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Ingredient Functionality &

Characterization
David Julian McClements
Biopolymers and Colloids Laboratory
Department of Food Science
Emulsifiers
Texture Modifiers
Thickening Agents
Gelling Agents
Weighting Agents
Emulsifiers:
Major Functions in Food Emulsions
Functional Properties
Emulsion Formation
Emulsion Stabilization
Modification of Interfacial Properties
Modification of Crystallization
Interaction with Biopolymers
Displacement
ice cream manufacture
Crystal modification
margarine manufacture
Polymer interaction
Bread manufacture
Emulsifiers: Formation
Emulsifier Factors Affecting Formation:
Concentration and Surface Load
sufficient present to cover all surfaces formed
Adsorption Kinetics
adsorbs fast enough to form protective coating
Interfacial Tension
lower gives smaller droplets
Protective Coating
Emulsifier layer should protect against aggregation


Movement
to surface
Incorporation
In surface
Film
Formation
Microfluidics
Emulsifiers: Stability
+ +
+
+
Charge
Thickness
Hydrophobicity
Emulsifier Factors Affecting Stability:
Colloidal Interactions
- Interfacial Thickness, Charge & Hydrophobicity
Resistance of membrane to disruption
- Interfacial rheology
Environmental
Responsiveness:
pH, I, T
Common Food Emulsifiers
Small Molecule Surfactants
Tweens, Spans, fatty acids, DATEM
Sucrose esters, polyglycerol esters, monoglycerides
Phospholipids
Egg, soybean, milk
Biopolymers
whey, casein, egg, gelatin, soy
modified starch, gum arabic, modified cellulose


Emulsifier Applications in Foods
Salad Dressings
Tweens
PGA
Proteins
Milk & Cream
Proteins
Phospholipids
Mayonnaise
Proteins
Phospholipids
Yolk particles
Nutritional Beverages
Proteins
Phospholipids
Soft Drinks
Gum Arabic
Modified Starch
Ice Cream
Proteins
Phospholipids
(Surfactants)
Sauces & Dips
Mono/diglycerides
Specifying Emulsifier Functionality
Choosing the most appropriate emulsifier
Physicochemical Factors
Emulsion type (O/W or W/O)
Minimum amount needed (C
min
)
Minimum droplet size achievable (r
min
)
Ingredient compatibility
Sensitivity to environmental stresses (pH, I, T)
Practical Factors
Ease of utilization
Reliability/Consistency of source
Long term stability
Sensory properties
Economic & Marketing Factors
Cost
Label friendliness
Currently no
standard method of
specifying
emulsifier
functionality
Surfactants:
Molecular Structure
Head Group
Electrical charge (non-ionic/ionic)
Chemical groups
Length and cross-section
Tail Group
Number of chains
Length of chains
Saturation of chains
+



Industrial Manufacture of Surfactants
Danisco
Commercial surfactants are
actually a complex mixture of
many different molecules
Tween 20 Structure: ChemBlink
Micelle
Reverse
Micelle
Vesicle
Non-spherical
Micelle
Self Assembly of Surfactants
Surfactants can form a variety of structures, with different
functional properties, depending on their molecular structure
Classification of Surfactants
Bancroft rule
The phase in which the surfactant is most
soluble (dispersible) forms the continuous
phase of emulsion
HLB number
The ability of a surfactant to stabilize an
emulsion depends on balance of hydrophilic to
lipophilic groups
HLB Classification Scheme
0.475 -CH
3
0.475 -CH
2
-
0.475 -CH-
Group
Number
Hydrophobic
Group
HLB = 7 + (hydrophilic groups) - (lipophilic groups)
CH
3
(CH
2
)
11
-O-S-O

Na
+
O
O
6.8 Sorbitan ring
2.1 -COOH
21.2 -COO

H
+
38.7 -SO
4

Na
+
Group
Number
Hydrophilic
Group
HLB Numbers of Some Food
Surfactants
Surfactant Name HLB Number
Sodium lauryl sulfate 40
Potassium Oleate 20
Tween 20 15
Decaglycerol monooleate 14
Ethoxylated monoglyceride 13
DATEM 8
Soy lecithin 8
Calcium stearoyl lactylate 5.1
Glycerol monoleate 3.4
Sorbitan trioleate 1.8
Oleic acid 1.0
Hydrophilic
Lipophilic
Oleic acid
Tween 20
HLB Classification Scheme
HLB Number Solubility Emulsion Type
Very Low (<3) Oil Unstable
Low (3-6) Oil W/O
Medium (6-8) Oil&Water Unstable
High (8-18) Water O/W
Very High (>18) Water Unstable
Benefits and Limitations of
Classification Schemes
Benefits
Provide information on emulsion type (O/W or W/O)
Enable rational selection of mixed surfactant systems
Limitations
Not applicable to biopolymers
No insight into:
Minimum droplet size that can be created
Amount of emulsifier needed
Stability of emulsion to environmental stresses
Testing Emulsifier Efficiency:
Fundamental Measurements
Surface Load ( )
mg/m
2
Maximum surface area that can be covered per gram
Binding Affinity (c
1/2
)
Amount of emulsifier required to reach saturation
Maximum Surface Pressure (
Sat
)
mN/m
Minimum droplet size achievable
Adsorption Kinetics
c
i
/t (measured under dynamic conditions)
Minimum droplet size achievable
0
5
10
15
20
25
30
35
40
0.0001 0.01 1
[Emulsifier]


