Dr.

Nguyen Minh Xuan Hong

4.1 Structure and classification

Food Chemistry 4.2 Properties

Chapter 4. Lipids
210251 4.2.1 Sensory properties
4.2.2 Melting point and crystallization
4.2.3 Amphiphilic properties, aquatic solubility
and emulsification properties
4.3 Reactions
4.3.1 Melting point change reactions
4.3.2 Reactions during heat treatment
Dr. NGUYỄN MINH XUÂN HỒNG 4.3.3 Lipid oxidation
Department of Food Biochemistry and Human Nutrition
4.4 Food emulsions
Faculty of Chemical Engineering and Food Technology
Nong Lam University Ho Chi Minh City 4.4.1 Formation and stability
nmxhong@hcmuaf.edu.vn 4.4.2 Emulsifiers and stabilizers
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 Lipidsare naturally occurring organic

compounds, commonly known as oils and fats.

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Oil and Fats have similar structure and properties

except the followings:

Criteria Oils Fats

Status at room
Liquid Solid
temperature

Main fatty acid Unsaturated Saturated fatty

composition fatty acids acids

Source Plants Animals

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 Lipids contain a broad group of chemically disperse
compounds that soluble in organic solvents.
 Food lipids contribute to quality attributes such as
texture, flavor, nutrition and caloric density.
 Their composition, crystalline structure, melting
properties and ability to associate with water and
non-lipid molecules are especially important to their
functional properties in many foods.
 During processing, storage and handling of foods,
lipids undergo complex chemical changes and react
with other food constituents, producing numerous
compounds both desirable and deleterious to food
quality.
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Dietary lipids play an important role in nutrition.
They supply calories and essential fatty acids, act
as vitamin carriers, and increase the palatability of
food, but for decades they have been at the center
of controversy with respect to toxicity, obesity and
disease.
 The physical stability of lipids is important in food
quality since most lipids exist as dispersion
/emulsions that are thermodynamically unstable.
 The stability of lipid emulsions is an important
quality attribute that can influence shelf-life,
appearance and texture.

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 Lipids has no single common structure. The most Structural composition of lipid
commonly occurring lipids are triglycerides and Fatty acid 1
composes of glycerol bonded
phospholipids. with three fatty acids.

Glycerol
 Triglycerides have a glycerol backbone bonded  If three fatty acids are similar Fatty acid 2
to three fatty acids.  simple triglyceride
 Phospholipids contains glycerol and fatty acids,  If fatty acids are not similar
they also contain phosphoric acids and a low-  mixed triglyceride Fatty acid 3
molecular weight alcohol.
 Found in membranes of animal and plants.
 Common phospholipids: lecithins, cephalins. 9 10

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1 Leaflet
2 Leaflets

 The lipid molecules have a globular (polar) head and a

straight region (non-polar). Each row of lipids is a leaflet.
 Therefore, the plasma membrane consists of two leaflets
with the non-polar regions pointing inward.

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 Glycerol (or glycerine, glycerin) is a simple polyol

 Membrane architecture is that of a lipid bilayer
 The lipids are amphipathic in that they have
• hydrophilic polar heads pointing out and
• hydrophobic portion forming the core
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(sugar alcohol) compound.
 It is a colorless, odorless, viscous liquid that is widely
used in pharmaceutical formulations.
 Glycerol has three hydroxyl groups that are responsible
for its solubility in water and its hygroscopic nature.
 The glycerol backbone is central to all lipids known as
triglycerides.
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R-COOH
H H H  Fatty acid (FA) is any aliphatic monocarboxylic
acid that can be liberated by hydrolysis from
H C C C H naturally occurring fats.

OH OH OH
 Fatty acid is organic acid that contains C, H & O
atoms in molecule.
Glycerol
 Almost without exception the fatty acids that
 Synonyms: Glycerin;
1,2,3 trihydroxy propane;
occur in foodstuffs contain an even number of
1,2,3 propanetriol carbon atoms in an unbranched chain.
 3 hydroxyl (OH) functional groups

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 Fatty acids can be divided into 2 groups

Hydrocarbon and Fatty acids according to their nutritive value:
 Essential fatty acids
 Non-essential fatty acids

 Fatty acids can also be divided into 2 groups

according to bonding system:
 Saturated fatty acids or SFA
 Unsaturated fatty acids or UFA
 Mono-unsaturated fatty acids or MUFA
 Poly-unsaturated fatty acids or PUFA

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Essential fatty acids are those that cannot be

constructed through any chemical pathways,
known to happen in humans.

They must be obtained from the diet.

Linoleic acid (C18:2) and linolenic acid (C18:3)

are the essential fatty acids.

