flavoring lynch

8/6/2019 Flavoring Lynch

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October2005

Flavoring Beverages:Opportunities and Challenges

Andrew G. Lynch, Ph.D.Quest InternationalGlobal Citrus Applications [email protected]


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What is Food Science ?

Food Science deals with the physical, chemical and biological

properties of food. Food Scientists are concerned with:

Nutrition and Safety

Stability

Processing and Packaging

Cost and Quality

There are very few things as personal as food!


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background

opportunities

challenges

citrus flavor stability

orange juice processingcloudsmilk & coffee drinks

flavoring beverages


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Quest forcreative difference

creative leader in the industry

corporate headquarters in Naarden, theNetherlands

two businesses: Flavours and Fragrances

total sales US$ 1.1 billion (2003)

creative and application centres and productionfacilities across Europe, the Americas and AsiaPacific

approx. 3,500 employees

key facts


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Quest forcreative difference

sales 2003: US$ 1.1 billion

60% flavours

40% fragrances


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background

opportunities

challenges

citrus flavor stability

orange juice processingcloudsmilk & coffee drinks

flavoring beverages


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0

4

8

12

16

20

24

26

30

34

38

- 5.0

- 2.5

0.0

2.5

5.0

7.5

10.0

12.5

15.0

17.5

Sales 2003 ($ billion)Projected

CAGR (04-07)

Carbonates StillDrinks

FlavoredAlcoholicBeverages

FlavoredBottledWater

Juices& Nectars

RtD Tea,& RtDCoffee

PowderBeverages

Sports &EnergyDrinks

20.0

22.5

opportunities - North American beverage market


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diet (low carbohydrate, low calorie)

healthy fats (shift from trans and hydrogenated fats)

shift from fanciful to more exotic natural flavor

e.g. Blood orange instead of orange

masking, suppressing & smoothing

innovative beverages

opportunitiesmarket trends


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1. lemon

2. orange

3. strawberry

4. chocolate

5. apple

6. peach

7. mango8. raspberry

9. vanilla

10. cranberry

8%8%

8%

9%

9%9%

10%

12%

14%

13%

Lemon

O nge

Strawberry

Cho olateApple

Peach

Mango

Raspberry

Vanilla

Cranberry

citrus flavors top the list, moving strawberry from #1 2003 to #3in 2004. cranberry and chocolate are new to the list.

opportunitiesnon-alcoholic beverage segment new launch top flavors 2004

Source: Global New Products Database (Mintel)


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Source: World Health Organization 2003

0 20 40 60 80

USA

GB

Germ

Austr

Br z

I

T

C bese

Overweight

percent

Obesit intheUSistruly nepidemic. Inthelast 10years,obesity rateshaveincreased bymorethan60%amongadults.

opportunitiesobesity


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bitterness

(soy, grapefruit, protein drinks, coffee)

sourness(coffee, fermented and acid products)

saltiness

(iso-tonic applications)

artificial sweetener

(low cal products, lingering aftertaste, lack of body)

opportunitiesmasking and suppressing


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sweetness

sugar flavors

aromatics beyond drinking

odor release prior to consumption, instantteas & coffees

visual

taste modification

opportunitiesenhancement


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dairy-based beverages

soy and juice combination drinks

meal replacement (juice/cereal/yogurt)

opportunitiesinnovation in beverages


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background

opportunities

challenges

citrus flavor stabilityorange juice processingcloudsmilk & coffee drinks

flavoring beverages


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packaging

regulatory

consistent quality of natural ingredients

stability

processing

flavor stability

physico-chemical stability

challenges


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GMO

natural & artificial

kosher

nature identical

global customers

globalization of flavors

Halal

TTB (formerly BATF)

challengesregulatory


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natural products have natural variation

focused quality assurance program is critical

catastrophe in one part of the world? Example: 2004 Florida

hurricanes significantly damage grapefruit crop

challengesconsistent quality of natural ingredients


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consistency in scale-up & transfer to other regions

processing impact on flavor/cloud

hot fill vs. cold fill

oxygen control

challengesprocessing


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fading

light induced degradation

acid hydrolysis

oxidation

challengesflavor degeneration


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background

opportunities

challenges


flavoring beverages


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oxidation of terpenes

citral in aqueous low pH

acid catalyzed hydrations

Source: ouseff, . and Nai , M. 2000. itrus Flavor Sta ility. n: Flavor

he istry, ed. By isch, S.J and Ho, . . A erican he ical Society. Pages

101-121.

