04-11-2024

CHEMISTRY
OF
LIPIDS

CONTENTS
 Introduction
 Classification of lipids

 Functions of lipids

 Fatty acids

 Triacyl glycerol

 Properties of triacyl glycerol

 Tests to check the purity of fats

 Steroids

 Cholesterol

1
 04-11-2024

INTRODUCTION
 Lipids (Greek: lipos-fat) are of great importance to the body
as the chief concentrated storage form of energy, besides their
role in cellular structure and various other biochemical
functions. As such lipids are a heterogeneous group of
compounds and, therefore, it is rather difficult to define them
precisely.
 Lipids may be regarded as organic substances relatively
insoluble in water, soluble in organic solvents (alcohol, ether
etc.), actually or potentially related to fatty acids and utilized
by the living cells.
 Unlike the polysaccharides, proteins and nucleic acids, lipids
are not polymers. Further, lipids are mostly small molecules.

CLASSIFICATION OF LIPIDS
 Lipids are broadly classified (modified from Blood) into
simple, complex, derived and miscellaneous lipids, which are
further subdivided into different groups.
1. SIMPLE LIPIDS:
Esters of fatty acids with alcohols. These are mainly of
two types
a. Fats And Oils (Triacyl Glycerols):
 These are esters of fatty acids with glycerol.
 The difference between fat and oil is only physical. Thus, oil is a
liquid while fat is a solid at room temperature.
b. Waxes:
 Esters of fatty acids (usually long chain) with alcohols other than
glycerol. These alcohols may be aliphatic or alicyclic. Cetyl alcohol
is most commonly found in waxes.

2
 04-11-2024

2. COMPLEX (or COMPOUND) LIPIDS:

 These are esters of fatty acids with alcohols containing groups
such as phosphate, nitrogenous base, carbohydrate, protein
etc.
 They are further divided as follows:

a. Phospholipids:
 They contain phosphoric acid and frequently a nitrogenous
base. This is in addition to alcohol and fatty acids.
i. Glycerophospholipids:
 These phospholipids contain glycerol as the alcohol

e.g. lecithin, cephalin.

ii. Sphingophospholipids:
 Sphingosine is the alcohol in this group of phospholipids

e.g., sphingomyelin.

b. Glycolipids:
 These lipids contain a fatty acid, carbohydrate and
nitrogenous base. The alcohol is Sphingosine, hence they are
also called as glycosphingolipids. Glycerol and phosphate are
absent
E.g. cerebrosides, gangliosides
c. Lipoproteins:
 Macro molecular complexes of lipids with proteins.

d. Other complex lipids:

 Sulfolipids, amino lipids and lipo polysaccharides are among
the other complex lipids.

3
 04-11-2024

3. DERIVED LIPIDS:
 These are the derivatives obtained on the hydrolysis of group
1 and group 2 lipids which possess the characteristics of
lipids.
 These include glycerol and other alcohols, fatty acids, mono-
and di acyl glycerols, lipid (fat) soluble vitamins, steroid
hormones, hydro carbons and ketone bodies.
4. MISCELLANEOUS LIPIDS:
 These include a large number of compounds possessing the
characteristics of lipids
E.g., carotenoids, squalene, hydrocarbons such as pentacosane
(in bees wax), terpenes etc

FUNCTIONS OF LIPIDS
Lipids perform several important functions:
1. They are the concentrated fuel reserve of the body
(triacylglycerols).
2. Lipids are the constituents of membrane structure and regulate
the membrane permeability (phospholipids and cholesterol).
3. They serve as a source of fat soluble vitamins (A, D, E and K).
4. Lipids are important as cellular metabolic regulators (steroid
hormones and prostaglandin).
5. Lipids protect the internal organs; serve as insulating materials
and give shape and smooth appearance to the body.

4
 04-11-2024

FATTY ACIDS
Fatty acids are carboxylic acids with hydrocarbon side chain.
They are the simplest form of lipids.
 Saturated and unsaturated fatty acids:

 Saturated fatty acids do not contain double bonds, while

unsaturated fatty acids contain one or more double bonds.
Both saturated and unsaturated fatty acids almost equally
occur in the natural lipids.
 Fatty acids with one double bond are monounsaturated, and
those with 2 or more double bonds are collectively known as
poly unsaturated fatty acids (PUFA).

5
 04-11-2024

TRIACYLGLYCEROLS

 Triacylglycerols (formerly triglycerides) are the esters of

glycerol with fatty acids. The fats and oils that are widely
distributed in both plants and animals are chemically
triacylglycerols. They are insoluble in water and non-polar in
character and commonly known as neutral fats.
 Triacylglycerols of plants, in general, have higher content of
unsaturated fatty acids compared to that of animals.

PROPERTIES OF
TRIACYLGLYCEROLS
A few important properties of triacylglycerols, which have
biochemical relevance, are discussed below
1. Hydrolysis:
 Triacylglycerols undergo stepwise enzymatic hydrolysis to
finally liberate free fatty acids and glycerol.
 The process of hydrolysis catalyzed by lipases is important for
digestion of fat in the gastrointestinal tract and fat
mobilization from the adipose tissues.
2. Saponification:
 The hydrolysis of triacylglycerols by alkali to produce
glycerol and soaps is known as saponification.