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Fatty acid Name Structure Food source

family
Omega-3 Alpha-linolenic acid (ALA) 18:3 (n-3) Walnuts, flaxseed oil,
soybeans, canola oil
Eicosapentaenoic acid 20:5 (n-3) Fatty fish and fish oils
(EPA)
Docosahexaenoic acid 22:6 (n-3) Fatty fish, fish oils,
(DHA) algal oils
Omega-6 Linoleic acid (LA) 18:2 (n-6) Corn, safflower,
soybean, cottonseed
and sunflower oils
Gamma-linolenic acid 18:3 (n-6) Evening primrose oil,
(GLA) borage oil, black
current seed oil
Arachidonic acid (ARA) 20:4 (n-6) Meat, poultry, eggs
27 Omega-9 Oleic acid (OA) 18:1 (n-9) Olive oil, grapeseed oil
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 Saturated fatty acid is long chain carboxylic acid and do

Non-essential fatty acids are those which are not have double bond, i.e. it has an acid group -COOH and
not necessary to be taken through diet, they are only carbon and hydrogen, with each carbon atom attached
synthesized through chemical pathways. by single bonds to the next atom.

 Example: arachidic acid, stearic acid, palmitic acid, etc.

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 Unsaturated fatty acids have at least one double bond

between two adjacent carbon atoms.
 The two carbon atoms are bound to each other through
double bonds and can occur in cis or trans configuration.
 Double bonds are a point of weakness, and not strength,
in organic molecules as they can readily be broken by a
wide range of substances.
cis and trans configuration

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Common Saturated fatty acids Common unsaturated fatty acids

No. of Common Systematic Formula No. of Common Systematic Name Formula
C atom Name Name C atom Name
4 Butyric Butanoic C3H7COOH 18 Oleic 9-octadecanoic C17H33COOH
6 Caproic Hexanoic C5H11COOH
18 Linoleic 9,12-octadecadienoic C17H31COOH
8 Caprylic Octanoic C7H15COOH
9,12,15-
10 Capric Decanoic C9H19COOH 18 Linolenic C17H29COOH
octadecatrienoic
12 Lauric Dodecanoic C11H23COOH
14 Myristic Tetradecanoic C13H27COOH
16 Palmitic Hexadecanoic C15H31COOH
18 Stearic Octadecanoic C17H35COOH
20 Arachidic Eicosanoic C19H39COOH
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C 22:6 (n-3)

C 20:5 (n-3)

C 18:3 (n-3)

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Methyl end Carboxyl end

Classification of lipids

n-9

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Major class Subclass Description

Simple lipids Acylglycerols Glycerol + fatty acids
Waxes Long-chain alcohol + long-
chain fatty acid
Compound Phosphoacylglycerols Glycerol + fatty acids +
lipids (or glycerophospholipids) phosphate + another group Simple lipids are the esters of fatty acids with
usually containing nitrogen
various alcohols.
Sphingomyelins Sphingosine +fatty acid +
phosphate + choline
Fats and Oils (triglycerides and triacylglycerols) -
Cerebrosides Sphingosine +fatty acid +
simple sugar
These are esters of fatty acids with a trihydroxy
Gangliosides Sphingosine +fatty acid + alcohol, glycerol. A fat is solid at ordinary room
complex carbohydrate moiety temperature, an oil is liquid.
that include sialic acid
Derived lipids Materials that meet the Examples: carotenoids, Simple Triglycerides - Simple triglycerides are
definition of a lipid but steroids, fat-soluble vitamins one in which three fatty acids radicles are similar or
are not simple or
compound lipids are of the same type. Example: Tristearin, Triolein.
Source: Nawar (1996) 43 44

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 Mixed Triglycerides are one in which the three fatty

acids radicles are different from each other. Example:
distearo-olein, dioleo-palmitin.

 Heterolipids are esters of fatty acids with alcohol and

possess additional groups also.

 Phospholipids or Phosphatids are compounds containing

 Waxes are the esters of fatty acids with high
molecular weight monohydroxy alcohols.
Example: Beeswax, Carnauba wax.
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fatty acids and glycerol in addition to a phosphoric acid,
nitrogen bases and other substituents. They usually possess
one hydrophilic head and two non-polar tails. They are called
polar lipids and are amphipathic in nature.
Phospholipids can be phosphoglycerides, phosphoinositides
and phosphosphingosides.
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 Phosphoglycerides are major phospholipids, they are Lecithin

found in membranes. It contains fatty acid molecules which
are esterified to hydroxyl groups of glycerol. The glycerol
group also forms an ester linkage with phosphoric acid.
Example: Lecithin, Cephalins.
 Phosphoinositides are said to occur in phospholipids of
brain tissue and soybeans. They play important role in
transport processes in cells.
Phosphosphingosides are commonly found in nerve
tissue. Example: sphingomyelins.
 Glycolipids are the compounds of fatty acids with
carbohydrates and contain nitrogen but no phosphoric acid.
The glycolipids also include certain structurally related Cephalin
compounds comprising the groups gangliosides, sulpholipids
and sulfatids.
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Phosphoinositides Sphingomyelin

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 Derived lipids are the substances derived from simple and

compound lipids by hydrolysis. These includes fatty acids,
alcohols, monoglycerides and diglycerides, steroids,
Ganglioside terpenes, carotenoids.

