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Fatty Acids: Saturated Unsaturated
Fatty Acids: Saturated Unsaturated
Fatty Acids: Saturated Unsaturated
1
Saturated fatty acids
The common names of these acids indicate the
specific source in which they are especially abundant
Or from which they have been isolated
Physical properties vary with the number of carbon
atoms
Acids with fewer than 12 carbon atoms are
conventionally called “the volatile fatty acids” since
they can steam distilled with relative ease
Members with carbon atoms higher than 10 are solids
at room temp
Solubility in water decreases with the chain length
Acids with more than 10 carbons are practically
water-insoluble 2
Unsaturated fatty acids
Oleic and linoleic acid, account for 34% and 29% of all the
edible oils produced by man annually
Acids with two or more double bonds are known as poly-
unsaturated acids
Poly-unsaturated fatty acids perform certain important
physiological functions, but
they cannot be synthesized in the body and must be supplied in the food
are referred to as “essential fatty acids”
Linoleic acid is the most abundant member of this group
Unsaturated fatty acids have considerably lower
melting points than corresponding saturated fatty
acids
Thus oleic acid with 18 carbon atoms is a liquid at
room temp
The industrial hardening by hydrogenation is based on
the saturation of the double bonds 3
Isomerism in fatty acids
Three possible types of isomerism
1) Single isomerism of a straight chain versus
branched chain
2) Isomerism caused by the position of the double
bond in the chain
In the case of more than one unsaturated double bond,
this type of isomerization can give two distinct kinds of
systems, conjugated and non-conjugated
3) cis-trans (geometrical) isomerism
In nature most unsaturated fatty acids occur
mainly in the cis-form
Trans??
4
Structure of Fatty acid
5
Fatty Acids
Fatty acids are almost entirely straight chain aliphatic
carboxylic acids.
Includes most natural fatty acids C4 to C22
Naturally occurring fatty acids share a common
biosynthesis.
The chain is built from two carbon units, and cis
double bonds are inserted by desaturase enzymes at
specific positions relative to the carboxyl group.
Even-chain-length fatty acids with a characteristic
pattern of methylene interrupted cis double bonds.
A large number of fatty acids vary in chain length and
unsaturation
Two numbers separated by a colon give,
respectively, the chain length and number
of double bonds: octadecenoic acid with 18
carbons and 1 double bond is therefore
18:1.
The position of double bonds is indicated in
a number of ways:
explicitly, defining the position and
configuration; or
locating double bonds relative to the methyl or
carboxyl ends of the chain.
Fatty acids in fats and oils
Major sources
Structure and stereospecific
melting behavior
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Phospholipids
Lipids containing phosphoric acid
Difficult to classify in view of its wide heterogeneity
Phosphoglycerides is the most important
(Structure below)
Two hydroxyls of the glycerol residue are esterified with fatty acids
The third hydroxyl is bound to phosphoric acid which in turn is
ester-linked with X-OH, usually an amine alcohol
27
Phospholipids
The phosphoric acid end of the molecule is strongly
polar hydrophylic
The fatty acid “tails” are non-polar
This dual structure (amphiphatic) makes the
phosphoglycerides valuable surface active agents and
emulsion stabilizers
Phosphoglycerides are important cell wall constituents
29
Role of lipids in Foods
The role of lipids in sensory characteristics is mainly
connected with texture and rheological properties
Refined fats have no taste of their own
The presence and physical form (dispersion) of fats,
determine the taste sensation and mouth feel
Flow properties of the food in the mouth are controlled by
the fat fraction
Spreadability, coating of the tongue, sensation of
swallowing, viscosity
30
Lipid Oxidation, Introduction
Off flavours are generally described as “rancidity” in fat-
containing foods
The principal source of “rancidity” in foods is the autoxidation of
lipid compounds
Autoxidation: Defined as the spontaneous oxidation of a
substance in contact with molecular oxygen
The fatty acid alkyl chain is susceptible to oxidation both at
double bonds and adjacent allylic carbons.