challengescitrus flavor stability


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soda base pH 2.7

Brix 10.6

Carbonation 7 g/L Good oxygen control

storage conditions 2 weeks at 4C and 2 weeks at 45 C

challengescitrus stability demonstration


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challengestypical off flavor formation in acidic aqueous solution

p-mentha-1,5-dien-8-ol

Citral

H+ O2

OH

p-cresol

O

p-methylacetophenone

OxidationAcid catalized

cyclization

CHO

CHO

Neral

Geranial


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0

50

100

150

200

250

300

350

400

450

4C storage 45C storage

p-cresol ion area

Control

0

1000

2000

3000

4000

5000

4C storage 45C storage

p-methyl acetophenone ion area

Control

challengesoff flavor formation in lemonade stored at high ambient temperatures


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metallic oxidized

moldy

deterioratedbitter

barny

Control 4C

Control 45C

3.53

2.5

2

1.51

0

0.5

challengessensory analysis of aged lemonades


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less off flavors

increased shelf life

citrus flavors that delivertraditional citrus favorites

with authentic taste profiles

challengeslemon flavors


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background

opportunities

challenges


flavoring beverages


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Oranges are processed to make not from concentrate(NFC) or frozen concentrated orange juice (FCOJ)

Quality must be controlled (variety, growing conditions, etc)

Processing must be closely controlled to:

Deactivate enzymes

Limit oxygen levels

Destroy pathogenic and spoilage microorganisms

Minimize chemical and flavor changes

Correct packaging and storage conditions must be used todeliver safe and stable product to consumers.

Orange Juice Processing


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Cross section of range

Flavedo

Albedo

Oil glands

Juice vesicles


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Citrus Materials: Basic Processing


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Fruit eception Juice Extraction

Clarification

NFC JFC

Bulk ransportation

eprocessing

Packaging

Distri ution

Peel il ecovery

Essence ecovery

Pasteuri ation Past/Evaporat

vervie of Production of range Juice Concentrate

Main Products By-Products

Oil PhaseWater-Phase Aroma

Peel Oil

Pulp, Limonene,

Citrus Pulp Pellets


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(1) Enzyme deactivation

Deactivation of pectin methyl esterase (PME)

PME cleaves methyl groups from pectin causing cloud loss and gelation

Calcium (from the juice) interacts with the demethylated pectin

Calcium pectate is insoluble and settles at the base of the container

For Florida-grown Valencia oranges, a heat load of 2-3 D values isgenerally sufficient for total enzyme destruction.

Typically pasteurization conditions employed are 95-98C for 10-30 secs.

Why does juice need to be pasteurized ?


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(2) Ensure a microbiologically stable product

Main micro-organisms of interest in OJ are:

Acid-tolerant bacteria, yeasts and moulds

Acid-tolerant bacteria, e.g., Lactobacillus plantarum (grow best at 20-37C) Spoilage characterized by diacetyl (buttery) off-notes and CO2

Saccharomyces cerevisiae is the most common spoilage microorganism

Spoilage characterized by alcoholic fermentation, off-flavors and CO2

Spore-forming microorganisms (thermo-resistant acidophilic bacteria)

In 1992,Alicyclobacillus classified as new genus

Spoilage characterized by an off-flavor like disinfectant or guaicol

Why does juice need to be pasteurized ?


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Thermal resistance of microorganisms is traditionally expressed in terms

of D values and Z values.