 The most common derived lipids are steroids, terpenes and

carotenoids.

Sulfatid  Steroids do not contain fatty acids, they are nonsaponifiable,

and are not hydrolyzed on heating. They are widely
distributed in animals, where they are associated with
physiological processes.
Example: Estranes, androstranes, etc.
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 Terpenes in majority are found in plants. Ex: Natural rubber,

germoil, etc.

 Carotenoids are tetraterpenes. They are widely distributed in

both plants and animals, exclusively of plant origin. Due to the
presence of many conjugated double bonds, they are colored
red or yellow. Ex: Lycopreene, Carotenes, Xanthophylls.

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 What is the quality of the product as it is received, in absolute

4.2.1 Sensory properties terms? Is it acceptable, or has it already become “rancid”?
 If the product as received is of more or less satisfactory
4.2.2 Melting point and crystallization quality, how long, under defined storage conditions, is it likely to
remain so?
4.2.3 Amphiphilic properties, aquatic solubility
 The answer to the first question can be obtained directly
and emulsification properties from a simple sensory test.
 It is accepted for most oils and fats that a completely
bland and tasteless products is ideal.

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Table 2. Aroma threshold values (odor and/or taste) of free fatty acids
in different food items
 However, the problem for the taster is the detection of very
small amounts of objectionable oxidation end-products. Fatty acid Aroma threshold (mg/kg) in
These are mainly aldehydes, but alcohols, ketones, Cream Sweet Coconut fat
carboxylic acids and lactones also play a part in off-flavors. Odor Taste cream Odor Tasteb
buttera
 Alternatively, specific classes of end-products can be 4:0 50 60 40 35 160
monitored by chemical analysis. 6:0 85 105 15 25 50
8:0 200 120 455 >1,000 25
 The answer to the 2nd question requires the development of 10:0 >400 90 250 >1,000 15
predictive tests to forecast stability or shelf life.
12:0 >400 130 200 >1,000 35
 These can be accelerated deterioration studies or they can 14:0 >400 >400 5,000 >1,000 75
be measures of the levels of oxidation intermediates, such as
16:0 n.d. n.d. 10,000 n.d. n.d.
peroxides.
18:0 n.d. n.d. 15,000 n.d. n.d.
 The formation of such intermediates, themselves without
flavor, is a warning of rancidity to come, since they will
aOdor/taste not separated,
bQuality of taste: 4:0 rancid; 6:0 rancid, like goat;
inevitably break down in the course of time to produce off- 8:0 musty, rancid, soapy; 10:0, 12:0 and 14:0 soapy
flavor end-products. n.d. : not determined.
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Table 3. Threshold valuesa of fatty acids depending on the pH-value of a

aqueous solution

Fatty acid Threshold (mg/kg) at pH

 Rancid flavors are chemically very complex, since they
3.2 4.5 6.0 are derived from any or all of the unsaturated fatty acids
4:0 0.4 1.9 6.1 originally present in the oil and each of these can oxidize
6:0 6.7 8.6 27.1 through several different mechanisms.
8:0 2.2 8.7 11.3  Descriptive terms such as rancid, painty, beany, green,
10:0 1.4 2.2 14.8 metallic, stale and so on are attempts to describe
sensations arising from the presence of very small
a Odor and taste quantities of oxidation end-products in an oil or fat.
 Some specific, well-recognized aldehydes have distinctive
characters. A few examples are given in the Table 4.

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Table 4. Characters and threshold levels of selected aliphatic aldehydes

 In evaluating an oil or fat for suspected oxidative deterioration,
Aldehyde Threshold (ppm) Character trained tasters should participate in a standard triangular test
cis-3-Hexenal 0.09 Green bean and inconsistent results should be rejected.
trans-2-Hexenal 0.60 Green
cis-4-Heptenal 0.0005 Cream to tallow  Following correct discrimination, flavor intensity should be
trans-6-Nonenal 0.00035 Hydrogenation based on a hedonic scale such as:
trans-2-cis-6-Nonadienal 0.0015 Beany  Bland 0
trans-2-trans-6-Nonadienal 0.02 Cucumber  Suspicion of off-flavor 1
trans-2-trans-4-Decadienal 0.10 Stale frying oil  Noticeable but very slight off-flavor 2
 More noticeable off-flavor 3
 These aldehydes are ultimately derived from linoleic  Distinct off-flavor 4
or linolenic acids. Most of them are dislikes, through  Disagreeable off-flavor, rancid 5
a few, such as cis-4-heptenal, can at suitable  Markedly disgreeable off-flavor, very rancid 6
concentrations, contribute positively to flavor.

