Lipid

FST3107
 What are Lipids?
 Definition: ‘natural substances soluble in non-polar organic
solvent and insoluble in water’.
 However, exception to the definition are:
 Short chain fatty acids, that are water soluble c1-c3, c4)
 Trans-fatty acids
 Synthetic fat substitutes (olestra)
 FDA uses a definition based on total lipids expressed as
total triacylglycerides and expressed as calorific value,
avoiding inclusion of non-calorific fat substitutes
Classification of lipids
 Derived lipids: units from which larger lipids are built, examples fatty
acid and alcohols
 Simple lipids: hydrolyzed to 2 components, usually alcohol and acid.
Examples acylglycerols, ether acylglycerols, sterols, sterol waxes and
wax esters
 Complex (conjugated) lipids: hydrolyzed to 3 or more components
glycerophospholipids (phospholipids), glyceroglycolipids (glycolipids) and
sphingolipids
Classification Scheme
Lipids
Complex Derived
Simple
1. Wax esters 1. Fatty acids
2. Sterol esters 2. Sterols
3. Triacylglycerol Phospholipids
Glycolipids
1.Cerebrosides
2.Gangliosides

Glycerophospholipids Sphingolipids
1.Phosphatidylcholine (PC) 1.Ceramides
2.Phosphatidylethanolamine (PE)
3.Phosphatidylinositol (PI) 2.Sphingomyelin
 LIPID COMPONENTS
Major lipid components Minor lipid
(~99% of fat components) components

Fatty acids Sterols

Acylglycerols (glycerides) Tocopherols
Phosphoacylglycerosl (phosphatides) Waxes
Pigments
Hydrocarbons
Glucosides
Vitamins

5
1. Fatty Acid
 Nomenclature:
 IUPAC convention: fatty acid (FA) or free fatty acid (FFA) are

named after the parent alkane

 Examples: octadecane and octadecanoic acid

 Double bond designation used the ∆ symbol to represent the carbon

number from the carboxyl group, with the carboxyl carbon being #1.
 A double bond between carbon 9 and 10 would be a ∆9 bond, e.g.
∆9 octadecanoic acid, ∆9,12 octadecadienoic acid and ∆9,12,15
octadecatrienoic acid
 Fatty acids

 Cis (c) and trans (t) conformations are expressed:

 Example as c 9 octadecaenoic acid

 All natural occurring fatty acids are cis

 Common or trivial names exist for many fatty acids:

 E.g.

 oleic acid =

 Linoleic acid

 Linolenic acid

 Formic acid

 Acetic acid
Fatty Acid Structure

=O
-H

-H
H - C - ( C )n - C - OH
-H

-H
Carboxyl
group
Methyl Carbon
group group(s)
Fatty acids
 Shorthand (n or 𝜔𝜔):
 The number of carbons in the chain is followed by colon, the number

of double bonds, followed by the number of the double bond closet to

the methyl end of fatty acid
 Carbons are numbered from the methyl (𝜔𝜔) end of the molecule

 The letter 𝜔𝜔 is often replaced with n

 Types of fatty acids
1. Saturated fatty acids: smaller molecular weight species are water soluble
but decrease in solubility as size increases
2. Unsaturated fatty acids: monounsaturated are most ∆9 (oleic acid).
Polyunsaturated fatty acids (PUFA), many of which are nutritionally
essential e.g. linoleic acid
3. Acetylenic fatty acids: ynoic acid or diynoic acid suffix with a denoting
acetlylenic bond, generally at ∆9 but these compounds are rare. E.g.
octadecynoic acid
4. Trans fatty acids: originates from bacteria, oil steam deodorization and oil
hydrogenation with nutritional consequences on biological function when
incorporated into nervous tissue
5. Methyl branching: occurs on the 𝜔𝜔2 carbon e.g. isoprenoid/terpenoid
biosynthesis pathways
Saturated Fats
 All the chemical bonds between the carbon are single bonds
C-C-C-
 No double bonds
 No space for more H atoms; fully “saturated”
 Solid at room temperature
 Butter, shortening, lard, coconut oil, palm oil, and fully hydrogenated
vegetable oils
 Poultry skin, whole milk
Poly-Unsaturated Fatty Acids
 Two or more double bonds
 Include omega-3 and omega-6 fatty acids (essential fatty
acids)
 Linolenic acid: omega 3 fatty acid
 Linoleic acid: omega 6 fatty acid
 Richest sources of poly-unsaturated fatty acids include:
 Vegetable oils
 Corn, sunflower, safflower, cotton seed oils
Fatty-acid Nomenclature
 Named according to
chain length
 C18
H2 H2 H2 H2 H2 H2 H2 H2
H3C C C C C C C C C O
C C C C C C C C C
H2 H2 H2 H2 H2 H2 H2 H2 OH
Fatty-acid Nomenclature
 Named according to the number of
double bonds
 C18:0

