Lipids

 By abdurezak wegbela
Lipids are Organic substances relatively insoluble in water but soluble
in organic solvents like chloroform, ether and benzene
are any fat-soluble (lipophilic), naturally-occurring molecule, such
as fats, oils, waxes, cholesterol, sterols, fat-soluble vitamins (such as
vitamins A, D, E and K), monoglycerides, diglycerides,
phospholipids, and others.
The main biological functions of lipids include
energy storage,
acting as structural components of cell membranes,and participating
as important signaling molecules.
Provide excellent insulation
Used for pharmaceutical preparation like cream,ointement,emultion
Although the term lipid is sometimes used as a
synonym for fats, fats are a subgroup of lipids called
triglycerides.
Lipids are formed mainly from alcohol and fatty acids
combined together by ester linkage
Chemically Esters of
Three Fatty acids ( Same or Different) with one
Glycerol (Trihydric Alcohol).
Classification of lipids
On the basis of the nature of the products obtained on
hydrolysis, Lipids are mainly divided in two types such as
simple Lipids and Compound Lipids.
Besides thus there is one more type called derived lipids .
Simple lipids :- Lipids which upon Hydrolysis yield one or
more fatty acids and an alcohol.
Compound Lipids :- Lipids which upon Hydrolysis yield in
addition to fatty acids and alcohol , compound such as
phosphoric acid , sugar ,etc
Derived Lipids:- Lipids which also do not contain any ester
linkage but may be considered to have been derived from
naturally occurring esterified materials .
 Most of this has been alcohols of complex nature. eg.
Certain steroids, Certain Vitamins ,and certain plant
pigments .
Lipids may be broadly defined as hydrophobic or
amphiphilic small molecules that originate entirely or in part
from two distinct types of biochemical subunits or "building
blocks": ketoacyl and isoprene groups.
Using this approach, lipids may be divided into eight
categories :
fatty acyls,
glycerolipids,
glycerophospholipids,
sphingolipids,
saccharolipids and
polyketides (derived from condensation of ketoacyl subunits)
sterol lipids and
prenol lipids (derived from condensation of isoprene subunits)
 Fundamental biosynthetic units of lipids

O O
CH3
C C
C CH2
CH2 CH
CH2 C
CH3 H
Acetyl Propionyl

Ketoacyl "building blocks" Isoprene "building block"

Fatty acyls
Fatty acyls (including fatty acids) are a diverse group of
molecules synthesized by chain-elongation of an acetyl-CoA
primer with malonyl-CoA or methylmalonyl-CoA groups.
The fatty acyl structure represents the major lipid building
block of complex lipids and therefore is one of the most
fundamental categories of biological lipids.
The carbon chain may be saturated or unsaturated, and may be
attached to functional groups containing oxygen, halogens,
nitrogen and sulfur.
Examples of biologically interesting fatty acyls are the
eicosanoids which are in turn derived primarily from
arachidonic acid and eicosapentaenoic acid, which include
prostaglandins, leukotrienes, and thromboxanes.
 Glycerolipids
Glycerolipids are composed mainly of mono-, di- and tri-
substituted glycerols , the most well-known being the fatty
acid esters of glycerol (triacylglycerols), also known as
triglycerides.
These comprise the bulk of storage fat in animal tissues.
Glycerophospholipids
Glycerophospholipids, also referred to as phospholipids,
are ubiquitous in nature and are key components of the
lipid bilayer of cells, as well as being involved in
metabolism and signaling.
Sphingolipids

Sphingolipids are a complex family of compounds that

share a common structural feature, a sphingoid base
backbone that is synthesized de novo from serine and a
long-chain fatty acyl CoA, then converted into
ceramides, phosphosphingolipids, glycosphingolipids
and other species.
The major sphingoid base of mammals is commonly
referred to as sphingosine.
 Saccharolipids