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 If a fat, a fatty acid, or some esters of fatty acids are

heated very slowly, they will melt, exist as a liquid as
 Melting point and crystallization are the physical the temperature rises, and then solidify again.
properties of the natural fats and oils.
 A second melting will then occur at a higher
 Fats and oils composition are not constant but vary temperature.
slightly with:
 Climate, soil and variety for vegetable oils  If the material is then chilled rapidly, it will melt at a
lower temperature when it is warmed again.
 Nutrition, season and breed for animal oils.
 This behavior has been known for many years, but it
 Fats do not melt sharply but soften over a range of
is only in recent times with the use of modern
temperatures and it is therefore impossible to apply
techniques that the explanation has been possible.
the melting point technique, used in the identification
of pure organic compounds to them.
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 Polymorphism: the occurrence of more than one

crystalline form.
 Polymorphism is found in many long-chain carbon
compounds.
In compounds with several crystalline forms, one
form is the most stable and tends to be established.

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 Polymorphism is important to the understanding

Triglyceride Melting point (C) of the melting-point behavior of fats, fatty acids
-form β’-form β-form and their esters. Furthermore, polymorphism plays
Tricaprin -15 18.0 31.5 a significant role in any operation where fats are
Trilaurin 15 35.0 46.4 solidified.
Trimyristin 33 46.5 57.0
 Environmental conditions must be controlled so
Tripalmitin 45 56.0 65.5 that the product will be uniform.
Tristearin 54.5 65.0 71.5
For example, when chocolates are dipped, the
Triolein -32 -12 5.0
formation of the high-melting forms is produced by
Trielaidin 15.5 37.0 41.5
controlling the temperature of solidification.
Trierucin 6 25 32.5
Trilinolein - -43 -13.1
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 Solid fats are plastic over a fairly wide range of
temperatures. By plastic meaning that they are soft and
can be deformed, but do not have the ability to flow.
The spreading quality of butter is the result of its plastic
nature.
When solid fats are examined microscopically, they are
composed of a mass of tiny crystals in a matrix of liquid
fat. The crystals are not enmeshed but are able to slide
by one another and consequently give the mixed fat its
plastic nature.
 A fat composed of only one kind of molecules does not
possess this property of plasticity since it is, at any given
temperature, composed of either entirely of crystals or as
liquid.
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 As a fat is warmed, the number of crystals
distributed through the liquid fat diminishes and the
amount of liquid increases so that the fat softens.
 If the number of crystals exceeds a critical amount,
the fat will be hard and brittle and will lose plasticity.
 On the other hand, if the amount of liquid exceeds
a critical level, the fat will flow.
 The low melting temperature that characteristics the
oils is associated with either
• a high proportion of unsaturated fatty acids,
e.g. corn oil and olive oil, or
• a high proportion of short-chain fatty acids,
e.g. milk fat and coconut oil.
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Fatty acid No. of C and DB bond Melting point (C)

Butyric acid C4:0 -7.9
Caproic acid C6:0 -3.4
Caprylic acid C8:0 16.7
Increasing
Increasing

Capric acid C10:0 31.6

Lauric acid C12:0 44.2
Myristic acid C14:0 54.1
Palmitic acid C16:0 62.7
Stearic acid C18:0 69.6
Arachidic acid C20:0 75.4
Elaidic acid C18:1 trans 43.7
Oleic acid C18:1 10.5
Decreasing
Increasing

Linoleic acid C18:2 -5.0

Linolenic acid C18:3 -11.0
Arachidonic acid C20:4 -49.5 76 77

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Amphiphilic or Amphipathic
or Amphiphile is a term
describing a chemical
compound possessing both
hydrophilic (water-loving,
polar) and lipophilic (fat-
loving) properties.

Phospholipids have amphiphilic character

Common amphiphilic substances are soaps, detergents
and lipoproteins.
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 Ethyl ether is the best solvent for stearic acid and