(
m
J
/
m
2
)

c
1/2
www.dataphysics.de
0
1
2
3
4
5
0 2 4 6 8 10
Emulsifier Concentration (wt%)
M
e
a
n

R
a
d
i
u
s

(

m
)
Depends on:
Solution Conditions
Mechanical Device
C
min
r
min
Testing Emulsifier Efficiency:
Practical Tests for Emulsion Formation
C
min
= minimum amount of
emulsifier to homogenize fixed
quantity of oil
r
min
= minimum achievable
droplet size
Factors Affecting Emulsion
Formation
C
min
& r
min
Depend on:
Adsorption Rate
Interfacial Tension Reduction
Packing Efficiency
Membrane Protective Effect
High C
min
Low C
min
Testing Emulsifier Efficiency
Practical Tests for Emulsion Stability
Emulsion
preparation
Emulsion
characterization
Droplet Size
Droplet charge
Rheology
Creaming
Long term storage, accelerated or environmental stress tests
or
Test
Initial
Emulsion
Minerals and pH
pH 2 to 8
NaCl 0 1 M, CaCl
2
0 100 mM
Thermal Processing
30-90 C for 30 minutes
Freeze Thaw Cycling
-20C / +20C
Dehydration
Spray drying or Freeze drying
Mechanical Agitation
Shaking, Stirring
Testing Emulsifier Efficiency
Stability to Environmental Stress
Stable Unstable
Stability to Environmental Stress
Influence of Emulsifier Type
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
-
Steric, (Electrostatic)
Electrostatic, Steric
Steric, Electrostatic
Electrostatic, Steric
Stabilizing
Mechanism
T
pH, I, T
-
pH, I, T
Environmental
Sensitivity
Surfactants
Non-ionic
Ionic
Polysaccharides
Proteins
Emulsifier Type
Thickness
Charge
Hydrophobicity
Rigidity
0
1
2
3
4
5
6
3 4 5 6 7
pH
M
e
a
n

D
i
a
m
e
t
e
r

(

m
)
WPI
GA
MS
Stability to Environmental Stress
Influence of Emulsifier Type
WPI stabilized emulsions are sensitive to pH, minerals, temperature
Comparison of Physiochemical
Properties of Emulsifiers
The choice of an appropriate emulsifier depends on many factors
(Freezing, Drying) High High Slow Yes
(No)
Polysaccharide
Freezing, Drying
Heating, I, pH
Low /
Medium
Medium Medium Yes Protein
Freezing, Drying
Heating, I
Low Low Rapid No
(Yes)
Surfactant
- Ionic
Freezing, Drying
Heating
Low Low Rapid No Surfactant
- Non-ionic
Environmental
Sensitivity
Amount
Needed
Interfacial
Tension
Adsorption
Rate
Natural Emulsifier
Type
Selecting an Emulsifier
Establish Operating Environment
pH, I, T, Mechanical stress, Water content
Establish Labeling Requirements
Natural? Kosher? Vegan? GMO? etc
Establish Maximum Cost-in-Use of Emulsifier
Identify Available Emulsifiers
Surfactants, Phospholipids, Biopolymers
Carry Out Product Tests
Particle Size, Amount Needed, Stability, Ease of Use
Texture Modifiers
Functional Properties:
Texture Modify the overall textural properties
and mouthfeel of the system
Stability Retard movement of droplets and other
particulate matter
Mode of Operation:
Thickening Agents: increase viscosity because of
their large molecular dimensions
Gelling Agents form gels because of their ability
to form intermolecular cross-links
S S
Thickening & Gelling Agents
Typical Food Ingredients
Polysaccharides
Agar, Alginic acid, Alginate, Carrageenan, Guar
gum, Gellan gum, Curdlan, Modified Celluloses,
Modified starches, Pectins, Xanthan
Proteins
Gelatin, Whey, Casein, Soy, Egg
Sugars & Polyols
Glycerol, Sorbitol, Lactitol, Mannitol
Trehalose
Xanthan Gum: IFR, UK
Thickening Agents
Molecular Characteristics
Charge Density
+
+
+
+
+
+ +
+
Low High
Molecular Weight
High
Low
Charge Sign
+
+
+
+
+
+
Negative Positive