Saccharolipids describe compounds in which fatty acids are

linked directly to a sugar backbone, forming structures that
are compatible with membrane bilayers. In the
saccharolipids, a sugar substitutes for the glycerol backbone
that is present in glycerolipids and glycerophospholipids.
The most familiar saccharolipids are the acylated
glucosamine precursors of the Lipid A component of the
lipopolysaccharides in Gram-negative bacteria.
Polyketides
Polyketides are synthesized by polymerization of acetyl and
propionyl subunits by classic enzymes as well as interative
and multimodular enzymes that share mechanistic features
with the fatty acid synthesis.
They comprise a very large number of secondary metabolites
and natural products from animal, plant, bacterial, fungal
and marine sources, and have great structural diversity.
Many polyketides are cyclic molecules whose backbones are
often further modified by glycosylation, methylation,
hydroxylation, oxidation, and/or other processes.
Many commonly used anti-microbial, anti-parasitic, and
anti-cancer agents are polyketides or polyketide derivatives,
such as erythromycins, tetracylines, avermectins, and
antitumor epothilones.
 Sterol lipids
Sterol lipids, such as cholesterol and its derivatives are an
important component of membrane lipids,along with the
glycerophospholipids and sphingomyelins.
Which also contain the same fused four-ring core structure,
have different biological roles as hormones and signaling
molecules.
The C18 steroids include the estrogen family whereas the C19
steroids comprise the androgens such as testosterone and
androsterone.
The C21 subclass includes the progestogens as well as the
glucocorticoids and mineralocorticoids. The secosteroids,
comprising various forms of vitamin D, are characterized by
cleavage of the B ring of the core structure.
Other examples of sterols are the bile acids and their
conjugates,which in mammals are oxidized derivatives of
cholesterol and are synthesized in the liver.
Prenol lipids
Prenol lipids are synthesized from the 5-carbon precursors
isopentenyl diphosphate and dimethylallyl diphosphate that
are produced mainly via the mevalonic acid (MVA) pathway.
The simple isoprenoids (linear alcohols, diphosphates, etc.)
are formed by the successive addition of C5 units, and are
classified according to number of these terpene units.
Structures containing greater than 40 carbons are known as
polyterpenes. Carotenoids are important simple isoprenoids
that function as anti-oxidants and as precursors of vitamin A.
Another biologically important class of molecules is
exemplified by the quinones and hydroquinones, which
contain an isoprenoid tail attached to a quinonoid core of
non-isoprenoid origin.
Vitamin E and vitamin K, as well as the ubiquinones, are
examples of this class.
Occurrence of Fats and Oils

Fats and oils can be either of plant or animal origin.

Vegetable oils: Extracted from seeds, eg. cotton
seed oil, soybean oil etc.
Vegetable fats: Extracted from coconut
Animal oils: eg. Cod liver oil, whale oil etc.
Animal fats: Lard and butter
Physical Characteristics of Fats and Oils

They are
Colorless liquid or solid, but maybe yellow or brown
due to impurities. •
 Lighter than water and immiscible with it •
Soluble in organic solvents such as petroleum ether,
benzene etc. •
Non-volatile •
Upon heating they decompose to give an irritating
odor
Form emulsions in the presence of
detergents/surfactants
Characterization of Physicochemical Properties
Solid Fat Content
The solid fat content (SFC) of a lipid influences many of
its sensory and physical properties, such as spreadability,
firmness, mouthfeel, processing and stability.
Food manufacturers often measure the variation of SFC
with temperature when characterizing lipids that are used in
certain foods, e.g., margarine and butter.
The solid fat content is defined as the percentage of the
total lipid that is solid at a particular temperature, i.e. SFC =
100Msolid/Mtotal, where Msolid is the mass of the lipid that is solid
and Mtotal is the total mass of the lipid in the food.
A variety of methods have been developed to measure
the temperature dependence of the solid fat content.
The density of solid fat is higher than the density of liquid
oil, and so there is an increase in density when a fat
crystallizes and a decrease when it melts.
 By measuring the density over a range of temperatures it is possible
to determine the solid fat content - temperature profile:

where d is the density of the lipid at a particular temperature,

and dl and ds are the densities of the lipid if it were completely
liquid or completely solid at the same temperature.
The density is usually measured by density bottles or
dilatometry.
Dilatometry is also used to monitor the progress of chemical
reactions, particularly those displaying a substantial molar volume
change (e.g., polymerisation). A specific example is the rate of
phase changes. Another common application of a dilatometer is the
measurement of thermal expansion.
 More recently, instrumental methods based on
nuclear magnetic resonance (NMR) have largely
replaced density measurements, because
measurements are quicker and simpler to carry out
(although the instrumentation is considerably more
expensive).
 Basically, the sample is placed into an NMR instrument and
a radio frequency pulse is applied to it.
This induces a NMR signal in the sample, whose decay rate
depends on whether the lipid is solid or liquid.
The signal from the solid fat decays much more rapidly
than the signal from the liquid oil and therefore it is possible to
distinguish between these two components.
Techniques based on differential scanning calorimetry are
also commonly used to monitor changes in SFC.
These techniques measure the heat evolved or absorbed by
a lipid when it crystallizes or melts.
By making these measurements over a range of
temperatures it is possible to determine the melting point, the
total amount of lipid involved in the transition and the SFC-
temperature profile.
 Melting point
In many situations, it is not necessary to know the SFC
over the whole temperature range, instead, only information
about the temperature at which melting starts or ends is
required.
A pure triacylglycerol has a single melting point that occurs
at a specific temperature.
Nevertheless, foods lipids contain a wide variety of
different triacylglycerols, each with their own unique melting
point, and so they melt over a wide range of temperatures.
Thus the "melting point" of a food lipid can be defined in a
number of different ways, each corresponding to a different
amount of solid fat remaining.
 •Some of the most commonly used "melting points"
are:

Clear point. A small amount of fat is placed in a

capillary tube and heated at a controlled rate.
The temperature at which the fat completely melts and
becomes transparent is called the "clear point".