Triacylglycerol+ 3 NaOH --------- Glycerol+ 3 R-COONa(soaps)

6
 04-11-2024

3. Rancidity:
 Rancidity is the term used to represent the deterioration of fats
and oils resulting in an unpleasant taste. Fats containing
unsaturated fatty acids are more susceptible to rancidity.
 Rancidity occurs when fats and oils are exposed to air,
moisture, light, bacteria etc. Hydrolytic rancidity occurs due to
partial hydrolysis of triacylglycerols by bacterial enzymes.
 Oxidative rancidity is due to oxidation of unsaturated fatty
acids. This results in the formation of unpleasant products such
as dicarboxylic acids, aldehydes, ketones etc.
 Rancid fats and oils are unsuitable for human consumption.

4. Antioxidants:
 The substances which can prevent the occurrence of oxidative
rancidity are known as antioxidants.
 Trace amounts of antioxidants such as tocopherols (vitamin
E), hydroquinone, Gallic acid and α-naphthol are added to the
commercial preparations of fats and oils to prevent rancidity.
 Propylgallate, butylated hydroxy anisole (BHA) and butylated
hydroxy toluene (BHT) are the antioxidants used in food
preservation.

7
 04-11-2024

TESTS TO CHECK PURITY OF FATS

AND OILS
 Adulteration of fats and oils is increasing day by day. Several
tests are employed in the laboratory to check the purity of fats
and oils. Some of them are discussed hereunder.
1. Iodine number:
 It is defined as the grams (Number) of iodine absorbed by 100
g of fat or oil.
 Iodine number is useful to know the relative unsaturation of
fats, and is directly proportional to the content of unsaturated
fatty acids. Thus lower is the iodine number, less is the degree
of unsaturation.
 Determination of iodine number will help to know the
degree of adulteration of given oil.

 The iodine numbers of common oils/fats are given

below.

8
 04-11-2024

2. Saponification number:
 It is defined as the mg (number) of KOH required to
hydrolyze (saponify) one gram of fat or oil Saponification
number is a measure of the average molecular size of the fatty
acids present.
 The value is higher for fats containing short chain fatty acids.
The saponification numbers of a few fats and oils are given
below.
Human fat : 195-200
Butter : 230-240
Coconut oil : 250-260

3. Reichert-Meissl (RM) number:

 It is defined as the number of ml 0.1 N KOH required to
completely neutralize the soluble volatile fatty acids distilled
from 5 g fat.
 RM number is useful in testing the purity of butter since it
contains a good concentration of volatile fatty acids (butyric
acid, caproic acid and caprylic acid).
 This is in contrast to other fats and oils which have a
negligible amount of volatile fatty acids.
 Butter has a RM number in the range25-30, while it is less
than 1 for most other edible oils. Thus any adulteration of
butter can be easily tested by this sensitive RM number.

9
 04-11-2024

4. Acid number:
 It is defined as the number of mg of KOH required to
completely neutralize free fatty acids present in one gram fat
or oil.
 In normal circumstances, refined oils should be free from any
free fatty acids. Oils, on decomposition-due to chemical or
bacterial contamination-yield free fatty acids. Therefore, oils
with increased acid number are unsafe for human
consumption.

STEROIDS
 Steroids are the compounds containing a cyclic steroid nucleus (or
ring) namely cyclo pentano perhydro phenanthrene (CPPP). It
consists of a phenanthrene nucleus (rings A, B and C) to which a
cyclopentane ring (D) is attached.
 The steroid nucleus represents saturated carbons, unless
specifically shown as double bonds.
 The methyl side chains (19 and 18) attached to carbons10 and 13
are shown as single bonds. At carbon 17, steroids usually contain a
side chain. There are several steroids in the biological system.
 These include cholesterol, bile acids, vitamin D, sex hormones,
adrenocortical hormones, sitosterols, cardiac glycosides and
alkaloids.
 If the steroid, contains one or more hydroxyl groups it is
commonly known as sterol (means solid alcohol).

10
 04-11-2024

CHOLESTEROL
 Cholesterol, exclusively found in
animals, is the most abundant
animal sterol. It is widely
distributed in all cells and is a
major component of cell
membranes and lipoproteins.
 Cholesterol (Creek: chole-bile)
was first isolated from bile.
Cholesterol literally means 'solid
alcohol from bile.'

STRUCTURE AND OCCURRENCE

 The structure formula of cholesterol is C27H46O. It has one
hydroxyl group at C3 and a double bond between C5 and C6.
An 8 carbon aliphatic side chain is attached to C17.
 Cholesterol contains a total of 5 methyl groups. Due to the
presence of an -OH group, cholesterol is weakly amphiphilic.
 As a structural component of plasma membranes, cholesterol is
an important determinant of membrane permeability,
properties. The occurrence of cholesterol is much higher in the
membranes of sub-cellular organelles.
 Cholesterol is found in association with fatty acids to- form
cholestervlesters (esterification occurs at the OH group of C3).

11