 Long-chain fatty acids are practically insoluble in
water; instead, they form a floating film on the water
surface.
 The polar carboxyl groups in this film are oriented
toward the water, while the hydrophobic tails protrude
into the gaseous phase.
 The solubility of the acids increases with decreasing
carbon number; butyric acid is completely soluble in
water.
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other saturated long-chain fatty acids since it is
sufficiently polar to attract the carboxyl groups.
 A truly nonpolar solvent, such as petroleum benzine,
is not suitable for free fatty acids.
 The solubility of fatty acids increases with an
increase in the number of cis double bonds.
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 When oil is added to water, it forms a separate layer
above the water; that is oil and water do not dissolve in
each other and are said to be immiscible.
 If oil and water are shaken vigorously, the two liquids
become dispersed in each other and an emulsion is
said to formed.
 Such an emulsion is unstable, however, and on
standing it reverts to the original two layers.
 Emulsions are described as being either:
 Oil-in-water (O/W)
 Water-in-oil (W/O)
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 The adsorbed film prevents the droplets from coalescing
and in some instance, may form a film which by virtue of it
mechanical strength, imparts stability.
 For example, protein emulsifiers are notable for the
mechanical strength of the adsorption film which they
produce.
 If an emulsifier contains charged groups, the adsorption
process gives rise to charged droplets which repel each
other.
 Such droplets will not coalesce and this factor therefore
promotes emulsion stability.
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 In order for oil and water to form a stable emulsion, a third
substance called an emulsifying agent or emulsifier
must be present.
 If the surface tension between
oil and water, known as
interfacial tension, is great, it is
difficult for a stable emulsion to
be formed.
 Emulsifiers lower interfacial
tension by becoming adsorbed
at the oil-water interface and
forming a film one molecule
thick around each droplet.
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 Lipids that show emulsification properties include:
 Lecithin (from egg yolk and vegetable oils)
 Glyceryl monostearate (GMS)
 Mustard – where a variety of chemicals in the
mucilage surrounding the seed hull act as emulsifiers
 Sodium stearoyl lactylate
 Diacetyl Tartaric (Acid) Ester of Monoglyceride
(DATEM) – an emulsifier primarily used in baking
 Many different emulsifiers are used in pharmacy to
prepare emulsions such as creams and lotions.
 Common examples include emulsifying wax, cetearyl
alcohol, polysorbate 20 and ceteareth 20.
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4.3.1 Melting point change reactions
4.3.2 Reactions during heat treatment
4.3.3 Lipid oxidation
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 The problem is further complicated by the fact that
glycerides are soluble in one another.
 A particular type of molecule may dissolve in the liquid
portion of the fat at a temperature considerably below its
melting point.
 Glycerides also have a tendency to supercool, i.e., to
remain as liquids at a temperature below their melting point
as they are cooled down from a high temperature.
 The consistency of a fat at 30C may be different if it is
heated slowly from room temperature than if it has been
quickly cooled from a higher temperature. After standing, it
will again come to equilibrium and the effects of
supercooling will disappear.
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 Natural fats are complex mixtures of glycerides each with
its characteristic melting point.
 As the temperature of the fat is raised, the melting point of
the first one and then another of these triglycerides is
exceeded.
 Eventually a temperature is reached at which all of the
glycerides have melted and the fat is liquid.
 The temperature at which this occurs is not sharply defined.
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 In general, fats which contain relatively large amounts of
unsaturated fatty acids have relatively low melting points
and are usually oils at room temperature, while those with
relatively large amounts of saturated fatty acids have higher
melting points.
 When a melting point of pure, simple triglycerides are
determined, it is found that lengthening the carbon chain of
the fatty acids increases the melting points.
 For example, the melting point of β’ form:
 Trimyristin (C14) is 46.5C
 Tripalmitin (C16) is 56.0C
 Tristearin (C18) is 65.0C
 Thus, fats which are mixtures of glycerides of long chain,
saturated fatty acids have higher melting points than those
which have either numerous unsaturated fatty acids or short
chain ones, or both. 89
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 Deep frying is one of the methods of food preparation used

in the home and in industry.
 Meat, fish, doughnuts, potato chips or french fries are dipped
into fat (oil) heated to about 180C.
 After several minutes of frying, the food is sufficiently tender
to be served.
 The frying fat or oil changes substantially in its chemical and
physical properties after prolonged use. This will result in a
decrease in iodine number.

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Table: Characteristics of partially hydrogenated soybean oil before and