Slip point. A small amount of fat is placed in a

capillary tube and heated at a controlled rate. The
temperature at which the fat just starts to move downwards
due to its weight is called the "slip point".
 Cloud point

This gives a measure of the temperature at which

crystallization begins in a liquid oil.
A fat sample is heated to a temperature where all the crystals
are known to have melted (e.g., 130oC).
The sample is then cooled at a controlled rate and the
temperature at which the liquid just goes cloudy is determined.
This temperature is known as the cloud point, and is the
temperature where crystals begin to form and scatter light.
 Smoke, Flash and Fire Points

They are particularly important for selecting lipids that are going
to be used at high temperatures, e.g. during baking or frying.
The tests reflect the amount of volatile organic material in oils
and fats such as free fatty acids.
The smoke point is the temperature at which the sample
begins to smoke when tested under specified conditions.
A fat is poured into a metal container and heated at a controlled
rate in an oven.
Smoke point is the temperature at which lipids begins to
break down to glycerol and free fatty acids, and produce bluish
smoke.
The smoke point is the temperature at which a thin continuous
stream of bluish smoke is first observed.
The glycerol is then further broken down to acrolein which
cause the irritation to eyes and throat.
 The flash point is the temperature at which a flash appears at
any point on the surface of the sample due to the ignition of volatile
gaseous products.

The flash point is the temperature at which the volatile

products generated by the liquid are being produced at a rate
where they can be temporarily ignited by application of a flame,
but cannot sustain combustion.

The fat is poured into a metal container and heated at a controlled

rate, with a flame being passed over the surface of the sample at
regular intervals.

The fire point is the temperature at which evolution of volatiles

due to the thermal decomposition of the lipids proceeds so quickly
that continuous combustion occurs (a fire).
 Rheology

The rheology of lipids is important in many food applications.

Rheology is the science concerned with the deformation and flow

of matter.
Most rheological tests involve applying a force to a material and
measuring its flow or change in shape.

Many of the textural properties that people perceive when they

consume foods are largely rheological in nature, e.g., creaminess,
juiciness, smoothness, brittleness, tenderness, hardness, etc.

The stability and appearance of foods often depends on the

rheological characteristics of their components.
 The flow of foods through pipes or the ease at which they can
be packed into containers are also determined by their rheology.

Liquid oils are usually characterized in terms of their flow

properties (viscosity), whereas viscoelastic or plastic "solids" are
characterized in terms of both their elastic (elastic modulus) and
flow properties.

A wide variety of experimental techniques are available to

characterize the rheological properties of food materials.
 One of the most important rheological characteristics of lipids is
their "plasticity", because this determines their "spreadability".

The plasticity of a lipid is due to the fact that fat crystals can form
a three-dimensional network that gives the product some solid-like
characteristics.

Below a certain stress (known as the "yield stress") the product

behaves like a solid with an elastic modulus because the crystal
network is not disrupted, but above this stress it flows like a liquid
because the crystal network is continually disrupted.

Rheological techniques are therefore needed to measure the

change in deformation of a lipid when stresses are applied.
 •Hydrolysis
Important chemical reactions of lipids •Rancidity
•Hydrogenation
Hydrolysis •Drying
•Acrolein formation

When fats are hydrolyzed with alkali or enzyme Lipase the yield
fatty acid and glycerol .
Lipases bring about splitting of fats in steps ,from triglycerides to
diglycerides to mono-glycerides and finally to glycerol and fatty
acids .
Lipases may work in the temperature range of 0° to 40° C .
 The fats are hydrolyzed with alkali yielding the free fatty acids
which react with alkali to form salts.

the salts are soaps and this process is termed as saponification .

Oxidation ( Rancidity ) :-
The development of off-flavours in lipids

Which deteriorates Fats and Oils

Resulting in an unpleasant taste ,odor and color of Fat/Oil
(Rancid Fat/oil)
This results in loss of nutritional value and is not suitable for
consumption.

Oxidation takes place of double bonds of the fatty acids ,

yielding short chain acids ; aldehydes etc.