Free-radical and photooxidation at allylic carbons are responsible
for deterioration of unsaturated oils and fats, resulting in
rancid flavors and reduced nutritional quality,
31
Introduction
Consequences of lipid autoxidation
Most significant – rancidity
Also flavour deterioration
Colour is affected – through accelerated browning
Nutritional value is impaired
Toxicity may occur
Texture may change due to side reactions between proteins and the
products of fat oxidation
Oxidative deterioration of lipids may be considered as a
spoilage factor affecting all the aspects of food acceptability
Lipid compounds most susceptible to autoxidation
are the unsaturated fatty acids
Especially those with more than one double bond
Autoxidative deterioration of lipids resembles
somewhat non-enzymic browning 32
Mechanism
1: Initiation 2: Propagation 3: Decomposition 4: Termination
34
Hydroperoxide
The various regions of the lipids are not equally
susceptible to activation
The methylenic group, adjacent to a double bond of a
fatty acid, is particularly labile
hydroperoxide is the primary products of lipid
autoxidation
They are non-volatile, odorless and tasteless
Formation and accumulation are measured as the increase
in the “peroxide value”
Indicates the progress of autoxidation, but not
necessarily the appearance of rancidity
35
Degradation of Hydroperoxides
Hydroperoxides are relatively unstable
As their concentration in the system
increases, they begin to decompose
On possible reaction is the monomolecular
decomposition of hydroperoxides into an alkoxy
and hydroxy radical
36
Polymerization
Polymerization
One of the consequences of lipid oxidation is the
formation of viscous, gum-like or solid polymers
(resins)
“Drying” of highly unsaturated oils used in paints is
the result of such polymerization
May occur through direct contact with free radicals
or through other reactions
37
Kinetic aspects
The course of autoxidation in lipids is
experimentally followed by measuring the;
Accumulation of peroxides
Rate of oxygen uptake
Concentration of secondary reaction products
Organoleptic evaluation
38
A. Peroxide value
One of the most widely used concepts in lipid
chemistry
measure of peroxide concentration of oil
39
B. Rate of oxygen uptake
More meaningful measure of the rate of
oxidation
method to determine
reaction of the oxidized fat with thiobarbituric acid
(TBA)
TBA reacts with oxidized fats to give a red
colored complex which is measured by
spectrophotometer
TBA test correlates well with the degree of
rancidity
40
… B. Rate of oxygen uptake
When the peroxide value (or oxygen uptake)
of an autoxidizing lipid is followed, a curve are
drawn
At first the PV increases slowly, uniform rate
As soon as the PV reaches critical value, a
sudden and drastic increase in rate is recorded
The first slow phase is termed “induction
period”
The autocatalytic nature of this course is
explained on the basis of the free radical chain
mechanism explained
41
… B. Rate of oxygen uptake
During the induction period initiation and propagation
occur
Since for each free radical which is transformed to a
hydroperoxide one new free radical is formed
The reaction proceeds at a slow uniform rate
As the concentration of of hydroperoxides increases,
hydroperoxide decomposition reactions take place at
an in increasing rate
These reactions generate more free radicals than
needed for the propagation of the chain reaction at a
constant rate - Autocatalytic
42
a. Heavy Metals as Catalysts
The main effect of these trace metals is to increase
the rate of hydroperoxide decomposition, and hence
the rate of free radical generation
Hydroperoxides are decomposed and free radicals RO
and ROO are formed as the metal oscillates between
its two oxidation states
The source of heavy metal ions in foods may be contamination
Equipment, piping, packaging materials, environmental contaminants
Or natural food components
Most important metal-containing natural food components are
the metallo-porphyrin substances (hematin compounds)
Hemoglobin, myoglobin
43
b. Enzymes as Catalysts
Catalyst of lipid oxidation in some foods –
lipoxidase
Lipoxidase catalyzes specifically the direct
oxidation of poly-unsaturated fatty acids
containing a cis-cis 1,4-pentadiene group
(linoleic and linolenic acid)
This enzyme is found in oilseeds, legumes,
cereals, leaves
If it is not inactivated by heat (blanching),
lipoxidase may cause rapid development of off-
flavours in frozen and dehydrated veggies
44
Antioxidants
Antioxidants are substances that retard
autoxidation
A substance may act as antioxidant in variety of
ways
Competitive binding of oxygen
Retardation of free radicals
Inhibition of catalysts
Stabilization of hydroperoxides
All these mechanisms are found in food systems
– the most important is blockage of propagation
45
Antioxidants
Antioxidation action increases the length of the induction period
The induction period increment is roughly proportional to the
concentration of antioxidant up to a certain level
Excess concentration of antioxidant is ineffective or may even
cause reversion of the protective affect
One of the principal classes of antioxidants are the natural or
synthetic phenolic compounds
Synthetic phenolic antioxidants approved for food use include
butylated hydroxyanisol (BHA)፣ butylated hydroxytoluene (BHT) and
propyl gallate (PG)
BHT and BHA are quite volatile at frying temp
PG forms dark compounds with iron ions
46
Natural antioxidants
(a) a-tocopherol,
(b) carnosic acid,
(c) sesamol. Synthetic antioxidants
(d) butylated hydroxyanisole (BHA),
(e) butylated hydroxytoluene (BHT), and
(f) propyl gallate.