D value is the time at a specified temperature for the microbial population

to decrease by 90% or one log cycle (also called the decimal reduction time)

Z value is the change in temperature needed to alter the D value by

one log cycle For example, if an organism has a z = 10C and a D80C = 1 min,then the D90C = 0.1 min and the D70C = 10 min.

Thermal processing of OJ


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Pasteurization destroys most vegetative microorganisms but has little effecton bacterial spores (Most spores do not grow < pH 4.5).

long term survival of some pathogens in unpasteurized refrigerated juice ispossible, therefore pasteurization is recommended

For microorganisms usually found in fruit juices, z values are typically 5-7.

Typical pasteurization temperatures are 75-95C for 15 to 30 secs

For a given increase in temperature, the rate of destruction of microorganisms and

enzymes increases faster than the rate of destruction of sensory and nutrientcomponents.

SummaryDeactivate enzymes, Ensure microbiological safety andminimize heat damage to nutrient and flavor components.

Thermal processing of OJ


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Theoretical ther al destruction curves ofpectin ethyl esterase,

ascospores and vegetative cells ofSaccharomyces cerevisae in

orange juice (The range Book,Tetra Pak)


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trend towards less glass and increased use ofpolypropylene and PET (polyEthyleneTerephthalate)

scalping(loss of flavor into the packaging material)

permeation(movement of compounds through packaging materials)

migration(movement of components of the packaging material intofood product)

Source: isch, S. 2000. Flavor and packaging interactions. n: FlavorChe istry, ed. By

isch, S.J and Ho,C.T. A erican Che ical Society. Pages 94-100.

challengespackaging


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Barrierproperties

OxygenOxygen

ff-flavor for ation

FlavorFlavor

Flavor fading (scalping,per eation)

Permeation rate = Diffusion x Solubility

P = D x S

oxidation


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Vita in C sta ility in different package types

(The range Book,Tetra Pak)

Vita in C degradation c r es for different

packages of orange ice stored at 3C

0

100

200

300

400

500

1 2 3 4 5 6Months

Vita

in

C

conte

gL

Alu-foil barrier,

anaerobic

storage

alu-foil barrier,

aerobic storage

EVOH barrier,

aerobic storage

AA + O2 =DHA + H20

AA= ascorbic acid(vitaminC), DHA=dehydroascorbic acid


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Properties of different poly ers: P = D x S

Polarpoly ers: PET, ethylene vinyl alcohol (EVOH) and polyamide (PA)

show very slow diffusion coefficients with polar and non-polar aromacompounds.

Non-polarpoly ers: low density polyethylene (LDPE), high densitypolyethylene (HDPE) and polypropylene (PP)

Limonene (non-polar aroma compound) has a high solubility in all the non-polar polymers and diffusion and consequent permeation rates differ byorders of magnitude in the different polymers in decreasing order

LDPE > HDPE > PP

Ethyl butyrate (polar aroma compound) has low solubility in non-polarpolymers. Losses of polar molecules are negligible with this type of barrier.


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Terpenes: the largest single che ical class ithin citrus volatiles

*Three month study of orange juice in Tetra-Pak laminated containers showed:

(a) Significant loss of limonene due to absorption/scalping by polymer barrier

F E-terpineol (formed from degradation of limonene) increased more rapidly

at higher storage temperatures

*Duerr et al.,Alimenta 1981, 20, 91-93


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Volatile contri ution to orange juice aro a

Contribution to typical aromas Contribution to off-notes

Important Desirable Precursors Detrimental

ethyl butyrate linalool linalool E-terpineol

neral limonene limonene carvone

geranial E-pinene valencene t-carveol

valencene 4-vinyl guaiacol

acetaldehyde 2,5-demethyl-4-

hydroxy-3-(2H) furanoneoctanal

nonanal

E-sinensal

F-sinensal


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background

opportunities

challenges


flavoring beverages


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provides turbidity to a beverage; visual enhancement that gives

finished beverage more value

many different types of cloud systems

weighting agents in clouds are regulated

sucrose acetate isobutyrate (SAIB)

brominated vegetable oil (BVO)

ester gum

blended systems

challengesclouds


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Neutral cloud

Goal: cloud with minimal taste impact

Most ade fro orange terpenes

Vegeta le oil as an alternative

typically less stability

cleaner taste

challengesclouds


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emulsion in beverage product breaks down giving rise to creaming

perform tests to predict stability

make assumptions for predictions microscope, particle size analyzer, shelf-life studies etc.