H2 H2 H2 H2 H2 H2 H2 H2
H3C C C C C C C C C O
C C C C C C C C C
H2 H2 H2 H2 H2 H2 H2 H2 OH

Common name:
Stearic acid
Fatty-acid Nomenclature
 Named according to the number of
double bonds
 C18:1
H2 H2 H2 H H2 H2 H2 H2
H3C C C C C C C C C O
C C C C C C C C C
H2 H2 H2 H2 H H2 H2 H2 OH

Common name:
Oleic acid
Fatty-acid Nomenclature
 Named according to the number of
double bonds
 C18:2
H2 H2 H H H2 H2 H2 H2
H3C C C C C C C C C O
C C C C C C C C C
H2 H2 H H2 H H2 H2 H2 OH

Common name:
Linoleic acid
Fatty-acid Nomenclature
 Named according to the number of
double bonds
 C18:3
H H2 H H H2 H2 H2 H2
H3C C C C C C C C C O
C C C C C C C C C
H2 H H H2 H H2 H2 H2 OH

Common name:
Linolenic acid
Fatty-acid Nomenclature
 Named according to the
location of the first double bond from
the non-carboxyl end (count from the
methyl end)
 Omega system (e.g., omega 3, ω3)
 n–system (e.g., n–3)
H H2 H H H2 H2 H2 H2
H3C C C C C C C C C O
C C C C C C C C C
H2 H H H2 H H2 H2 H2 OH
Fatty-acid Nomenclature
H2 H2 H2 H H2 H2 H2 H2
H3C C C C C C C C C O
C C C C C C C C C
H2 H2 H2 H2 H H2 H2 H2 OH
Omega 9 or n–9 fatty acid

H2 H2 H H H2 H2 H2 H2
H3C C C C C C C C C O
C C C C C C C C C
H2 H2 H H2 H H2 H2 H2 OH
Omega 6 or n–6 fatty acid

H H2 H H H2 H2 H2 H2
H3C C C C C C C C C O
C C C C C C C C C
H2 H H H2 H H2 H2 H2 OH
Omega 3 or n–3 fatty acid
Fatty Acid Synthesis Issues
Ω-3 Ω-6 Ω-9
C-C-C=C-C-C=C-C-C=C-C-C-C-C-C-C-C-COOH

 Animals can synthesize a fatty acid with a

double bond in the omega 9 position but not
at either 3 or 6 positions
 Omega-3 and omega-6 fatty acids must be
derived from diet
 Cold water fish accumulate high levels of
omega 3 fatty acids from their diet
 Omega System and
Essential Fatty Acids
 Linoleic acid is an omega-6 fatty acid
 Linolenic and arachidonic acids are omega-3 fatty
acids
 Linoleic and linoleic acids are essential fatty acids
 Arachidonic acid can be synthesized from linoleic acid, so
not essential
Melting Points
 Affected by chain length
 Longer chain = higher melting temp

Fatty acid: C12:0 C14:0 C16:0 C18:0 C20:0

Melting point: 44°C 58°C 63°C 72°C 77°C

Which fatty acids are liquid at room temperature?

Which fatty acids are solid at room temperature?
Chain Length
 In most fats with a mixture of fatty acids, the
chain length of the majority of fatty acids will
determine the “hardness” of the fat
 <10 carbons = liquid
 Between 10 and 20 carbons = ???
 >20 carbons = solid

Acetic Acid (2 C) Vinegar Liquid

Stearic Acid (18 C) Beef Tallow Solid

Arachidic Acid (20 C) Butter Solid

Melting Points
 Affected by number of double bonds
 More saturated = higher melting temp

Fatty acid: C18:0 C18:1 C18:2 C18:3

Melting point: 72°C 16°C –5°C –11°C

Which fatty acid is liquid at room temperature?

