends on Sugar type (fructose in fruits caramelizes very quickly) pH ndash extremes (high and low) promote caramelization

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 47: Food Chemistry

Genetically Modified Foods

Produced when organisms with modified DNA are used in food production Used to

Provide pest or disease resistance Bt corn contains toxin from bacillis thuringiensis that kills

insect pests Fungal-resistant potatoes Nematode-resistant bananas (nematode = worm)

Improve quality and range of crop Development of higher-yielding rice varieties Development of corn that can grow in dryer environments

Produce medicines or other products in large quantities Use of chickens that have been modified to lay eggs

containing human interferon (combats tumors and viruses) Use of cows to produce milk rich in omega-3 fatty acids

(polyunsaturated fats essential to growth development brain function)

Moth larva

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 48: Food Chemistry

Genetically Modified Foods

Drawbacks Are GM foods safe Will GM food production alter the natural ecosystem Do we understand enough about genetic

modification GM foods

Can cause allergic reactions in some people Have a slightly different composition from natural foods ndash

alters diet Produce altered pollen ndash might escape and cross with natural

species Long-term effects might be catastrophic unknown so far

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 49: Food Chemistry

Texture Food texture is related to physical properties

Hardness Elasticity Viscosity

These properties can be altered by Cooking Use of dispersed systems

Dispersed system = a stabilized macroscopically homogeneous mixture of two immiscible phases

(this means two substances that would not ordinarily mix ldquoappear tordquo on a macroscopic level (although at the molecular level they are still separate)

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 50: Food Chemistry

Texture Many types of dispersed systems name depends on

the physical states of the substances mixed LiquidSolid or SolidLiquid

Solid particles suspended in a liquid is called a suspension

Ex Blood (blood cells suspended in plasma) Liquid dispersed throughout a solid medium is called a

gel Ex Fruit Jelly (water trapped in a solid protein matrix)

LiquidLiquid Stable blend of two liquids that donrsquot mix is called an

emulsion Ex Mayonaisse (oil droplets suspended in aqueous system)

LiquidGas or GasLiquid Gas bubbles trapped in liquid medium is called a foam

Ex Whipped cream or egg whites Liquid droplets suspended in gas are called aerosols

Ex Aromas from food carried through the air

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 51: Food Chemistry

Texture Dispersed systems will slowly separate over

time Separation can be slowed by adding emulsifiers

Emulsifiers are stabilizers used to keep immiscible substance together

Have surfactant capability (can bind to both substances in suspension)

Similar to micelles in the action of soaps

Ex Lecithin Found commonly in egg

yolks One end is highly charged

and water soluble (bonds toaqueous phase) the otheris not (bonds to non-aqueous phase)

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 52: Food Chemistry

Texture Lecithin in mayonnaise

Lecithin is the emulsifier Mayonnaise made by beating eggs with

vinegar and oil Lecithin is found in eggs ndash charged

hydrophilic end bonds well to vinegar uncharged hydrophobic end bonds to oil

Vigorous beating produces many small oil droplets maximizing surface area for lecithin to act on and produce a stable emulsion

Stabilizers like sodium phosphate or metals are added to prevent separation (chefs use metal bowls)

hydrophilic

hydrophobic

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
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  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 53: Food Chemistry

Stereochemistry in Food Many food-specific compounds have a chiral

carbon atom and thus exist as two different enantiomers (optical isomers) Optical isomers are mirror images of one another ldquoOptical activityrdquo refers to the fact that the two mirror

image isomers rotate the direction of plane-polarized light in opposite directions

Enantiomers that rotate polarized light in a clockwise direction are said to be dextrorotatory (dex-tro-rota-tory) and have a + rotational value (d +) ndash In Latin dexter means ldquoright siderdquo

Enantiomers that rotate polarized light in an anti-clockwise direction are said to be laevorotatory (lay-vo-rota-tory) and have a ndash rotational value (l -) ndash In Latin laevus means ldquoleft siderdquo

There are two systems used to provide specific names to each enantiomeric form

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 54: Food Chemistry

Stereochemistry in Food Older system used for naming sugars and amino

acids Enantiomeric forms are labeled ldquoLrdquo and ldquoDrdquo

Again Laevus for left and Dexter for right Based off a compound called glyceraldehyde

chiral carbon

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
  • Fats and Oils
  • Shelf Life
  • Shelf Life (2)
  • Shelf Life (3)
  • Shelf Life (4)
  • Shelf Life (5)
  • Shelf Life (6)
  • Shelf Life (7)
  • Shelf Life (8)
  • Shelf Life (9)
  • Shelf Life (10)
  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 55: Food Chemistry

Stereochemistry in Food When a 3D sketch of glyceraldehyde is viewed with the C=O

bond pointing away from the observer the ldquoLrdquo form will have the ndashOH group on the left the ldquoDrdquo form will have the ndashOH group on the right

Chiral sugars are named the same way by pointing the C=O group away and describing the location of the ndashOH group (ldquoLrdquo form ndashOH on left ldquoDrdquo form ndashOH on right