challengescloud ringing


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Stokes La :

V = 2gr2 (po-p)

9nov = velocity

r = droplet radius

g = gravity

po - p = difference in density

no = viscosity

v = negative crea ing

v = 0 sta le cloud

v = positive sedi entation



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stable

ringing

phase separation,

shrinkage of cloud layer



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background

opportunities

challenges


flavoring beverages


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milk-coffee drinks contain coffee, milk,

sweeteners, flavors, salts, hydrocolloids, proteins,

emulsifiers amongst other components

complex mixture of ingredients

physico-chemical and flavor stability issues(processing and storage)

milk-coffee RTD challengesmatrix complexity

Milk ff TD t i


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E ulsifiers, Proteins

Hydrocolloids

Beverages ith i proved sta ility & fresher coffee flavour

Application, Sensory & Flavour expertise&D

Processing Effect of heating, antioxidants,pH, 2 content, sta ili ing salts,ho ogeni ation etc.

Dairy/non-dairy fat ith ilk flavour

Coffee

Black

Coffee

Fresh hole ilk

Fresh ski ed ilk

Ski / hole ilkpo ders

Specialty proteins Alternative syste s

Caseinate

Whey proteins

thers

Clouds

thers

Milk coffee TD atrix

Milk coffee TD atrix


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coffee consumption is growing

2.5 billion liters of canned coffee are

consumed annually in Japan alone!

served hot during winter & cold in summer

beverage manufacturers are adopting coffee

house trends into RTDs

milk-coffee RTD opportunitiesconsumption


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coffee contains over 830 volatile components!

some of the key flavor components responsible for freshroast coffee character are:

2-furfurylthiol

coffee aroma and taste is dependent on the type of coffee used

species: Arabica or Robusta

origin

degree of roasting

milk-coffee RTD challengesflavor complexity


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at temperatures > 60C, acidity increases, sourness increases andvolatiles are lost resulting in an unpleasant drinking experience

milk is added to coffee for:

appearance

taste

mouthfeel



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LC Fractionation of Ara ica Coffee (filtered re )

ko ffie e xt ra c t01:1_U V1 ko ffie e xt ra c t01:1 _p H 1 ko ffie ext ra c t01 :1_ Con d1 ko ffie ext ra c t01:1_

lo wA B ko ffie e xtra c t01:1_

ract ions

koffie extract01:1_Injec t

0.0

0.5

1.0

1.5

2.0

A U

4.5

5.0

5.5

6.0

6.5

7.0

pH

0 100 200 300 400 ml

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 1 7 18 19 20 21 22 23 24 2 5 26 27 28 29 30 31 32 33 34 35


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coffee flavors are needed to compensate for the damage to the coffeevolatiles during the extraction and beverage processing stages

fruity (eg. acetaldehyde)

phenolic (eg. guaiacol)

earthy (eg. 2-ethyl-3,5-dimethylpyrazine)

roast (eg. 2-furfurylthiol)

sweet (eg. methylpropanal)

opportunities for flavored coffees include; vanilla Irish Cream chocolate and caramel macadamia Nut and Hazelnut

amaretto and almond

coconut

fruit flavors eg.orange & raspberry



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The co position of ilk

CONSTITUENTCONSTITUENT

WaterWaterTotal solidsTotal solids

FatFat

ProteinProtein

LactoseLactose

MineralsMinerals

MEAN VALUE %MEAN VALUE %

87.087.013.013.0

4.04.0

3.43.4

4.84.8

0.80.8

RANGE %RANGE %

85.585.5 89.589.510.510.5 14.514.5

2.52.5 6.06.0

2.92.9 5.05.0

3.63.6 5.55.5

0.60.6 0.90.9


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S h i i f i ll (A) d


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Sche atic representation of a su - icelle (A) and a

casein icelle (B) co posed of su - icelles (fro

Sch idt, 1982)