after simulated deep fat frying* A review of reactions occurring in heat treated fats and oils
Characteristic Fresh oil Heated oil Fat/oil heating Reaction Products
Iodine number 108.9 101.3 1. Deep frying without Autoxidation Volatile acids
Saponification number 191.4 195.9 food Isomerization aldehydes
Free fatty acids 0.03 0.59 Polymerization esters
Hydroxyl number 2.25 9.34 alcohols
DG 1.18 2.73 Epoxides
Composition of fatty acids (weight %) Branched chain fatty acids
14:0 0.06 0.06 = Dimeric fatty acids
16:0 9.90 9.82 Mono- and bicyclic
18:0 4.53 4.45 compounds
18:1 (9) 45.3 42.9 Aromatic compounds
18:2 (9, 12) 37.0 29.6 Compounds with trans double
18:3 (9, 12, 15) 2.39 1.67 bonds
20:0 0.35 0.35 = Hydrogen, CO2
22:0 0.38 0.38 = 2. Deep frying with As under 1. and in As under 1. and in addition
Other 0.50 0.67 food added addition free fatty acids, mono- and
*The oil was heated for 80 h (8 h/day) at 195C.
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 In all foods, the first mode of spoilage is microbial.
However, after microbes have been controlled by
processing, oxidation becomes the set of chemical
reactions most limiting shelf-life and degrading the
quality of foods.
 Consumers commonly recognize lipid oxidation
by characteristic painty or oily “rancid” off-flavors or
odors, but the impact of the reaction is far greater
than this.
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 Lipid oxidation is not limited merely to foods, as radicals,
hydroperoxides, epoxides, and aldehydes are involved in
normal physiological processes in living tissues, including
aging, cancer, atherosclerosis, Alzheimer’s disease and
other dementias, inflamatory bowel disease and muscular
degeneration.
 Lipid oxidation primarily involves the reaction of
oxygen with unsaturated fatty acids.
 Lipid oxidation in foods is most commonly associated
with fats and oils in bulk or in oil phases of emulsions,
and certainly that is where the reaction is most obvious
to consumers.
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 As the most sensitive chemical functional groups in biological
molecules, unsaturated fatty acids essentially harvest
oxidizing potential from the atmosphere and transform it into
highly reactive chemical species.
 Once initiated, the free radical chains of lipid oxidation are
responsible for a cascade of oxidation that affect structural
proteins and enzymes, nucleic acids, polysaccharides,
vitamins and lipids.
 The overall effect is to alter physical properties and degrade
molecular functionality as well as to destroy the palatability of
foods.
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 Oxidation occurs wherever unsaturated fatty acids are found
and that means in:
 Triacylglycerols: in adipose tissues and marbling fats, oil
bodies in grains, essential oils in fruits, chocolate, bulk oils
and oil phases of emulsion.
 Phospholipids: in membranes (particularly muscle foods,
organ meats, vegetables), bran layers, egg yolks and natural
and synthetic emulsifiers.
 Free fatty acids: hydrolysis products of triacylglycerols and
phospholipids resulting from acids, bases, heat with and
without water and lipase action; found especially in foods that
are heated, have microbial contamination or contain dairy or
tropical lipids.
 Fatty acid esterified to other molecules such as sterols
and alcohols (as in waxes).
 This means that lipid oxidation can be rather pervasive in
foods, even in low-lipid formulations. 99
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 Lipid oxidation has long been recognized as a free radical
chain reaction which occurs in three stages: initiation,
propagation and termination.
 Lipid oxidation is autocatalytic: once started, the reaction is
self-propagating and self-accelerating.
 Many more than one lipid molecule is oxidized and more
than one LOOH is formed per initiation. Chain lengths of up
to several hundred lipid molecules have been measured.
 Very small amounts of pro-oxidants or antioxidants cause
large rate changes.
 The reaction produces multiple intermediates and products
that change with reaction condition and time.
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 Hydroxyl radical (HO), the most strongly oxidizing radical
known, is produced by reduction of hydrogen peroxide that is
produced by enzymes in living tissues and by metals in foods.
It is so reactive that it abstract hydrogens rather non-
selectively from acryl chain. However, also because it is so
reactive, it does not migrate, so must be generated very close
to its target.
 The perhydroxyl radical (HOO), is also generated by
decomposition of hydroperoxide, as well as from protonation
of superoxide anion, O2-, the reduction product of oxygen. Its
reactions are slower than HO, but competitive with organic
peroxyl radicals. Particularly when generated in enzyme
reactions, HOO can be an effective initiator of lipid oxidation,
O2-, however, reacts only with lipid hydroperoxides and does
not react with unoxidized lipids.
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 Lipid oxidation is so constantly present in foods
that it often seems to initiate itself.
 However, in foods and biological systems, many
reactions occur that produce radicals.
 Even in trace quantities these radicals can
initiate lipid oxidation by abstracting hydrogens
and generating the first lipid alkyl radical, L.
ki
L1H L1
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 Organic peroxyl radicals abstract hydrogens several
orders of magnitude more slowly than alkoxyl radicals, but
even so, ROO and RO arising from oxidation of non-lipid
molecules in the reaction system very effectively start
oxidation chain reactions in lipids.
 These radicals are needed only to start the lipid oxidation
chain reaction, so only trace levels are needed. Once
started, the lipid oxidation chain is autocatalytic. The
presence of any non-lipid radicals then competes with lipid
radicals and may either augment lipid oxidation or have no
effect.
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Propagation

 Propagation is the heart of the oxidation process. In it, oxygen

adds at diffusion controlled rates to relatively unreactive lipid Free radical chain reaction established
alkyl radicals, L, converting them to reactive peroxyl radical,
LOO, that establish the free radical chain and keep it going.
ko
 Peroxyl radicals abstract hydrogens from adjacent lipid L 1 + O 2 L1OO 
molecules to form hydroperoxides, LOOH, and generate new kβ

L radicals in the process. kp1

L1OO + L2H L1OOH + L2
 Each new L radical in turn adds oxygen, forms a peroxyl
kp1
radical, abstract a hydrogen from another lipid, forms another L2OO + L3H L2OOH + L3 etc. LnOOH
hydroperoxide, and generates a new L radical to provide the
driving force in the chain reaction. The process continues
indefinitely until no hydrogen source is available or the chain is
intercepted.
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Free radical chain branching (initiation of new chains)

LnOOH kd1 LnO + OH- (reducing metals)