Which fatty acids are solid at room temperature?
Fatty acids

 Because of the presence of double

bonds, unsaturated fatty acids are
more reactive chemically than are
saturated fatty acids.
 This reactivity increases as the
number of double bonds increases.
 Although double bonds normally
occur in a non-conjugated position,
they can occur in a conjugated
position (alternating with a single
bond) as illustrated below
Isomerism of Unsaturated Fatty
Acids

 Isomers = compounds having same

molecular formula & molecular weight
(MW), different in structure
 Two important types of isomerism among fatty acids:

A. Geometric
B. Positional

30
A. Geometric Isomerism
• Cis or trans form, depending on
configuration of the hydrogen atoms
attached to the carbon atoms joined by
the double bonds kink/bent

• Cis isomers are those naturally

occurring in food fats and oils
• Trans isomers occur:
• naturally in ruminant animals e.g. cows,
sheep and goats, and
• Partial hydrogenation of PUFAs

31
  E.g. Elaidic and oleic acids

• Packing
• Melting
• Solidification

Cis-9-Octadecenoic acid (oleic acid)

Trans-9-Octadecenoic acid (elaidic acid)

Trans configuration melts at higher

temperature, cis normally in liquid state at
RT 32
 B. Positional Isomerism
 The location of the double bond differs among the isomers.

 Petroselinic acid, which is present in some animal and vegetable fats and
oils, is cis-6-octadecenoic acid and a positional isomer of oleic acid, cis -9-
octadecenoic acid.

 Vaccenic acid, which is a minor acid in tallow and butterfat, is trans-11-

octadecenoic acid and is both a positional and geometric isomer of oleic
acid.

33
Cis-9-Octadecenoic acid (oleic acid)

Petroselinic acid = cis -6-

octadecenoic acid; 18:1 cis-
6

trans -11-octadecenoic acid (oleic acid)

Cis -11-octadecenoic acid (oleic acid)

34
PHYSICAL PROPERTIES OF TRIACYLGLYEROLS

 depend primarily on the molecular structure,

interactions, and organization of the triacylglycerol
molecules
 the strength of the attractive interactions between the
molecules and the effectiveness of their packing
within a condensed phase largely determine their
thermal behavior, density, and rheological properties
PHYSICAL PROPERTIES OF TRIACYLGLYEROLS
a.rheological properties

 Most liquid triacylglycerol oils are Newtonian liquids with viscosities between ~30 and
60mPa.s at room temperature
 viscosity of liquid oils tends to decrease steeply with increasing temperature and can
be conveniently described by a logarithmic relationship.
 “solid fats” actually consist of a mixture of fat crystals dispersed in a liquid oil matrix
 Solid fats normally exhibit a type of rheological behavior known as “plasticity.”
 A plastic material behaves like a solid below a critical applied stress, known as the yield
stress (τ0), but behaves like a liquid above this stress.
 Important implications of the products
PHYSICAL PROPERTIES OF TRIACYLGLYEROLS
b.Density

 density of a lipid is the mass of material required to fill a given volume

 important when designing food processing operations, since it
determines the amount of material that can be stored in a tank or flow
through a pipe of a given volume
 certain food applications because it influences the overall properties of
the system, for example, the creaming rate of oil droplets in oil-in-water
PHYSICAL PROPERTIES OF TRIACYLGLYEROLS
c.thermal properties

 most important thermal properties of lipids from a practical standpoint

are the specific heat capacity (CP), thermal conductivity (κ), melting
point (Tmp), and enthalpy of fusion (ΔHf)
 knowledge of the temperature at which a lipid starts to breakdown due
to thermal degradation is important, for example, frying or grilling.
 thermal stability of lipids can be characterized by their smoke, flash and
fire point
Composition of fats & oils  Several general trends:

 Cocoa butter, coconut oil: triacylglycerols high in saturated FA

 Coconut & palm oils – high medium chain FAs (8:0 to 14:0,
predominantly 12:0)
 Most vegetable oil (esp. oilseeds) – highly unsaturated,
primarily FAs with C18
 Oils high in oleic – canola, olive

 Oils high in linoleic – soybean, corn

 Oils high in linolenic – linseed

39
Acylglycerols (glycerides)
Over 99% of FAs are esterified to glycerol  acylglycerols -
decreased cytotoxicity, modify surface activity

“Free OH
groups”  polar
 emulsifier

(A) Triacylglycerol
(B) 1,2-diacylglycerol
Partial glycerides : short chains are
(C) 1,3-diacylglycerol strongly polar than long chains
(D) 3(l)-monoacylglycerol 40
 Mono- and Diacylglycerols
 Very minor amount; can be considered as:

 A tracer of a not fully completed biological triacylglycerols synthesis

(unripe fruits, seeds)

