3.

0 Lipids
 Introduction
 TAG & Fatty Acids
 Physical Properties of TAGs
 Functionality of Fats & Oils
 Mechanisms of Fatty Acid Oxidation
 Fat Replacers & Mimetics
……………. Continue ………….
 A lipid is any material from a biological source that
dissolves with organic solvents inlcuding hexane,
acetone or petroleum ether.

 There are 4 major classes of lipids:

 Triacyglycerols (TAGs) – calorie dense food material
 Sterol – cholesterol is an example of a steroid
 Phospholipids – Used as emulsifiers in food manufacturing
 Waxes – Esters of long chain alcohols and fatty acids
(coating in plant)
 Vitamins – Vitamin A, D, E and K are sometimes classed as
lipids
…………… Continue …………..
 Owing to their high degree of saturation, animal derived TAGs
tend to be fats whilst plant and fish derived TAGs are generally
oils.

 The major plant sources of oils are

 Legumes (soybean, sesame seed)
 Tree crops (palm, coconut)
OILs
 Oilseeds (rapeseed, cottonseed).

 Animal fats include

 Fish Oil
 Beef tallow @ rendering fat
 Butter fat FATs
 4.0 Lipids
 Introduction
 TAG & Fatty Acids
 Physical Properties of TAGs
 Functionality of Fats & Oils
 Mechanisms of Fatty Acid Oxidation
 Fat Replacers & Mimetics
 4.2 TAG & Fatty Acids
PO4 Phospholipids
C18

C18

C16

Fatty Acids – Carboxylic Acids Glycerols – 3 (OH) Triacyglycerols/

Triglycerides
+
Short COOH OH
Medium Edible Fat
Long C(O)O – Esterification (glycerol ester, 99%) & Oil
……………. Continue ………….
 The edible fats and oils we eat are triacylglycerols
(commonly called triglycerides).

 They are esters between glycerol (an alcohol with

three OH groups) and any three of several long-
chain carboxylic acids.

 Fatty acids are the carboxylic acids used to make

molecules of triacylgycerols.
C18:1; C18:1; C16:0
 Esterification has an impact on the stability of fats
and oils.

 Phospholipids resemble TAGs except that the 3rd Triglycerides

hydroxyl group (-OH) of glycerol is attached to
phosphate moiety which is then attached to a
further group
a. Fatty Acids
 Generally, FA can divided into 2 category:
 Saturated – no double bond
 Unsaturated – one or more double bond

 Unsaturated fatty acids also classed according to the

omega system.

 The omega number is the location of the first double

bond counted from the methyl (CH3) end of the fatty
acid chain.
Double No
 Most polyunsaturated fatty acids (PUFAs) lipids Double
contain either omega-3 or omega-6 fatty acids bond
(Eicosapentanoic acid, EPA and arachidonic acid). bond

Oleic acid
(18:1 cis ε-9)
…………... Continue …………..
 Alternative arrangements around a C=C double
bond lead to geometric isomers for unsaturated
fatty acids.
H H
 Cis (Z) fatty acids are the most common form of
fatty acids in nature. Unsaturated
 They can rearrange to form trans (E) fatty acids
during the hydrogenation of edible oils.

 Oleic acid (18:1 cis 9) gives rise to the trans fatty Trans
acid isomer elaidic acid (18:1 trans 9) during
partial hydrogenation of vegetables oil.

 Trans fatty acid has 2 hydrogen atoms on opposite

sites of the double bond but the cis fatty acid has 2
hydrogen on the same side. Cis
 4.0 Lipids
 Introduction
 TAG & Fatty Acids
 Physical Properties of TAGs
 Functionality of Fats & Oils
 Mechanisms of Fatty Acid Oxidation
 Fat Replacers & Mimetics
4.3 Physical Properties of TAGs
- Subtopic:

 Melting Point

 CS1 – Hydrogenation of Vegetables

 CS2 – Saponification of TAGs

 CS3 – Interesterification
                                           

a. Melting Point
 Melting point (MP) is one of the important
physical properties of TAGs.
H H
 The MP is the temperature at which a lipid
transforms from solid to the liquid state. Saturated