 In lipid oxidation, termination is almost a misnomer since
lipid oxidation never fully stops.
kd2
LnOOH LnOO + H+ (oxidizing metals)
 A specific radical may be terminated and form some product,
kd3
LnOOH LnO + OH (heat and UV) but usually there is another radical left behind, so the chain
reaction continues.
LnO  kp2 LnOH
LnOO + L 4H LnOOH + L 4  Net oxidation slows down when radical quenching processes
kp1
HO HOH
kp3 exceed the rate of new chain production, and the momentum
kp4 of oxidation shifts from radical propagation and chain
L1OO + LnOOH L1OOH + LnOO expansion to generation of stable products.
kp5
L1O + LnOOH L1OH + LnOO  Thus, termination in the discussion here refers to converting
i– initiation; o-oxygenation; β-O2 scission; p-propagation;
an individual lipid radical to a product, not stopping the overall
d-dissociation; t-termination; ts-termination/scission reaction. The cumulative effect on a food system is determined
by the number of radical chains being terminated.
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Termination (formation of non-radical products)

 Lipid free radicals terminate to form non-radical products by
four major mechanisms:
Ln Ln Radical recombinations
 Radical recombination
kt1
Ln O  + Ln O  Polymers, non-radical monomer products
 α and β scission reactions of alkoxyl radicals when proton kt2 (ketones, ethers, alkanes, aldehydes, etc.)
sources (e.g. water) are present to stabilize the products Ln OO Ln OO kt3

 Co-oxidation of non-lipid molecules such as proteins

Radical scissions
 Group eliminations or dismutation LOO kts1
non-radical products
LO kts2 (aldehydes, ketones, alcohols, alkanes, etc.)
 The mechanism dominating in a given food are influenced
by the nature and concentration of the radicals, the
temperature and oxygen pressure and the solvent. i– initiation; o-oxygenation; β-O2 scission; p-propagation;
d-dissociation; t-termination; ts-termination/scission

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4.4.1 Formation and stability

 Emulsions are a class of disperse systems consisting of two
4.4.2 Emulsifiers and stabilizers immiscible liquids. Emulsions DO NOT occur naturally.
 The liquid droplets (the disperse phase) are dispersed in a
liquid medium (the continuous phase).
 Several classes of emulsion may be distinguished, namely
oil-in-water (O/W), water-in-oil (W/O) and oil-in-oil (O/O).
 The latter class may be exemplified by an emulsion
consisting of a polar oil (e.g. propylene glycol) dispersed in a
nonpolar oil (paraffinic oil), and vice versa.

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Examples of emulsions

 In order to disperse two immiscible liquids a third

component is required, namely the emulsifier; the
choice of emulsifier is crucial not only for the formation of
the emulsion but also for its long-term stability.

 Emulsions may be classified according to the nature of

the emulsifier or the structure of the system.

Hydrophilic head Lypophilic tail 

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Table 11. Examples of Food Emulsions

Food Type of Main emulsifiers present or

Emulsion added
Milk, cream O/W Proteins (caseinogen)
 An emulsion occurs when two substances that do not
normally mix are forced into a mixture in which one of
Butter W/O Proteins (caseinogen)
the substances is evenly dispersed in the form of small
Mayonnaise, salad O/W Egg yolk (lecithin), GMS, droplets throughout the other substance.
cream mustard
Margarine W/O Proteins (caseinogen),  Under normal conditions, fat (either liquid oil or solid fat)
lecithin, GMS and water do not mix, but these two substances are the
Ice-cream O/W Proteins (caseinogen), GMS, most common ingredients in culinary emulsions.
plus stabilizers (gelatin,
gums, alginates)  An emulsion consists of two phases,
 The dispersed phase
 The continuous phase
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 Natural starches, such as those in garlic, or modified

starches, such as corn starch or arrowroot, are also used.

 Emulsion stability refers to the ability of an emulsion to  An appropriate "surface active agent" (or "surfactant")
resist change in its properties over time. can increase the kinetic stability of an emulsion so that
 To make an emulsion stable enough to keep the oil in the size of the droplets does not change significantly with
suspension, additional ingredients, known as emulsifiers, time. It is then said to be stable.
are necessary to attract and hold together both the oil and
liquid.
 Commonly used emulsifiers include egg yolks (which
contain the emulsifier lecithin), vegetable gums, some
fatty acids like magnesium stearate, and glycerides.

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 Several processes relating to the breakdown of emulsions

may occur on storage, depending on:
• The particle size distribution and the density difference Creaming Sedimentation Flocculation
between the droplets and the medium;
• The magnitude of the attractive versus repulsive forces,
which determines flocculation;
• The solubility of the disperse droplets and the particle
Phase Ostwald
size distribution, which in turn determines Ostwald inversion Coalescence ripening
ripening;
• The stability of the liquid film between the droplets, which
determines coalescence; and
• Phase inversion.
Schematic representation of the various breakdown processes in emulsions.
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Creaming

Sedimentation
 This process results from external forces,
usually gravitational or centrifugal.

