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![Page 1: Hydrocolloids Structure and Properties - · PDF fileHydrocolloids Structure and Properties The building blocks for structure Timothy J. Foster. Natural Materials This shows a layer](https://reader033.vdocuments.net/reader033/viewer/2022052607/5a72af887f8b9aa2538dd8e8/html5/thumbnails/1.jpg)
18 month Meeting, Unilever Vlaardingen, March 29‐31, 2010
Hydrocolloids Structure and PropertiesThe building blocks for structure
Timothy J. Foster
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Natural MaterialsThis shows a layer of onion (Allium) cells.
Manufactured MaterialsFoams Emulsions
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Targeting Hydrocolloids For Specific Applications:
Approach
Ingredient
Microstructure
ProcessOral
Response
Material Properties
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Ingredient(enzymes)
DECONSTRUCTION
Controlled oral response
(taste, flavour, texture)
In body functionality
Process(mouth/gut)
PackagingDistributionStorage
Process
Ingredient
CONSTRUCTION
Controlling Structure
Designed texture/appearance/behaviour
ReconstructionReconstructionInteraction with body mucins(associative and new phase separation)
Microstructure changes as a function of enzyme action
Re-assembly of structures as a function of digestion breakdown products and body secretions
(micelle formation, delivery vehicles)
Impact on / of starting materials / structures
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Single Biopolymer systems
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Hydrocolloid Structure/ FunctionNeed:
- define biopolymer primary structure
- understand the nature of the interaction / rates
- understand the solvent effects
- measure material properties
- test influence of primary structure variation and changes in environmental conditions on mechanical properties.
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ThickeningPectinAlginateStarchLBGGuar gumXanthan
Emulsification• Gelatin• Milk proteins• Egg proteins• Soya proteins• Pea proteins• Gum Arabic
Hydrocolloid Materials & Function
GellingPectinAlginateStarchAgarCarrageenanGellanGelatinMilk proteinsEgg proteins
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Gelling• Pectin• Alginate• Starch• Agar• Carrageenan• Gellan• Curdlan• Celluosics• Succinoglycan• Scleroglucan• Mixtures
Thickening• Pectin• Alginate• Starch• LBG• Guar Gum• Xanthan• lamda Carrageenan• Cellulosics• Beta Glucan
Emulsification• Gum Arabic• Propylene glycol Alginate• Sugarbeet pectin• OSA starch
Hydrocolloid Materials & Function
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A protein is a polymer of amino acids
• Primary structure– amino acid sequence
• Secondary structure– spatial structure through interactions between amino acids that
are near along the amino acid chain (e.g. α‐helix, β‐sheet)
• Tertiary structure– spatial structure through interactions between amino acids that
are far away along the amino acid chain
• Quaternary structure– association of different amino acid sequences (e.g. haemoglobin)
Protein structure
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Protein
Protein Structure:Backbone
random coilsbeta sheetalpha helix
Charge
Determines Properties:Interfacial properties
foamsemulsions
Gel forming
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Color caption:
α-Helix
β-Sheets
Cysteines
Structure of globular proteins
α‐lactalbumin (α‐la)
β‐lactoglobulin (β‐lg)dimeric form at neutral pH
bovine serum albumin(BSA)
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Turbid Gels
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• How do they differ?
OH
OHOH
OH
CH2OHO
H
H
H
H
Carbohydrates…what do they look like?