 The melting point of a fat is determined by the

type of fatty acid constituents and their position
on the glycerol backbone.
Trans
 Among variables affect the melting point of
pure fatty acids and TAGs are:
 Degrees of saturation (saturated > unsaturated)
 Geometric isomerism (trans > cis)
 Chain length (C10 > C8) Cis
…………. Continue …………..
Fatty acid Common Fatty Acids Structure
Melting Polarity
of carbon point (°C)
atoms

Myristic acid 14 CH3(CH2)12COOH 54

Palmitic acid 16 CH3(CH2)14COOH 63

Stearic acid 18 CH3(CH2)16COOH 70

Oleic acid 18 CH3(CH2)7CH=CH(CH2)7COOH 4

Linoleic acid 18 CH3(CH2)4CH=CHCH2CH=CH(CH2)7COOH -5

Linolenic acid 18 CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH -11

 ………….. Continue ………….
 During melting the ordered crystalline array of
TAG molecules is transformed into a
disordered, mobile, ensemble within a liquid
state.

 This requires an input of kinetic energy in the

form of heat.
Cis-9-octadecenoic
 The generally low melting point of cis fatty
acids is explained by the marked “kink” within
their structure.

 This irregular shape leads to inefficient

packing of cis fatty acids as compared with
trans fatty acids and saturated fatty acids
within a crystalline network Trans-9-octadecenoic
 ……………. Continue ………….
 Table 1. Temperature of Cocoa Butter Crystalline Forms

- α is the lowest melting point.

- For example, monoacid TAG (StStSt), is cooled from the melt, it crystallize in the
least dense, lowest melting point.
- Further cooling of the α form, the chain associates more compactly – gradual
transition into the β form take place.
- β’ (more stable than β)
CS 1: Hydrogenation of
Vegetable oils
 Vegetable oils (liquids) are generally less
expensive to produce than animal fats
(solids).

 Using hydrogenation, chemists can break

some of the carbon-carbon double bonds Hydrogenation Process
and replace them with hydrogen to make
them chemically identical to the
triacylglycerols in animal fats.

 Breaking one of the three double bonds in

the molecule above can make the product
melt above room temperature (25oC).
CS 2: Saponification of TAGs
 The hydrolysis of
triacylglycerol in the presence
of sufficient sodium hydroxide
is called saponification.

 The fatty acids are released

Na+
as sodium salts and the
mixture of these salts of long- Na+
chain fatty acids is soap.
Na+
CS 3: Interesterification
 Process changing the position of 1st
fatty acid radicals on the
glycerides in a fat/oil is known as 2nd
interesterification @ ester
interchange.
3rd

 In the present of certain catalyst, Interesterification

the fatty acid radicals can be
made to move between hydroxyl 2nd
positions so that an essential
random fatty acid distribution
3rd
results.
1st
 4.0 Lipids
 Introduction
 TAG & Fatty Acids
 Physical Properties of TAGs
 Functionality of Fats & Oils
 Mechanisms of Fatty Acid Oxidation
 Fat Replacers & Mimetics
4.4 Functionality of Fats and Oils
 Fats impart physical properties to foods and
thereby affect the sensory, nutritional, safety
and storage characteristics. C=C cis

 This section will focused on the texture of fats

as ingredients.
C=C trans
 The texture of a TAG depends on several
physical attributes, chief amongst which are the
melting properties and the solid fat content.

 Crystallization behaviour is affected by the ?

presence of different fatty acid substituents on
the glycerol backbone and the number of TAG
types present in different edible oils. compatible
 ………… Continue ………….
 When an oil solidifies, TAG
molecules having “compatible” fatty
acids may tend to co-crystallize.

 This leads to the formation of fat

crystal particles or crystallites
suspended in a melted oil Crystal nucleus
continuous phase.

 Interactions between dispersed

particles leads to a three-
dimensional fat crystal network Crystal
entrapping the liquid oil phase.
a. Plasticity
 A plastic fat flows when force is applied and regains
its original consistency when the force is removed.

 Another feature of a plastic fat (margarine, coconut

oil, palm oil) is its tendency to melt over a wide
temperature range.