a. Lipid autoxidation in Food Systems –
Oxidized flavors
Immediately recognizable effect of lipid oxidation
in foods is the development of undesirable odors
and off-flavors
“rancid” products are largely short-chain
carbonylic compounds formed as a result of
peroxide decomposition
The overall organoleptic nature of rancidity
depends somewhat on the system
48
a. … Oxidized flavors
The rancidity in low-moisture foods is usually described as
“old oil” or “tallow-like”
Lipid oxidation in water-rich foods such as milk resutls in
49
b. Effect of Colour
Lipid oxidation may affect indirectly the colour of
foods
In carotenoids, propagation of the lipid oxidation
chain through free radicals may cause oxidative
destruction of the carotenoid pigments
This type of deterioration is important in dehydrated
vegetables and usually involves the catalytic action of
lipoxidases
50
c. Effect on Texture
The interaction between proteins and the products of
lipid oxidation may result in changes of texture
The mechanism of interaction involves propagation of
the free radical chain to the protein system
Various groups in the protein molecule are capable of
converting to free radicals by losing a hydrogen atom
to a free radical of lipid origin
The protein “free radicals” thus formed tend to
combine by cross-linkages
51
Lipid Oxidation at High Temp
Of interest in connection with food processing
operations involving high temp:
Toasting, roasting, baking, frying
Most important characteristics of heated oils
are:
Despite the accelerated rate of oxidation, peroxide
values are usually very low, due to the rapid
decomposition of the peroxides formed
The flavor of heated oils is not rancid (unlike fats
oxidised at low temp) due to the elimination of
the volatile breakdown products by
evaporation – steam distillation effect
52
… Lipid Oxidation at High Temp
Polymerization is one of the predominant
termination processes.
The viscosity of oils increases considerably due
to the process of heating
The degree of unsaturation, measured as the
“iodine value” decreases sensibly, indicating
direct saturation of the double bonds.
Poly-unsaturated acids are affected first
Hydrolysis of the fat occurs and fatty acids are
liberated, especially in the process of frying
53
Lipid nature of Carotenoids
Carotenoids
Large group of pigments
Widely distributed in the plant and animal kingdoms
Yellow-orange to purple in colour
Insoluble in water
Soluble in fats and organic solvents
Classed as Lipochrome pigments
Food products of animal origin such as milk, butter,
egg yolk, some fish and shellfish, contain carotenoids
dispersed in the lipid components
54
Lipid nature of Carotenoids
Carotenoids are much more stable to oxidation in their
natural form than in pure systems.