P i l ti f id h i id


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Possi le reactions of side-chain residues

ofproteins at high te peratures 1

--CHCH22--CONHCONH22 + H+ H22OOAsparagineAsparagine

--CHCH22COOH + NHCOOH + NH33Aspartic acidAspartic acid

--(CH(CH22))22--CONHCONH22 + H+ H22OOGlutamineGlutamine

--(CH(CH22))22--COOH + NHCOOH + NHGlutamic acidGlutamic acid

--CHCH22--OO--POPO3322-- + H+ H22OOPhosphoserinePhosphoserine

--CHCH22--OH + HPOOH + HPO4422--SerineSerine

--CHCH22--OO--POPO3322--

PhosphoserinePhosphoserine

=CH=CH22 + HPO+ HPO4422--

DehydroalanineDehydroalanine

--CHCH22--SH + OHSH + OH--CysteineCysteine

--CHCH22--SS-- + H+ H22OO

R1R1--CHCH22--SS--SS--CHCH22--R2R2

R3R3--CHCH22--SS--

R1/R2R1/R2--CHCH22--SS--

R3R3--CHCH22--SS--SS--CHCH22--R1/R2R1/R2

1.1.

2.2.

3.3.

4.4.

5.5.

6.6.

P i l ti f id h i id


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Possi le reactions of side-chain residues

ofproteins at high te peratures 2

--CHCH--SS-- ++ --SS--CHCH22--CysteineCysteine

--CHCH22--SS--SS--CHCH22CystineCystine

--CHCH22--SS--

CysteineCysteine

=CH=CH22 + HS+ HS--

DehydroalanineDehydroalanine

=CH=CH22 + HS+ HS--CHCH22-- --CHCH22--SS--CHCH22LanthionineLanthionine

--(CH(CH22))44--NHNH33++ + H+ H22C + OHC + OH

--

LysineLysine

--(CH(CH22))44-- +NH+NH--CHCH22-- + H+ H22OO

LysinoalanineLysinoalanine

--(CH(CH22))44--NHNH33++ ++--OO22CC--CHCH22LysineLysine Aspartic acidAspartic acid

--(CH(CH22))44--NHNH--COCO--CHCH

22++

HH22O +O +II--NN--(B(B--aspartyl)lysineaspartyl)lysine

--(CH(CH22))44--NHNH33++ ++--OO22CC--(CH(CH22))22

--

LysineLysine Glutamic acidGlutamic acid

--(CH(CH22))44--NHNH--COCO--(CH(CH22))22-- ++HH22O +O +II--NN--((KK--glutamtyl)lysineglutamtyl)lysine

7.7.

8.8.

9.9.

10.10.

11.11.

12.12.


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Bro ning (Maillard) reactions in ilk

in milk the main Maillard reactants are lactose and lysine

the rate of Maillard reaction in milk is dependent on pH, time,

temperature and water activity

some of the compounds identified from dry extracts of milksystsems incubated at pH 6 or 7 and water activity 0.75 to0.80 included: 5-hydroxymethyl-furfural, furfuryl alcohol,furfural, maltol, acetol, 2-oxo-proponal, acetaldehyde, and

formic, acetic, propionic, butyric and lactic acids

H t t ilit H


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Heat sta ility versus pH curves

for nor al ski ilk heated at 140C

6.26.200

1010

2020

3030

4040

5050

6.46.4 6.66.6 6.86.8

pHpH

HEAT COAGULATION TIME (HCT) (min.)HEAT COAGULATION TIME (HCT) (min.)

77 7.27.2

milk Bmilk A

maximum

minimum


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Changes hich can occur to ilk constituents on heating 1

calcium and phosphate are converted from soluble tocolloidal state

formic acid and lactulose are formed from lactose attemperatures > 100C

hydrolysis of the phosphoserine residues at hightemperatures

the titratable acidity of the milk increases and pHdecreases

solubility of the whey proteins decreases significantly attemperatures > 75C


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Alkaline urea-PAGE of solutions of sodiu caseinate


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heated at different pH values and te peratures.