 Sign of hydrolysis (enzymatic) (deteriorating fats)

 Liquid or solid depending on FA compositions

 Can be commercially prepared: esterification

 Affinity for both water and non-polar substances  emulsifiers

 Higher vapor pressure than TAG  distillation process

41
 Any monoacylglycerol is either a 1-
monoacylglycerol or a 2-monoacylglycerol
 Diacylglycerols can also have many other
combinations of fatty acids attached at either the
C-1 and C-2 positions or the C-1 and C-3
positions

42
 Fats & oils are composed of mixed
triacylglyceroles

Fatty acids located at different positions on glycerol

molecules, thus fat may contain different
triacylglocerols

43
Stereospecific numbering (sn system)

44
Positional distribution of fatty acids:
Plant triacylglycerols:

 Preferential placement of unsaturated fatty acids at sn-2 position; usually

linoleic acid

 Saturated acids, exclusively at 1,3 positions

 Individual saturated and unsaturated FAs equally distributed at sn-1 and sn-3

Animal triacylglycerols:

 Saturated acid at sn-2

 16:0 acid preferentially esterified at sn-1, 14:0 at sn-2 position

 Short-chain FAs selectively at sn-3

45
 PUFA at sn-2
Phosphatides / Phospholipids / Phosphoglycerols
 Ester of glycerol with phosphate group; consist of alcohols
(usually glycerol, fatty alcohol), FAs, orthophosphoric acid,
nitrogen-containing compound
 In crude vegetable oil: 0.1 – 3.0%
 Oil insoluble; co-extracted as micelles with
triacylglycerols (during refining)
 Phosphorus content  quality of fats and oil
 Amphipathic molecules = Emulsifier

46
47
 Classified into 5 main groups, based on the nature of
substituents on the glycerol-phosphoric acid:

 X = H, phosphatidic acid

 X = CH2CH2N(CH3)3, phosphatidyl choline (lecithin)

 X = CH2CH2NH2, phosphatidyl ethanolamine (cephalin)

 X = CH2CH(NH2)COOH, phosphatidyl serine

 X = inositol, phosphatidyl inositol

Different charges as a
function of pH 
solubility  removal
method

48
phosphatidyl ethanolamine

49
 Non-hydratable phosphatides = Ca and Mg
salts of phosphatidic acids
 Less hydrophilic  less easily removed

50
MINOR COMPONENTS OF LIPIDS
Minor lipid components
Free fatty acids
Alcohols
Sterols
Tocopherols
Waxes
Pigments
Hydrocarbons
Glucosides
Vitamins
51
Free Fatty Acids
 Non-esterified fatty acids

 Some unrefined oils may contain as much as several

percent free fatty acids.

 The levels of free fatty acids are reduced in the refining

process - only a few hundredths of one percent.

 FFA levels  fats & oils quality

52
Fatty Alcohols Dodecanol

 Primary long carbon chain alcohols can be derived

from FAs by converting COOH group to a
hydroxymethylenic (CH2OH)
 Little importance in most edible fats; lauryl, steryl
(commercially important) ; amphipathic
 Larger quantities are found in some marine oils.
 Fatty alcohols = 4-6 carbons, and up to 22 C atoms
(colorless oily liquids)
 Wax alcohols = those with longer chains (usually
waxy solids)

53
 Sterols
 Basic sterol structure = steroid alcohol; condensed four-ring system with
17 C atoms

 Found in both animal fats and vegetable oils - a substantial difference

biologically between the two; cholesterol & phytosterol (campesterol,
sitosterol, stigmasterol)

 Fat soluble. Levels = 0.05 – 0.6%; extreme range = 0.6-1.7% in corn germ
oils

54
Substitution at the skeleton by one OH and one or more methyl
and side-chain alkyl groups, together with some unsaturation
causes the main differences between the different classes of sterols

55
Sterol ester formed when the OH group of a sterol
and a fatty acid undergo an esterification reaction

Rice bran oil is a rich source of

esters of ferulic acid and a
mixture of sterols and
triterpenols = “γ-orizanol'’

Sterol glucosides: hydroxyl group at C3 on the

sterol is linked to the sugar by a glycosidic bond

56
Tocopherols and Tocotrienols
 Basic structure: tocol molecule, a chromo structure
containing a farnesyl side chains, substituted by 1,2,
@ 3 methyl groups

• Proportions may
change during
processing, storage 57
 Members of vitamin E, fat-soluble antioxidants
 Alpha-tocopherol has the highest vitamin E activity and the
lowest antioxidant activity.