Crystalline pure lycopene or a solution of lycopene n
chloroform fades in a matter of a few hours when
exposed to air, while the same pigment in its natural
form in tomatoes is quite stable
The oxidation of carotenoids and the autoxidation of
fats have many points in common and are interrelated
in food systems
Free radicals formed in the course of fat oxidation may
participate in the oxidative attack on carotenoids
The enzyme lipoxidase may also take part in
carotenoid oxidation
55
Lipid nature of Carotenoids
Breakdown of Carotenoids
Because of their highly unsaturated nature, they oxidize very quickly,
particularly at the double bonds
As double bonds are saturated and finally broken down, the
characteristic color of carotenoids bleaches
The most important factor in the oxidation of carotenoids is
the presence of oxygen or strong oxidizing agents
The destruction is more rapid at high temp
The effect of temperature may accelerate oxidation directly,
also render the carotenoid more susceptible to breakdown
by denaturing the protective protein
Bleaching is more rapid in the absence of water
Moisture content levels can have a protective effect on
carotenoids
56
Carotenoids in Food Systems
Mixtures of natural carotenoids extracted form plant
tissues and synthetic ß-carotene are commercially
available as food colorants
Both in the oil-soluble and water-dispersible forms
Chemical instability of carotenoids:
Loss of carotenoids is a problem in fat rich systems
(butter/margarine), and in low moisture foods
Loss of characteristic colour
Formation of undesirable odors due to breakdown products
57
Carotenoids in Food Systems
Opaque containers, package under nitrogen –
prevents destruction
Carrots – coating of starch can be sprayed on before
dehydration
The bleached colour of the carotenoids, caused by
oxidation, is often a very important indication of
deterioration in food product
Citrus essential oils
Colour of carotenoids can be undersirable
Bleaching of wheat flour during storage in air
58
Lipid nature of Vitamin A
Vitamin A is now termed Retinol
In relationship with carotenoids
ß-carotenoids consists of two molecules of vit A,
bound tail to tail
ß -carotene is converted to vit A, with the help of
enzymes in the intestinal mucosa
The name provitamin A given to B-carotene
The conversion involves oxidation at the middle point,
by a specific enzyme, ß-carotene-15, 15-
oxygenase
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Lipid nature of Vitamin A
A peroxide is formed
Cleavage of the peroxide yields two molecules of
retinal (the aldehyde form of vit A)
The majority of retinal is reduced to retinol by a non-
specific enzyme
Retinol is carried into the blood stream and any
amount in excess of the required level in blood is
stored in the liver, in the form of fatty-acid esters
In the blood retinol is carried by a very specific
protein, retinol binding protein
60
Lipid nature of Vitamin A
Function of vit A is connected with vision
In the eye, retinol, is oxidized to retinal
Retinal combines with certain proteins termed
opsins, to formvisual pigments of the retina
Vit A and β-carotene, are soluble in fats and oils
when the oils become rancid (due to oxidation) the vitamin
suffers considerable losses
butter or vit-enriched margarines, subjected to prolonged
storage
Vitamin can be destroyed by light
The effect of packaging is an important factor in the
retention of vit A
61
Terpenes, Essential oils
Essential oils are widely distributed in many different parts
of the same plant
Roots, stem, leaves, flowers, fruits
The aromatic material may be actually dissolved in the juice,
or the essential oils are secreted in numerous oils sacs or
glands located in the epicarp, adjacent to the chromoplast
Essential oils are mixture of various volatile organic substances along
with non-volatile waxy materials
The term “oil” implies that these substances are insoluble in water but
soluble in non-polar solvent
The greater part of essential oils consists of terpenoids and their
derivatives
Terpenoids are naturally occuring isoprenoid hydrocarbons (terpenes)
and their oxygenated derivatives
62
Lipid Nature of Cholesterol
Cholesterol is the most abundant sterol of the animal
as structural element of cell membranes of many tissues in
conjunction with phospholipids
also occurs in ester combination with fatty acids
Closely related to cholesterol is lanosterol, found in the
fatty component of wool
lanosterol is an effective fat-water binding agent, hence the use
of lanolin in “moisturizing creams”
Lanosterol is an intermediate in the biosynthesis of cholesterol
Cholesterol also serves as a precursor in the biosynthesis of
ergosterol (vit D) and steroid hormones and bile acids
bile acids are synthesized in the liver, from cholesterol
Bile acids: emulsify fats and thus facilitate digestion and
absorption.
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