EEs1s1--caseincasein

EEs2s2

--caseinscaseins

FF--caseincasein

OO--caseincasein

KK--caseincasein

1 2 3 4 5 6 7

Alkaline ureaAlkaline urea--PAGE ofPAGE ofunheated sodiumunheated sodiumcaseinate (1); sodiumcaseinate (1); sodiumcaseinate, pH 7, heatedcaseinate, pH 7, heatedat 110at 110C (2), 120C (2), 120C (4),C (4),of 130of 130C (6) for 5 min.C (6) for 5 min.

and sodium caseinate,and sodium caseinate,pH 10.0, heated atpH 10.0, heated at110110C (3), 120C (3), 120C (5)C (5)or 130or 130C (7) for 5 min.C (7) for 5 min.Lynch, Andrew, Ph.D thesis,NUI, Cork, Ireland, 1995.


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Coffee-milk mixtures usually have near neutral pH values and careful

processing is required to ensure a stable product with good organoleptic

properties

controlled temperature & duration of heating during coffee extraction

homogenization is required if milk fat or other fat is used

sufficient amount of surface active material must be present

check coffee-milk/ingredient and flavor compatibility

pH of the mixture needs careful control sterilization/UHT processing is required for long shelf-life products

milk-coffee RTD challengespreparation of milk-coffee beverages


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under homogenization optimum homogenization

milk-coffee RTD challengeswhy homogenize?


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OIL

Creaming Aggregation

creaming

Coalescence

separation

Reversible Irreversible

STABLE UNSTABLE

milk-coffee RTD challengesemulsion stability


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close approach of

droplets

interfacial filmrupture

coalescence

steric stabilization

interfacial rheology

no interfacial filmrupture

flocculation

milk-coffee RTD challengesdroplet stabilitly


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E ulsifiers

Surface active molecules

Contain water-loving hydrophilic part and oil-lovinglipophilic part

Reduce surface tension

Orientate at oil / water or air / water interface

Interact with other ingredients (e.g. protein, starch)


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E ulsifiers : Che ical Characteristics

odine value unsaturated fatty acids

gram iodine absorbed per 100 g emulsifier

Peroxidase value oxidation level

meq. oxygen bound as peroxide per kg emulsifier

Acid value free fatty acids

mg KOH needed to neutralise 1 g emulsifier

Saponification value free + bound fatty

acids

mg KOH needed to saponify 1 g emulsifier


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Co position of e ulsifiers

rganic Acids

Water Soluble Fraction Oil Soluble Fraction

AceticLactic

Citric

Tartaric

GlycerolPolyglycerol

Propylene glycol

Sucrose

Sor itol

TalloLard

Pal

Soya

Polyols ils / Fats


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Hydrophilic / Lipophilic Balance of E ulsifiers

HLB related to oil solu le and

water solu le proportions of the olecule

ncreasin

/O e ulsion O/ e ulsion

HLB alueonly for non-ionic e ulsifiers

HLB alue 0 { - ( V AV)}


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Monoglyceride : Saturated

E-o--OH-OH

CO

Fatty

acid

GMP

(glyceromonopalmitate)

S di t l 2 L t l t


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Sodiu stearoyl-2-Lactylate

CH3|CO

Fatty

acid

CH3 CHO

| |

CHO--CO

|

COO (Na )- +

ilk ff RTD


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P rti l i t r Qm)

0.01 0.1 1 100

2

4

6

Sampl f r

Onepassat 00

passesat 00

passat 00

milk-coffee RTD challengeseffect of homogenization pressure on particle size distribution

b


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background

opportunities

challenges


flavoring beverages

A1


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Flavoring Beverages:Opportunities and Challenges

A.G. Lynch


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Slide 81

A1 Andrew, 10/24/2005

flavoring lynch

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