 May be partially removed by processing.

 Not present in appreciable amounts in animal fats.
 Added after processing to improve oxidative stability in
finished products.

58
 Pigments
 Carotenoids, chlorophylls, gossypol
 Carotenoids - color from yellow, orange to deep red.
 Chlorophyll - green coloring matter of plants
 Levels of most of these color bodies are reduced during the normal processing of oils
to give them acceptable color, flavor, and stability.

59
Oxidized (acid,
T > 150ºC) 
bleaching of
color
 Bleaching
earth,
activated
carbon

60
 Glucosides
 Ethers of mostly monosaccharide tetrosid, pentosid, hexosid sugars with a
non-sugar component
 Many oil-bearing seeds and fruit parts contain glucosides; e.g. amygdalin
 Esterification of glucosides by FA via OH groups (e.g. sterol &
diacylglycerol glucosides)  oil insoluble = separation via
HYDRATION
 Often found together with lecithin sludges (degumming process)
 Sterol glucosides (e.g. saponin): surface active

61
 Vitamins
 Most fats and oils are not good sources of vitamins
other than vitamin E.
 The fat-soluble vitamins A and D sometimes are
added to foods which contain fat – margarine & milk.

62
FACTORS AFFECTING PHYSICAL CHARACTERISTICS OF FATS
AND OILS
 Physical characteristics of a fat or
oil:
 Degree of unsaturation
 Length of carbon chains
 Isomeric forms of fatty acids
 Molecular configuration
 Type and extent of processing

Physical and chemical characteristics (e.g.

liquid vs. solid, melting point, solidification, iodine value
 FINAL QUALITY ATTRIBUTES)
63
 Unsaturated fatty acids Saturated fatty acids
Liquid at room temperature, Solid at room temp
refrigerated, frozen storage (not necessarily true, e.g. coconut
(not necessarily true, e.g. linseed oil)
oil)
Melting point (MP) increase with: Higher melting point
• chain length,
• positional isomerism,
• trans isomerism (e.g. oleic v
elaidic acids),
• conjugation
MP decreases with number of 10 carbons chain length: liquid
double bonds, esterification of the > 10Cs: MP increases  solid
acid group

Packing of FAs: Trans configuration higher MP than cis

• MP for oleic (5ºC) vs elaidic (44ºC)
64
 Fatty acids determine the characteristics of the fat
 CHAIN LENGTH
 Short chain = less than 6 carbons
 Medium chain = 6-10 carbons
 Long chain = 12 or more carbons
 The shorter the carbon chain, the more liquid the fatty acid is

COOH
liquid at
COOH
room temp

COOH

COOH
semisolid at
room temp
COOH

COOH

COOH
solid at
COOH room temp

COOH
65
Greater number of double bonds, FA molecule more bend,
weaker VDW
66
 Packing of FAs: Trans configuration higher melting
point (MP) than cis
• MP for oleic (5ºC) vs elaidic (44ºC)
 Higher MP for straight chain FA than branched FA
 Higher MP for TAG with more symmetrical
distribution of FAs on glycerol molecule

Temperature at which TAG melts depends on

PACKING of the molecule in CRYSTALS

67
Molecular Configuration of
Triacylglycerols
 The molecular configuration of triacylglycerols can also affect the
properties of a fat or oil.
 Triacylglycerol = ‘turning-fork’ structure

68
Variety of different structural organization (solid
and liquid states), depending on molecular
characteristics (chain length, degree saturation,
polarity)

Crystal structure of oleic

acid 69
 Polymorphism of Fats

 Fatty acid chains tend to orient and align, and maintain this
orientation as temperature is decreased below the melting point 
formation of CRYSTALS
 Type of crystal formed depend on molecular structure & composition
of lipids, cooling rate, presence of nuclei, holding temperature, shearing
Cooling liquid oil (rapid vs. slow rate):

1. Small crystals vs. large crystals

2. Solid solution (homogenous crystals) vs. mixed crystals (heterogenous
crystals)
70
71
 Solidified fats exhibit POLYMORPHISM, i.e., they can exist in several
different crystalline forms, depending on the manner in which the molecules
orient themselves in the solid state

 POLYMORPHISM: Crystalline phases differ in structure, similar chemical composition,

identical liquid phase

 Crystalline structure with different molecular packing (hexagonal, orthrombic,

triclinic)

 Three fundamental polymorphs : α, β’ and β.