1
23
4
5
6CH2OHO
OH OH
OH
OHHH
H
HH
CH2OHO
OH
OH OH
OHH
H H HH
Glucose
OH
CH2OHO
OH OH OH
HH
H
H
HMannose
CH2OHO
OH
OH
OH
OHH
H
H
HH
Galactose
Gulose
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Sugar Interactions• Glycosidic linkage
OH
OHOH
OH
CH2OHO
H
H
H
H
HOH
CH2OHO
H
H
HOH
OH
OH
OH
OHOH
O
CH2OHO
H
H
H
H H
HOH
CH2OHO
H
HOH
OH
+H20
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Polysaccharide Structure /
Functionality
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Sources of hydrocolloidsBotanical
starch, cellulose, galactomannans, pectin, gum arabic, karaya, tragacanth, beta glucan
Seaweeds
agar, carrageenan, alginate
Animal
gelatin, chitosan, hyaluronan
Bacterial
xanthan, gellan, dextran
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Structural Features
• Linear – (homo- and hetero-)
• Linear – branched– (homo- and hetero-)
• Branched– (homo- and hetero-)
• Ordered helices– (single, double, triple)
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Polysaccharide thickeners
• The most efficient thickeners are;
• Linear, • High molecular mass• Charged
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Alternative HydrocolloidsAloe Gum
Cashew Gum Gum GhattiGum Karaya Oat gumOkra Gum Gum TragacanthCaramania Gum (almond) Cassia Gum Cassava Starch Cherry GumChia Gum Chickpea FlourCocoyam Flour Combretum GumCowpea protein /starch CyclodextrinsDetarium microcarpum polysaccharide Fenugreek gumFlaxseed Gum Gleditsia macracanthaHsian-tsao Leaf gum (Taiwan/China) Lesquerella GumLichenin Lucaena galactomannanLupin Protein Manna GumMoussul Gum (Plum) Opuntia FicusPortulaca Oleracea Prickly PearPsyllium gum Quince seed gumRice Flour Rye bran (beta d glucan / arabinoxylan)Sassa Gum Sorghum flourSoy Bean Polysaccharide Tamarind gumTara Gum Tremella Aurantia PoysaccharideTropical Starches YamYellow Mustard Gum
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Typical Solution Properties
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Hydrocolloid Structure/ Function
Need:
- define biopolymer primary structure
- understand the nature of the interaction / rates
- understand the solvent effects
- measure material properties
- test influence of primary structure variation and changes in environmental conditions on mechanical properties.
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Galactomannans• Galactomannans include guar gum, locust bean gum (carob),
fenugreek, cassia and tara gum.
• They have a high molecular mass (~ in excess of 500kDa) and consist of β 1,4 linked mannose residues with galactose units linked α 1,6.
• The M:G ratio is ~2:1 for guar, 3:1 for tara and 4:1 for locust bean gum.
• The galactose units are not evenly distributed along the chain.
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• LBG can be fractionated wrt temperature of solubility.• Cold soluble LBG (30C) has a higher G/ M than that soluble at high temperature (80C).• LBG soluble at 80C has a galactose content of 16.6%, and gels at ambient temperature.• Cold soluble LBG does NOT gel even when frozen & thawed.• Not necessary for ice to be present, a non‐ionic interaction, dependent on solvent quality.
LBG Structure / Functionality
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Gelation Rate Gelation Rate Gelation Rate
[LBG]1.0 1.3 2.0
Sucrose (%)20 50 65
Temperature-8 10
- Self association is kinetically controlled as a function of the number of available junction zones
- The distribution of galactose sidechains is all important in dictating functionality.
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Properties of Hydrocolloids
0 10 20 30 40 50 60 700
0.01
0.02
0.03
0.04
0.05
0.06
Strain (%).
Load (KN).
3%Gelatin
3%Agar
Typical polymer gel propertiesDependent on Solvent quality, Polymer fine structure, Junction zone type / quantity
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Effect of Shear during Gelation: Fluid gel Particle formation
• Composite properties are dependent upon the number and size of particles produced.
• This in turn is dependent upon the polymer used, the polymerconcentration and the shear field.
0 1 2 3 4 510
100
1,000
10,000
100,000
1,000,000
[Agar]
G'(Pa)
Quiescent
Sheared
Storage Modulus of Agar Gels FormedQuiescently and Under Shear
Measurement Temperature = 10C
POURABLE
SPREADABLESPOONABLE
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0.1 10.01
0.1
1
Level of Dilution
Viscosity (Pas)
Xanthan
Fluid gel
• Due to the colloidal nature of their properties they providebetter dilution characteristics than their molecular counterparts.