 Plasticity ascribed to the presence of a mixture of

crystal polymorphs having different stability (Table 1)

 Nonplastic fats (cocoa butter) produce a sharp

melting transition from solid to liquid when heated
over a range of temperatures.
……………. Continue ………….
 Table 1. Temperature of Cocoa Butter Crystalline Forms

Polymorphs of Tm (oC) Storage stability

cocoa butter
VI 36.3 26oC, stable

V 33.8 16oC, 2-14 wks

IV 27.5 16oC, 2 days to 2 wks

III 25.5 10oC, 1-3 days

II 23.3 5oC, < 2h

I 17.3 0oC, 15 min

 ………….. Continue ………….
 The melting profile of plastic fats is broad whereas
non-plastic fats exhibit sharp melting profiles.

 Plasticity also refers to the property of a material to

undergo permanent deformation.

 For edible fats, this quality translates into

spreadability

 The spreadability of butter is associated with a

broad melting temperature range over which both
solid and liquid TAG fraction co-exist.
CS 1: Butter
 The plasticity of milk fat has received much
attention owing to its role as butter.

 At room temperature, butter must remain a

free standing solid and be spreadable with a
slight application of force.
Fat crystals
 The spreadability of butter is associated with
a broad melting temperature range over
which both solid and liquid TAG fractions co-
exist.
Oil Phase

 Plasticity is the result of an interacting 3-

dimensional network of fat crystals within a Solid Liquid
continuous oil phase.
 ……….. Continue …………
 Therefore, plasticity is affected by TAG Myristic Acid 54oC
composition.
Stearic Acid
CH3(CH2)16COOH
 The long chain saturated fatty acids
fraction is necessary for the plastic 70oC
behaviour associated with butter.
4oC
 Removal of saturated fatty acids (~20%
CH3(CH2)7CH=CH
total) from milk produces a pourable oil (CH2)7COOH
at room temperature. Oleic Acid
b. Shortening and Anti-Staling
 Shortening produces a tenderizing action on Fat
baked cereal products. Protein

 This effect arises when protein particles become

coated with fats, leading to interference with the Protein
Fat
gluten network formation.
Prevent association
 Fats and oils, as well as the breakdown products
(free fatty acids, mono- and di-acylglycerides), A A
interact with carbohydrates. FAT
A A
 Formation of the amylose-fatty acid complex
appears of moistness and help to maintain soft
crumb texture. Prevent hardness
 4.0 Lipids
 Introduction
 TAG & Fatty Acids
 Physical Properties of TAGs
 Functionality of Fats & Oils
 Mechanisms of Fatty Acid Oxidation
 Fat Replacers & Mimetics
4.5 Mechanisms of Fatty Acid
Oxidation
- Subtopic:

a. Factors that influence the rate of oxidation.

b. Antioxidants vs. Oxidation
c. Mechanisms of antioxidants
4.5 Mechanisms of Fatty Acid
Oxidation
 Lipid oxidation generally is caused by two types of reactions:
i. Auto-oxidation
ii. Photo-oxidation

 Auto-oxidation causes fats and oils to spoil and unsuitable for

consumption.

 Rancidity = process of auto-oxidation and the resulting

deterioration in flavour of fats and fatty foods.

 Auto-oxidation is divided into 3 parts:

i. Initiation
ii. Propagation
iii. Termination
Auto-oxidation - i. Initiation
 Hydrogen is removed at carbon next to
double bond.
Steal
Metals
electron
 Two free radical are formed.
H--------C=C--------H
 Initiated by light or metals.

 RH R. + H. Light Supply
energy
ii. Propagation
 Free radical combine with oxygen to form peroxy-
free radicals.
 R. + O2 RO2 .

 Peroxy-free radicals react with another unsaturated

molecule to produce another peroxide and a new
free radical.

 Chain reaction
. .
 RO2 + R=H ROOH + R
iii. Termination
 When free radicals react with themselves to
yield non-active products, i.e. ketones

R-CH-R + R . R-C-R + RH
O . O
- Non-active products from termination
- R. + R. RR
- R. + ROO . ROOR
. .
- ROO + ROO ROOR + O2
 ………… Continue …………..
 Hydroperoxides formed during
propagation are primary oxidation
products.
Oxygen Secondary
update products
 The oxidation products are unstable and
decompose into secondary oxidation
products which are responsible for the off
flavour.
Peroxides
Induction Primary
period products
 During the initiation process, the amount
of hydroperoxides increase slowly
(induction period).
 ………… Continue ………….