 Thermodynamic stability & melting point decrease in order of, β > β’ > α

72
Greater stability derived from greater PACKING
DENSITY of fatty acyl groups, and favored by
HOMOGENITY among constitutive fatty acids

73
Crystals formed affect physicochemical
properties of fats & final product properties

74
 TAGs often crystallize in the alpha (α) crystal form initially

 The CRYSTALS forms of fats CAN TRANSFORM from

lower melting to higher melting crystals.

 The rate of transformation and the extent to which it

proceeds are governed by:

 Molecular composition and configuration of the fat

 Crystallization conditions

 Temperature and duration of storage

75
 Fats that tend to crystallize in:

 β forms; soybean, olive, corn, cocoa butter, lard

 β’ forms; cottonseed, palm, rapeseed, milk fat, beef fat (tallow), salmon,
butterfat

 Hydrogenation and esterification can be used in a controlled manner to

produce fats and oils with different melting and crystal habits to fit demands
for a wide variety of food uses

76
Crystal structure are important  affect physicochemical
properties of fats & final product properties

α-crystal Β’-crystal β-crystal

Partially coalesced α- Fine, tiny needles crystal (1 Large crystals:
crystals and ice micron) • required for flakiness
crystals surrounding  shiny surface of (e.g. bakery
air bubbles forming chocolate, confections, shortening, e.g. lard)
network   smoothness, gloss in • Cocoa butter stability
structure and margarine, spreads in chocolate
texture of ice cream  Plasticity for margarine,
shortening, baking fats
Chains are perpendicular to Clumps are responsible
each other  can for grainy, sandy texture
incorporate large amount of
tiny bubbles in interstitial
spaces
77
α-crystal Β’-crystal β-crystal
Cocoa butter replacers Tempering is required
(CBR) and cocoa butter for β form, which is
substitutes (CBS) can used for chocolate,
crystallize (upon simple cocoa butter, and cocoa
cooling) into B’ crystals butter equivalents (CBE)
without tempering

Responsible for white

bloom in chocolate

78
 The crystals in the solid phase are not fixed, but are
able to slide by one another. This results in PLASTICITY,
the ability of a fat to flow when external force is applied

 The balance between two phases is critical

 Too much crystals  hard brittle fat with no plasticity
 Too little crystal s fat which flows(melts)
 This limits give useful temperature range for each
fat & designing shortening etc.

 Plasticity of a fat depends on:

1. Amount of solids (crystals) at given temperature
2. MP of component triglycerides
3. Polymorphic form of component triglycerides

79
 Plastic Non-plastic
 Many fatty acids, wide  Fatty acids few in number and similar length
melting point range,  Very narrow melting point range
workable over wide  Stays hard and solid at temperature below
temperature range mp
 Melts fast when mp reached

• All shortenings and solid fats are mixtures of crystallized fractions (10-30%) dispersed
in liquid fractions
• Proportion of solid to liquid fat controls texturization (e.g. stiffness and run) and
perceived consistency 80
 Fat phase transition

In practice, solid
Sharp melting, fat content, or

Solid fat content (%)

narrow range the proportion of
(e.g. butter oil) fat crystallized,
will vary 10 to
30%

Mixture of triacylglycerols
(e.g. lard, vegetable
shortening)  Broad melting
range: desirable PLASTIC
properties

A solid fat can be visualized as a mass of interlocking

crystals (solid phase) entrapping a liquid phase

81
Melting points of the most stable polymorphic forms of
selected triacylglycerol molecules

Melting point of
TAG depends on:
chain length,
chain branching,
degree of
unsaturation of its
constituent FAs,
relative position
along glycerol
molecule
L = Lauric acid, C12:0,
M = Myristic acid, C14:0;
P = Palmitic acid, C16:0,
S = Stearic acid, C16:1;
O = Oleic acid, C18:1;
Li = Linoleic acid, C18:2;
Ln = Linolenic acid, C18:3
82
A. Reactions which modify properties of lipid

IMPORTANT REACTIONS OF LIPIDS

Modification of fats and oils
 Fats have the ability to enhance the
palatability of foods
 Because of this there is a great emphasis on
the crystallization and melting behavior of
fats
 Unique fatty acid distribution of some natural
fats makes them undesirable for certain
applications
Modification of fats and oils
 Common processes for modifying lipids
 Blending

 Dietary interventions

 Genetic manipulation

 Fractionation

 Interesterification

 Hydrogenation
 Modifications of fats & oils
 Modification methods
 Hydrogenation
 Interesterification
 Fractionation
 Winterization