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
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  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
  • Fats and Oils (4)
  • Fats and Oils (5)
  • Fats and Oils (6)
  • Fats and Oils (7)
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  • Shelf Life (2)
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  • Shelf Life (11)
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  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
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  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
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  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 56: Food Chemistry

Stereochemistry in Food ldquoLrdquo and ldquoDrdquo system is also used in naming

enantiomeric amino acids 19 of the 20 amino acids have a chiral carbon

The 4 substituents on this carbon are a COOH group an R group a hydrogen atom and a NH2 group

Naming follows the CORN rule Amino acid is positioned so that the C-H bond is facing

away from the observer ldquoDrdquo form has the remaining substituent groups COOH R

and NH2 arranged clockwise ldquoLrdquo form has the remaining substituent groups COOH R

and NH2 arranged anti-clockwise

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
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  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
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  • Shelf Life (2)
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  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
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  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 57: Food Chemistry

Stereochemistry in Food Ex CORN rule applied to alanine

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
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  • Nutrients (carbohydrates)
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  • Fats and Oils (2)
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  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
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  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 58: Food Chemistry

Stereochemistry in Food A more modern system exists where ldquoLrdquo and ldquoDrdquo are

replaced with ldquoRrdquo and ldquoSrdquo (R S system) Used for other compounds outside of sugars and

proteins Naming based off of a ldquorankingrdquo system of chiral carbon

substituent groups Each substituent is given a rank according to its molar mass

specifically the mass of the actual atom bound to the chiral carbon

In cases where there are two like atoms bound to the chiral carbon the mass of the next atom is used in the rank

Molecule is positioned with ldquolowest rankingrdquo substitutent pointed away from the observer remaining substituents will decrease in order of rank

If remaining substituentsrsquo ranks decrease in a clockwise direction ndash R enantiomer

If remaining substituentsrsquo ranks decrease in an anti-clockwise direction ndash S enantiomer

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
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  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
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  • Fats and Oils
  • Fats and Oils (2)
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  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
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  • Stereochemistry in Foods (2)
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Page 59: Food Chemistry

Stereochemistry in Foods Ex 2-bromo butane

Substituents on the chiral carbon are CH3 C2H5 H and Br Ranks H lt CH3 lt C2H5 lt Br

Note that two substituents begin with a ldquoCrdquo atom ndash rank determined by next atom (3 H are lower mass than a C so CH3 ranks lower)

Not part of this example but count double bonds as two of that atom (Ex COOH rank determined by C then 3 O atoms as one of these O atoms is double bonded and counts as two O atoms)

chiral carbon

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
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  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
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  • Shelf Life
  • Shelf Life (2)
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  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
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  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 60: Food Chemistry

Stereochemistry in Foods

In ldquoRrdquo form remaining substituentsrsquo ranks decrease clockwise (Br C2H5 CH3)

In ldquoSrdquo form remaining substituentsrsquo ranks decrease anti-clockwise (Br C2H5 CH3)

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
  • Fats and Oils (3)
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  • Shelf Life
  • Shelf Life (2)
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  • Shelf Life (8)
  • Shelf Life (9)
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  • Shelf Life (11)
  • Shelf Life
  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
  • Stereochemistry in Food (5)
  • Stereochemistry in Food (6)
  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
  • Stereochemistry in Foods (3)
Page 61: Food Chemistry

Stereochemistry in Foods Two enantiomers of the same compound may have

different flavors R-carvone = spearmint flavor S-carvone ndash caraway seed

flavor R-limonene = orange flavor S-limonene = lemon flavor

Biosynthesis tends to be stereospecific ndash ie natural flavor compounds are 100 one enantiomer and not the other

Artifical flavors are produced as a racemic mixture (5050 mix of both enantiomers) as this is much cheaper which can affect flavor Care must be taken to ensure one

enantiomer is not toxic

  • Food Chemistry
  • Nutrients
  • Food Groups
  • Nutrients (carbohydrates)
  • Nutrients (carbohydrates) (2)
  • Nutrients (fats and oils)
  • Nutrients (fats and oils)
  • Nutrients (proteins)
  • Nutrients (water and vitaminsminerals)
  • Fats and Oils
  • Fats and Oils (2)
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  • Shelf Life
  • Shelf Life (2)
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  • Color
  • Color (2)
  • Color (3)
  • Color (4)
  • Color (5)
  • Color (6)
  • Color (7)
  • Color (8)
  • Color (9)
  • Color (10)
  • Color (11)
  • Color (12)
  • Color (13)
  • Color (14)
  • Color (15)
  • Color (16)
  • Color (17)
  • Genetically Modified Foods
  • Genetically Modified Foods (2)
  • Texture
  • Texture (2)
  • Texture (3)
  • Texture
  • Stereochemistry in Food
  • Stereochemistry in Food (2)
  • Stereochemistry in Food (3)
  • Stereochemistry in Food (4)
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  • Stereochemistry in Foods
  • Stereochemistry in Foods (2)
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