 After the induction period, there is a sudden

increase in peroxide content.
Oxygen Secondary
update products
 Peroxides are easy to determine
(peroxide value) – often used to
measure the progress of oxidation.
Peroxides
Induction Primary
 Hydroperoxides decompose to form alkoxy period products
and hydroxyl radicals.
.
R-CH(OOH)-R R-CH-R + OH
O.
Photo-Oxidation
 Oxidation of lipids can be caused
by at least two other mechanisms
i. Photo-oxidation
ii. Enzymic oxidation by lipoxygenase. O2
3
O2
1

 Light-induced oxidation @ photo-

oxidation results from the
reactivity of an excited state of Unsaturated
oxygen, known as singlet oxygen
1O .
2
146 – 273 92
kJ/mole kJ/mole
 Ground-state or normal oxygen is
triplet oxygen (3O2). > reactive
…………… Continue ………….
 Singlet oxygen is short-lived and reverts
Sensitizers
back to the ground state with the emission
of the light – fluorescent.
3
O2 1
O2
 Wavelength (λe) of the emitted light is
higher than absorb light (λa)(excitation). 146 – 273 92
kJ/mole kJ/mole

 E = hv; v = c/λ Emitted

light
 Sensitizers compound in foods: 3
O2
- Chlorophyll
- Myoglobin Absorb light
- Riboflavin
Oxidation products
………….. Continue ……………
Photo- Auto-oxidation
oxidation
1st Initiator Sensitizers Free radical

1st Substrate Oxygen (3O2) Lipid

2nd Initiator Singlet oxygen Peroxy free

(1O2) radical
2nd Substrate Unsaturated Unsaturated

Oxidation product Hydroperoxides; Off-flavour

compound
a. Factors that influence the
rate of oxidation
 Amount of oxygen.
Sensitizers
 Degree of unsaturation.
3
O2 1
O2
 Presence of antioxidants, i.e. vitamin E,
BHA and BHT. 146 – 273 92
kJ/mole kJ/mole
 Presence of prooxidants, i.e. copper,
heme compounds and iron. Emitted
light
 Nature of packaging materials.

 Light exposure.

 Temperature of storage.
Oxidation products
b. Antioxidants vs Oxidation
 Antioxidants are generally used to reduce auto-
oxidation and minimize oil and fat rancidity.

 Antioxidants = substances that can help retard

oxidation.

 Antioxidants are added into fats or fat-containing

foods to prolong the wholesomeness and palatability
of the food.
 ………….. Continue …………..
 An antioxidant should:

 Have no harm effect to the body.

 Not contribute any objectionable flavour, odour and colour.
 Effective at low concentrations.
 Fat soluble.
 Readily available.
 Able to resist processing.
 Economical.

 Most common antioxidants used in foods include

tocopherol, BHA and BHT.
c. Mechanism of Antioxidants
 Antioxidants function by interrupting free radical chain
mechanism.

 This process often require the antioxidants to take up

the free radical and become a harmless free radical
itself.

 Inhibitors of food oxidation include:

(1) Chelating agents which reduce the concentration of free
metal cations in solution.
(2) Free radical quenchers which form stable and less
reactive free radicals.
(3) Reducing agents (electrons donors).
(4) Agents that remove or reduce the concentrations of
oxygen and/or hydrogen peroxide.

 Antioxidants used in combination are often much better

than single antioxidant due to its synergistic effect.
…………… Continue ………….
 Schematic explanation of antioxidant (AH)
with auto-oxidation.

 R. + AH RH + A .
 RO . + AH ROH + A .
 ROO . + AH ROOH + A .
 R. + A. RA
. .
 RO + A ROA
 4.0 Lipids
 Introduction
 TAG & Fatty Acids
 Physical Properties of TAGs
 Functionality of Fats & Oils
 Mechanisms of Fatty Acid Oxidation
 Fat Replacers & Mimetics
4.6 Fat Replacers & Mimetics
- Subtopic:

a. Fat substitutes
(i) Olestra (Emulsifier)
(ii) Caprenin (Structured Lipid)

b. Fat Mimetics
4.6 Fat Replacers & Mimetics
 There are nearly 300 materials proposed as fat replacers which
include modified starches, fiber, gums, emulsifier, restructured
protein and cellulose.