 Consistency, melting point, enhancing oxidative stability

 Development of fats and oils products for various product
applications

 May be performed before/ after deodorization, steam refining,

or blending 86
Modification of fats and oils

 Modified in order to change the solid fat content (SFC) of

lipids
 The fraction or percentage of a lipid that is solid at a

given temperature
 Enables less expensive lipids to be used

 Can reduce unsaturation, reducing susceptibility to

oxidation
 Can also increase unsaturation, potentially increasing

nutritional quality
Typical fats and oil processing
Hydrogenation
Liquid  plastic form, melting, oxidative
stability

• E.g. hydrogenation of oleic acid

into stearic acid

• Products: margarine, shortenings

89
 The degree of hydrogenation of unsaturated oils controls
the final consistency of the product; liquid, semi-solid, solid

Partial hydrogenation vs. complete hydrogenation

90
Steps in the hydrogenation of a C=C double bond at a catalyst surface
(Ni, nickel, sulfur-treated @copper chromite):

1. The reactants are adsorbed on the

catalyst surface and H2 dissociates.

2. An H atom bonds to one C atom.

The other C atom is still attached to
the surface.

3. A second C atom bonds to an H

atom. The molecule leaves the
surface.

Competition for catalyst surface

vs. selective hydrogenation

91
 Interesterification
E.g. Oil for deep frying, margarine with low trans fat

Name the fatty acids at sn-2 ?? 92

Interesterification process
 Chemical interesterification / rearrangement

 Random

 Directed

 Enzymatic interesterification

93
 Interesterified products

 Usually combined with other processing

techniques; hydrogenation, fractionation
 As basestocks for blending
 Development of specialty fat and oil products
 Interesterification may rise, lower or have no
effect on melting point
94
SFC
/
SFI

95
Solid Content Index of Cocoa Butter before and
after Interesterification

Before interesterification

After interesterification
 Fractionation  different melting
points
Filtration /
1. Dry fractionation;
Nuclei for centrifugation
CRYSTALLIZATION / hydraulic (winterization,
press dewaxing,
SEPARATION hydraulic
Cooling of oil
Growth of fat of solid (fat
to pressing, crystal
crystals crystals) and
supersaturation fractionation)
liquid phases
2. Solvent
fractionation
3. Aqueous
detergent
• Palm stearin & palm olein; Cocoa butter equivalents / substitutes fractionation
• Cooling rate / method  crystal form, size, separation efficiency
• Decreasing rate of crystallization : α > β’ > β
97
 Blending
 Basestocks are blended to produce various fat
and oil products with specified
composition, consistency, and stability
 e.g. shortening, frying fats, margarine oils, salad
oils, specialty products

 Consistency controls: e.g. evaluations for

solids fat index, iodine value, melting points,
fatty acid composition, etc.

98
Plasticization
 Development of the desired edibility,
appearance, stability, texture, etc, in
solidified fat and oil products via
controlled crystallization / plasticization

 Shortening, margarine, other solidified fat

and oil products  PLASTIC SOLID

99
β’-crystals : preferred for most
plastic shortening and
margarines esp. for creaming,
baking performance

How do we formulated soybean oil

products (β-forming products) with
wide plastic range ? 100
PRODUCTS PREPARED FROM FATS
AND OILS
 Salad and Cooking Oils
 Shortenings (Baking and Frying Fats)
 Hard Butters
 Margarine and Spreads
 ‘Butter‘
 Dressings for Food
 Toppings, Coffee Whiteners,
Confectioners Coatings, and Other
Formulated Foods
 Lipids for Special Nutritional
Applications
 Vanaspati
101
Shortening vs. Margarine vs.
Butter ???

102
103
104
Shortening
 Shortening: vegetable fat (100%
fat); exception puff-pastry and roll-in
shortenings may contain moisture
 Different types of shortenings for
specific food products
 Various forms; plasticized, liquid,
flakes, chips, powdered 105
 How to obtain right properties / performance
of shortening?
Influences consistency, crystal
structure, and performance

Modification
& blending of Plasticization Filling Tampering
oils / fats

1. Solidification :
usually shock-
chilling
process
2. Working @
crystallization
106
unit
 Wide plastic range bakery shortening