Rancid Fat is inedible

Two types of rancidity are as follow

a) Hydrolytic rancidity – when fat is hydrolysed by lipase,

free fatty acids are released. The formation of low
molecular wt. fatty acids causes the deterioration of fats

b) Oxidative rancidity – The oxidation of unsaturated fatty

acids by oxygen results in the formation of peroxides.
The peroxides further degrades aldehydes and ketones
having pronounced off-odour.
Prevention of Rancidity of Fat/Oil By :

Good storage conditions

Less Exposure to light
Low Oxygen, moisture
No very High temperatures
No Bacteria or fungalcontamination
Addition of Antioxidants
Hydrogenation :-

By catalyst hydrogenation , unsaturated plant fats get converted

in to more saturated and solid fat .
It is also called “Hardening of Oils”
 It is generally done over finely divided nickel.
Hydrogenation converts PUFAs with cis form to trans form.
Hydrogenolysis :-

If excess of hydrogen , under pressure , is passed through oil or fat in

the presence of copper- chromium catalyst, it split up into glycerol and
higher aliphatic alcohols.

The process of splitting a compound by means of hydrogen is termed

as hydrogenolysis.
Acroline formation :-
If fats are heated in cooking ,some of the glycerol released by the
hydrolysis of the fat undergoes decomposition to yield acroline
which may be responsible for head ache or severe smarting of the
eye .
 Reading assignment

Determination of Total Lipid Concentration

Solvent Extraction
Semi-Continuous Solvent Extraction
Continuous Solvent Extraction
Nonsolvent Liquid Extraction Methods
Analysis of Oils and Fats(purity of oil and fat)

(i) Acid value :

It indicates the amount of free acid present in the oil or fat.
 It is defined as the number of milligrams of KOH
required to neutralize the free acid present in one gram
of the oil or fat.
 It is determined by dissolving a weighed amount of oil or
fat in alcohol and titrating it against a standard solution
of KOH using phenolphthalein as an indicator.
 Acid number checks the purity of Refined
oils.

 Refined oils are free from free fatty acids

and has zero Acid number.

 Increased Acid number of refined oil

suggests bacterial/chemical contamination
and unsafe for human consumption.
(ii) Saponification value :

It is a measure of fatty acids present as esters in oils and

fats.
 It is defined as the number of milligrams of KOH
required to saponify one gram of the oil or fat ie. number
of milligrams of KOH required to neutralize the free
acids resulting from the hydrolysis of one gram of an oil
or fat.
1 gram of Fat/oil with long chain fatty acids has
lower saponification number.
Since in 1 gram of Fat has few -COOH groups
of fatty acids to react with KOH.

1 gram of oil containing short chain fatty acids

has high Saponification number.
Since it has more COOH groups for KOH
reaction.
(iii) Iodine value :

Iodine value of a fat or oil is a measure of its degree of

unsaturation.
It is declared as the number of grams of iodine taken
up by 100 grams of fat or oil for saturation.

For a saturated acid glyceride, the iodine value is zero.

Thus, the iodine value for a fat is low whereas for oil is
high.
As iodine does not react readily, in actual practice,
iodine monochloride is used.
Iodine Number is calculated by method of
Iodometry.
Iodine number is directly proportional to
unsaturated bonds of PUFAs in a Fat/Oil.

High value of Iodine number of oil indicates

more content of Unsaturated Fatty acids in it.
(iv) Reichert-Meissl value, (R/M value) :
 It indicates the amount of steam volatile fatty acids
present in the oil or fat.
 It is defined as the number of millilitres of 0.1 N KOH
solution required to neutralize the distillate of 5 grams of
hydrolysed fat or oil.
It is determined by hydrolysing a known weighed
amount (5 grams) of the fat with alkali solution and the
mixture is acidified with dilute sulphuric acid and steam
distilled. The distillate is cooled, filtered and reacted
against 0.1 N KOH
Tests To Check Purity of Importance/Significance
Oils
Iodine Number Index of unsaturation and
content of unsaturated
fatty acids

Saponification Number To know Chain Lengths of

Fatty acids

Acid Number Checks purity of Refined

oils

Reichert Meissl (RM) Useful in testing the purity

Number of butter
Detergents
Soap, cleansing agent or detergent made from animal
and vegetable fats, oils, and greases; chemically, the
sodium or potassium salt of a fatty acid, formed by the
interaction of fats and oils with alkali.
Oils and fats used are compounds of glycerin and a
fatty acid, such as palmitic, or stearic acid.
When these compounds are treated with an aqueous
solution of an alkali, such as sodium hydroxide—a
process called saponification—they decompose,
forming glycerin and the sodium salt of the fatty acid.
The fat palmitin, for example, which is the ester of glycerin
and palmitic acid, yields sodium palmitate (soap) and
glycerin upon saponification.

The fatty acids required for soap making are supplied by

tallow, grease, fish oils, and vegetable oils such as coconut
oil, olive oil, palm oil, soybean oil, and corn oil.

Hard soaps are made from oils and fats that contain a high
percentage of saturated acids, which are saponified with
sodium hydroxide.