 This section provides a brief overview of the fat replacers which

are either fat substitutes or mimetics.

 Fat substitutes are lipid-like substances intended to replace fats

on a one-to-one basis.

 Fat mimetics are protein or carbohydrate ingredients which

function by imitating the pyhsical, textural, mouthfeel and organic
properties of real fats.
 ……….. Continue ……………
Fat Replacers

Fat substitutes Fat mimetics

Microparticulate Microparticulate
Emulsifier Structured lipids
protein Carbohydrates
- Olestra - Caprenin
- Simplesse - Avicel
- Sucrose-FA - Solatrin
- Daily-Lo - Oatrim
a. Fat Substitutes
 The fat substitutes are intended to replace the
functionality of natural fats on a one-to-one weight
basis.

 Fat substitutes can divided into 2 group:

 Emulsifier
 Structured lipids

 Their functional role in foods for both Olestra

(emulsifier) and Caprenin (Structured lipids) will be
thoroughly discuss.
a (i) Olestra (Emulsifier)
 Olestra®, also known as Olean, is an emulsifier
produced by reacting sucrose with 6-8 moles of
C12 and C22 fatty acids in the presence of a
catalyst.

 Less completely esterified sucrose fatty acid

esters (2-3 moles of fatty acids) have been
produced which are hydrophobic and also more
digestible.
+
 Similar surfactants have been produced by
attaching a hydrophobic fatty acid to hydrophilic Sucrose/sugar alcohol
sugar alcohols.

 Sobestrin is produced by esterifying sorbitol.

Olestra Sobestrin
a (ii) Caprenin (Structured Lipids)
 Caprenin is a well known example of an
medium chain triacylglycerides (MCTs), in
which a glycerol backbone is substituted by
caprylic acid (C8:0), capric acid (C10:0) and
behemic acid (C22:0).

 This fat replacer yields 5 kcal/g as compared to

9 kcal/g for normal fat.

 MCTs have lower melting points, high solubility

in water and are resistant to oxidation.
C8:0 M
 The MCTs are not transferred to the body’s C10:0 C
store of adipose tissue but are metabolized C22:0 T
directly in the liver.

Caprenin
 ………… Continue …………..
 Therefore, the calorie reduction is apparently due
to the less efficient metabolism of C8:0 and C10:0 Vegetable Oil
fatty acids within the body.

Hydrolyzed
 To produce MFTs, ordinary vegetable oil is first
hydrolyzed and medium and short chain saturated
fatty acids are isolated by fractionation.
Isolated

 The medium fatty acid fraction is then reattached

to glycerol with the aid of a catalyst. MFTs

Reattached
 MFTs differ from natural fats by their relative glycerol
absence of long chain fatty acids.
Structured lipids
b. Fat Mimetics
 The fat mimetics are nonlipid compounds that are able to
stimulate the physical functionalities of fats, namely qualities
like creaminess and smoothness.

 Carbohydrate fat mimetics (Avicel®) include microparticulate

cellulose.

 These materials provide the mouthfeel and flow properties of

fat but are lacking the flavor characteristics associated with
edible fats.

 Microparticulate cellulose also retains moisture and acts as a

texturizer and stabilizer.

 Carbohydrate fat mimetics have been suggested as useful in

dairy products, sauces, frozen desserts and salad dressings.
…………. Continue …………….
 The microparticulated proteins include Simplesse®
(1-4 kcal/g) which is made from whey protein or milk
and egg protein.

 This material provides the mouthfeel of fat.

 The ingredient may be used in dairy products, salad

dressing, margarine and mayonnaise-type products,
baked goods, coffee, creamer, soups and sauces.

 FDA has granted both Oatrim and Simplesse GRAS

Learning Outcomes
 Students are able to:

 List out 4 major classes and 2 sources of lipid

 Differentiate molecular structure between TAG and
Fatty Acids
 Discuss in details both physically and functionality of
TAGs
 Identify factors that affect the lipid oxidation as well
as the mechanism involved in lipid oxidation
 Distinguish between fat substitutes and fat mimetics