 When such forces exceed the thermal motion of the droplets

(Brownian motion), a concentration gradient builds up in the
system such that the larger droplets move more rapidly either
to the top (if their density is less than that of the medium) or to
the bottom (if their density is greater than that of the medium)
of the container.
 In the limiting cases, the droplets may form a close-packed
(random or ordered) array at the top or bottom of the system,
with the remainder of the volume occupied by the continuous
The various breakdown processes in emulsions. liquid phase.
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Flocculation

 Flocculation describes clustering of individual dispersed
droplets together, whereby the individual droplets do not lose
their identity.
 Flocculation is thus the initial step leading to further aging of
the emulsion (droplet coalescence and the ultimate
separation of the phases).
 Flocculation occurs when there is an attractive force between
the droplets, so they form flocs, like bunches of grapes.
 This refers to the process whereby there will be an
exchange between the disperse phase and the medium.
 For example, an O/W emulsion may with time or change
of conditions invert to a W/O emulsion.
 In many cases, phase inversion passes through a
transition state whereby multiple emulsions are produced.

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 This effect results from the finite solubility (etc.) of the liquid
phases.
 Liquids which are referred to as being immiscible often have
mutual solubilities which are not negligible.
 With emulsions which are usually polydisperse, the smaller
droplets will have a greater solubility when compared to larger
droplets (due to curvature effects).
 With time, the smaller droplets disappear and their molecules
diffuse to the bulk and become deposited on the larger
droplets.
 With time, the droplet size distribution shifts to larger values.
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 Emulsifiers and stabilizers are food
additives, commonly used interchangeably
because they both serve the same end goal;
stabilizing an emulsion.
 Emulsifiers however are different from
stabilizers and each serves a unique
purpose depending on the desired finished
product.
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 This refers to the process of thinning and disruption of the
liquid film between the droplets, with the result that fusion
of two or more droplets occurs to form larger droplets.
 The limiting case for coalescence is the complete
separation of the emulsion into two distinct liquid phases.
 The driving force for coalescence is the surface or film
fluctuations; this results in a close approach of the droplets
whereby the van der Waals forces are strong and prevent
their separation.
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 The primary function of an emulsifier is to decrease the
natural repulsion of two oppositely charged molecules.
 A secondary function of an emulsifier is to increase viscosity.
 Emulsifiers are among the most frequently used types of food
additives. They are used for many reasons. Emulsifiers can
help to make a food appealing.
 Emulsifiers have a big effect on the structure and texture of
many foods.
 They are used to aid in the processing of foods and also to
help maintain quality and freshness.
 In low fat spreads, emulsifiers can help to prevent the growth
of molds which would happen if the oil and fat separated. 133
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Foods that Commonly Contain Emulsifiers  Emulsifier, in foods, any of numerous chemical additives that
encourage the suspension of one liquid in another, as in the
Biscuits Toffees Bread mixture of oil and water in margarine, shortening, ice cream
and salad dressing.
Margarine / low fat
Extruded snacks Chewing gum
spreads  Closely related to emulsifiers are stabilizers, substances that
maintain the emulsified state.
Breakfast cereals Frozen desserts Coffee whiteners  The consistency of food products may also be improved by
the addition of thickeners, used to add body to sauces and
Cakes Ice-cream Topping powders
other liquids and texturizers.
Desserts / mousses Dried potato Peanut butter  This class of additives has a dual purpose: they make food
more appetizing by improving appearance and consistency
Soft drinks Chocolate coatings Caramels
and they augment keeping qualities (i.e., extend shelf life).

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 Emulsifiers perform many essential functions

in food products including:
 Stabilizers are chemicals that inhibit separation of
 Stabilizing emulsions suspensions, emulsions and foams.
 Securing the right mouthfeel and product  They are substances added to foods to preserve consistency
appearance or maintain a solution, mixture or suspension.

 Overcoming raw material variations  Stabilizers are food additives and are used by the food
industry for processed foods.
 Extending shelf life
 Stabilizers may for example inhibit the separation of emulsion
or to prevent the color of foods from changing.
 They may furthermore bind the suspended solids in a liquid
or maintain an acidic environment.
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 Whereas emulsifiers will actually link fat and water

 Antioxidants, preventing unwanted oxidation of materials.
together, stabilizers are large molecules that will
 Sequestrants, forming chelate complexes and inactivating
get in between individual particles contained within
traces of metal ions that would otherwise act as catalysts.
 Emulsifiers and surfactants, for stabilization of emulsions.
the dispersed phase, keeping them from coalescing
 Ultraviolet stabilizers, protecting materials, especially plastics,
(pooling together).
from harmful effects of UV radiation:  These "large molecules" can take the form of
◦ UV absorbers, chemicals absorbing ultraviolet radiation and proteins, starch, pectin, plant particles and food
preventing it from penetrating the materials; principally the same
as sunscreens.
grade gums.
◦ Quenchers, dissipating the radiation energy as heat instead of  Because most of these molecules are water
letting it break chemical bonds; often organic nickel salts, e.g.
soluble, they will usually be utilized with fat-in-water
nickel phenolates.
emulsifications.
◦ Scarvengers, eliminating the free radicals formed by ultraviolet
radiation; often hindered amine light stabilizers (HALS).
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 Examples of stabilisers are gelatine, pectin

and carrageenan.

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