Unemulsified Emulsified

General-purpose Cake and icing shortening

shortening
Cookie shortening Icing & filling shortening
Cookie filler shortening Yeast-raise shortening
Pie crust shortening Specialty cake shortening
Biscuit shortening Mix shortening
Donut shortening
Danish roll-in shortening
Puff paste shortening
107
 Margarine
 Margarine: Plastic or liquid emulsion containing not
less than 80% fat: water-in-oil emulsion
 Blending fats and oils (vegetable oils, animal fat, marine
oil) – neutral @ modified
 Margarine oil formulation with unmodified oils /
hydrogenated oils / interesterified oils different
consistency, oxidative stability

108
109
110
111
Fats & Oils Analysis

112
113
114
A. Reactions which lead to the degradation of lipids

IMPORTANT REACTIONS OF LIPIDS

1. Oxidation (oxidative rancidity)
 General description
 Atmospheric oxidation of fats and oils
 General reaction characteristics
 Autocatalytic
 Has an induction point
 Accelerated by metals, light, and temperature
 Surface dependent
 Unsaturation dependent
 Produces a variety of oxidation products
Deterioration reactions
 Mechanism of lipid oxidation
 Free radical chain mechanism
 Initiation
Alkyl radical
RH R· + H·

 Removal of a H atom from a C adjacent to a double bond

 H atom is usually from the methylene group
 Example:

R-CH=CH-CH2-R’ R-CH=CH-C·H-R’

Methylene group
Deterioration reactions
 Propagation
 Alkyl radical (i.e. fatty acid free radical) combines with O2 to

first form peroxy radical

Peroxy radical: initial product during propagation

R· + O2 ROO·

 Peroxy radical then combines with fatty acid to form

hydroperoxide and another alkyl radical

ROO· + RH ROOH + R·
Hydroperoxide
Deterioration reactions
 Termination
 Reaction of 2 radicals, resulting in a non-propagating product

R · + R· RR

ROO· + ROO· ROOR + O2

RO· + R· ROR

ROO· + R· ROOR

2RO· + 2ROO· 2ROOR + O2

Deterioration reactions
 Nutritional implications of oxidation
 Loss of β-carotene (provitamin A)
 Loss of fat-soluble vitamins (A, D, E, K)
 Loss of essential fatty acids
 Possible build up of polymeric material
 Loss of protein quality
 Free radicals will react with protein
 Carbonyl-amine reactions (i.e. Maillard browning reaction)
 Other implications
 Loss of color and flavor = shelf life limitations
 Warmed over flavors in refrigerated foods
 2. High heat (frying)
 Lipolysis in heated fats – deep fat frying
 Usually at temperatures > 180ºC
 Results when oil is reused
 Moisture from food can cause hydrolysis (i.e.
lipolysis)
 Causes color changes (i.e. darkening) , an
increase in viscosity, a decrease in smoke point,
and potentially toxic products
3. Saponification
 Hydrolysis with a strong base
 Triglycerides split into glycerol and the salts of fatty acids
 The salts of fatty acids are “soaps”==formation of soaps
 Alkali soaps eg Na and K
 Critical reaction in food oil processing; removes free fatty acids and other
non-triglycride contaminants during refining
 Detrimental when occurs in food; leads to foaming, soap formation and off
flavors
4. Lipid hydrolysis
 Lipid are hydrolyzed by fat-splitting enzymes (lipases),
by water, heat, strong acid or alkali to glycerol and
fatty acids
 Unpleasant odors result from the short chain fatty
acids (c4-c10) which are volatile
Antioxidants
 General definition
 Substances that slow or prevent oxidative reactions
that would result in undesirable changes
 Examples: the development of off-flavors, discoloration,
and loss of nutritive value
 Antioxidants
 Synergists
 Oxygen displacers (e.g. inert gases)
 Protective coatings
 Antioxidants
 Major antioxidants used in foods

2 and 3-tert-butyl-4-hydroxyanisole butylated hydroxytoluene

propyl gallate
 Functions of Lipids
• Insulation
• Cushion around critical organs
• Provides energy (adipose cells = compact energy
storage)
• Protein-sparing
Characteristics Of Food
• Part of all cell membranes
Fat Sources
• Transport of fat-soluble vitamins
• Essential fatty acids Visible Fat
In food, fat enhances: .Butter, margarine, salad
oils and dressing,
• Taste
• Smooth shortening fat meat
• Flavor
texture
• Aroma
• Creamy Invisible Fat
• Crispness
feeling
• Juiciness .Cheese, cream portion of
• Feeling full homogenized milk, egg
• Tendernes
s yolk, nuts, seeds, olives…..