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Mixed Biopolymers
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Aqueous-based two-phase systems
Microstructure
o/w emulsion water-in-water emulsion
25 μm
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0 2 4 6 8 10 12 14 16 18 200.0
0.2
0.4
0.6
0.8
1.0
1.2L
BG
(W
T%
)
MICELLAR CASEIN (WT%)
*
**
25% LBG / 75% PR75% LBG / 25% PR 50% LBG / 50% PR
Phase diagram measured at 5C
Phase Separation phenomena is used in the creation of foodproducts.
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Aqueous-based two-phase systems
Example: Aqueous mixture of gelatin and maltodextrin
Top phase: Gelatin
Bottom phase: Maltodextrin
For charged polymers (polyelectrolytes) salt (type and concentration) as well as pH are important parameters.
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Influence of varying polymer characteristics
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0 2 4 6 8 10 12 14
0
2
4
6
8
10
12
Isothermal Binodal Evolution Owing to Ordering
δ [SA2] / δt = 0.4 % / min
LH1 / SA2 No Salt20oC
[LH
1] /
% w
/w
[SA2] / % w/w
• Schematic phase diagram showing the binodal as a function of ordering at 20 °C
Phase separation driven by molecular ordering of one of the biopolymers.
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Process effectsStructure induced phase separation.• Measure of gelatin helices required to induce phase separation in a 4% LH1e:4% SA2 mixture , in water, when quenched to 20oC (top) and 25oC (bottom).• Morphology when quenched to 20oC.
2 4 6 8 100
2
4
6
8
10
12
14
16
% Helix% Helix%
Hel
ix
t / min
0.0
0.5
1.0
1.5
TurbidityTurbidity
τ / cm-1
10 20 30 40 500
2
4
6
8
10
12
14
16
% Helix
% H
elix
t / min
0.0
0.5
1.0
1.5
τ / cm-1
Turbidity
1min
4min
29min
20oC
25oC
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Effect of shear during cooling / gelation of the gelatin
Process effects on mixed biopolymer systems.
Gelling biopolymer forms the dispersed phase.
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Structures based on aqueous-based two-phase systems
Scheme developed by Tolstoguzov*
*V Tolstoguzov Journal of Texture Studies 11, 3 (1980) 199-215
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Gel particle suspensions
Modification of (shear) rheology: Effect of fibre alignment
0.01 0.1 1 10 1001
10re
lative
vis
cosi
ty
shear stress [Pa]
50 μm
Dispersed phase volume: 20%
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Gel particle suspensions
Deposition: Non-food example
SEM micrograph by M Kirkland WO2003061607 A1
κ-carragenan fibres deposited on a hair. Spherical particles of the same composition wash off during rinse.
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Milk ProteinLBGAirIce
Ice Cream
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Short textureie. snaps
Comparative Properties
-0.00020
0.0002
0.0004
0.0006
0.0008
0.001
0.0012
0.0014
0.0016
0 20 40 60 80 100Displacement (mm)
Load
(kN
)
Conventional Formulation
MarasFormulation
Extensible textureie. stretches
GB 9930531US 20010031304
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0%
20%
40%
60%
80%
100%
120%
140%
160%
Sahlep
Guar
Xanthan
CM
C
LBG
Gelatin
Carrageenan
% m
ean
stra
in to
failu
re
All products here compared at 30% Overrun
Prior Art formulations
Hydrocolloid functionality in Maras Ice Cream
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Conclusion
• The fine structure of hydrocolloids plays a role in their properties (viscosity and gelation)
• Influence of process can alter the functionality (single and mixed systems)
• Hydrocolloid:Hydrocolloid interactions determine the gross properties of composites
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0
500
1000
1500
2000
2500
3000
3500
4000
0 300 600 900 1200 1500 1800 2100 2400 2700
Time / s
Visc
osity
/ cP
STRUCTURE CREATION
150 um
STRUCTURE RETENTION
150 um
Point of dilution
Acknowledge ALL past and present colleagues for support and stimulation