Unbranched Branched
Branching
Conformation
Random Coil Globular Rigid Rod
Biopolymer Solution Rheology
Influence of Particle Concentration
Biopolymers Increase Fluid Viscosity
No Biopolymer
Biopolymer
Greater
Energy
Dissipation
=
0
(1 + 2.5 )
Thickening Agents
Quantifying their Functionality
Rotating
Polymer
Trapped
Water
polymer
sphere
V
V
V
R =
Volume Ratio:
Factors Influencing RV:
Molecular Weight
Degree of Branching
Electrical Charge Density
Conformation
Interactions
=
0
(1 + 2.5 R
v
)
1
10
0.01 0.1 1 10
Concentration (kg m
-3
)
R
e
l
a
t
i
v
e

V
i
s
c
o
s
i
t
y
Thickening Agents
Influence on Solution Rheology
Dilute
c*
Semi-Dilute
Concentrated
c* 530 / R
v
(kg m
-3
)
1
10
0.01 0.1 1 10 100
Concentration (kg m
-3
)
R
e
l
a
t
i
v
e

V
i
s
c
o
s
i
t
y
1
100
1000
5000
R
v
Thickening Agents
Influence of Structure on Rheology
44 69 383 Gelatin
810 1270 345 Collagen
2.3 3.6 68 Hemoglobin
1.7 2.7 14.1 Lysozyme
R
V
[] [] [] []
(g/mL)
MW
(kDa)
Proteins
* Adapted from Peter Wolf (2005)
Thickening Agents: Effective Volumes
R
v
0.64 [] (in g mL
-1
)

C
Thickening Agents: Effective Volumes
70 110 50 Pectin
124
500
1540
193
780
2,400
100
300
1,000
Xanthan
64
157
99
245
500
1,000
Amylose
45
109
71
170
100
300
LBG
40
77
62
120
100
200
Guar
173
350
270
550
100
300
Alginate
R
V
[] [] [] []
(g/mL)
MW
(kDa)
Polysaccharides
* Adapted from Peter Wolf (2005)
Thickening Agents
Influence of Molecular Properties on R
V
Effect of Branching
Branched:
Low R
V
Linear:
High R
V
Effect of Salt (Charged Polymer)

Low Salt:
High R
V
High Salt:
Low R
V

+
+
+
+
Effect of Chain Length
High MW:
High R
V
Low MW:
Low R
V
0.001
0.01
0.1
0.001 0.01 0.1 1 10 100 1000
Shear Stress (Pa)
V
i
s
c
o
s
i
t
y
Thickening Agents
Shear Thinning Behavior
Entangled
Extended
Elongated
Aligned
Less resistance
to flow
More resistance
to flow
Decreasing
Concentration
Gelling Agents:
Molecular Basis of Functionality
Why do some biopolymers form gels?
What determines gel characteristics?
Eggs
Globular Proteins
Heat-set
Irreversible
Gell-O
Flexible Proteins
Cold-set
Reversible
Pudding
Starch
Cold/Heat-set
Irreversible
Food Gels:
Many Different Gel Mechanisms
Deserts
Polysaccharides
Ca
2+
-set
Irreversible
Molecular Basis of Gelation
Molecular
Characteristics:
- MW, Conformation,
Flexibility, Charge
Physical Properties:
- Texture, Appearance,
Stability,
Mouthfeel
Microscopic behavior:
- Interactions,
Organization
Design
Understanding
Hydrogen
bonding
Hydrophobic
attraction
Ca
2+
COO


OOC
Salt
bridge
Covalent
bond
VDW
attraction
Gelling Agents:
Gelation Mechanism
S S
Particulate gel Filament gel
Gel Structure and Properties
Gel Strength
Gel Appearance
Water Holding Capacity
Reversibility
Setting Mechanism
Heat, Cold, Ions, pH etc
Environmental Responsiveness
Key Properties:
Pore
Size
Bond
strength
Structural-unit
dimensions
Bond
number
Thickening & Gelling Agents
Selection Criteria
Physicochemical Characteristics
Rheology: Viscosity Enhancement Capacity; Gel
strength, Gelation Temperature, Reversibility, etc
Dispersion & Solubility Characteristics
Appearance (Transparent, Turbid, Opaque)
Environmental Sensitivity (pH, T, I)
Ingredient Compatibility
Other Characteristics
Legal Status
Label Friendliness
Cost, Reliability of Supply
Weighting Agents:
Retardation of Creaming
V
V
=
=
-
-
2
2
r
r
2 2

g/9
g/9

1 1
Stokes Law:
Stokes Law:
Role of weighting agents
Role of weighting agents
:
:

Incorporation of dense oil


Incorporation of dense oil
-
-
soluble material in the oil
soluble material in the oil
phase reduces the density difference (
phase reduces the density difference (

), thereby
), thereby
slowing gravitational separation.
slowing gravitational separation.
Weighting Agents
Creaming Velocity of Oil Droplets
-0.5
-0.3
-0.1
0.1
0.3
0.5
-100 0 100 200

(kg m
-3
)
U
/
r
2

x

1
0
6

(
m
-
1
s
-
1
)
Stable to Creaming
Sedimentation
Creaming
Commonly Used Weighting
Agents
Name Density Characteristics
BVO 1290 kg m
-3
Viscous Liquid
SAIB 1150 kg m
-3
Viscous Liquid
Ester Gum 1080 kg m
-3
Solid
Damar Gum 1060 kg m
-3
Viscous Liquid
Factors: Legal Limits, Ease of Utilization, Labeling, Reliability
SAIB: sucrose acetate isobutyrate
BVO: brominated vegetable oil
Weighting Agent Content
Weighting Agent Content
:
:

WA WA
= [
= [

AQ AQ
-
-

O O
]/ [
]/ [

WA WA
-
-

O O
]
]
Alternative Strategies to
Traditional Weighting Agents
Filled
Hydrogel Particles
Make density of particle equal density of surrounding aqueous phase:
Density of oil < density of water
Density of biopolymers > density of water
Density of solid fat > density of liquid oil
Solid Lipid
Nanoparticles
Multilayer
Emulsions
Importance of Ingredient
Interactions
Functional ingredients can interact with other components,
which can either improve and adversely affect their
performance
Interactions Change:
Charge
Conformation
Hydrophobicity
Solubility
Association
Interactions: Electrostatic,
Hydrophobic, Hydrogen bonding
0
5
10
15
0 0.05 0.1 0.15 0.2 0.25
[Pectin] (wt%)
d
3
2

(

m
)

Example of Ingredient Interactions:


Emulsifier and Thickening Agent
Emulsifier: -Lg
Thickening Agent: Pectin
+ ++ +
+ ++ +
+ ++ +
+ ++ +
+ ++ +
+ ++ +
pH 3
Importance of Order of Ingredient
Incorporation
The order of ingredient addition may have a large
impact on product properties:
Homogenization - viscosity, competitive adsorption
Thermal Processing - thermally labile substances
Ingredient interactions - pH, salt, surfactants, chelating agents
Example of Importance of Order of
Ingredient Addition:
NaCl Addition &Thermal Stability
0.1
1
10
100
30 50 70 90
Temperature (
o
C)
D
i
a
m
e
t
e
r

(

m
)
Heat + 0mM
0 mM + Heat
Heat + 150mM
150 mM + Heat
Surface
Denaturation
Thermal
Denaturation
Thermal stability of -Lg stabilized O/W emulsions (pH 7)
Wrap Up
Clearly establish functional characteristics
of each component in product
- Why is it there?
- What role(s) does it play?
- Is there a better alternative?
- Is there a cheaper alternative?
- Is there synergism/antagonism?
Water 0-25 172.840 E 433 Polysorbate 80 Polyoxyethylene (20) sorbitan
monooleate
Water 0-25 172.838 E 436 Polysorbate 65 Polyoxyethylene (20) sorbitan
tristearate
Water 0-25 172.836 E 435 Polysorbate 60 Polyoxyethylene (20) sorbitan
monostearate
Oil 0-15 - E 492 STS Sorbitan tristearate
Water 0-25 172.842 E 491 SMS Sorbitan monostearate
Oil/Water* 0-10 172.859 E 473 Sucrose esters of FA
Oil 0-25 172.856 E 477 PGMS Propylene glycol esters of FA
Water 0-25 172.854 E 475 PGE Polyglycerol esters of FA
- 172.830 - SMG Succinic acid esters of MG
Oil NL 172.852 E 472b LACTEM Lactic acid esters of MG
Oil NL 172.828 E 472a ACETEM Acetic acid esters of MG
Oil NL 184.1505 E 471 MG Monoglycerides
NON-IONIC
Water 0-50 184.1101 E 472e DATEM Diacetyl tartatric acid esters of MG
Water NL 172.832 E 472c CITREM Citric acid esters of MG
Oil 0-20 172.844 E 482 CSL Calcium stearoyl lactylate
Water 0-20 172.846 E 481 SSL Sodium stearoyl lactylate
Oil/water NL 172.863 E 470 FA Fatty acid salts
Oil/water NL 184.1400 E 322 Lecithin
IONIC
Solubility ADI (mg/kg) US FDA EU number Abbreviation Chemical Name
Food Grade Surfactants