Lipids

1. Introduction

Lipids are a heterogeneous group of organic compounds that are insoluble in water and soluble
in non-polar organic solvents (Chloroform, hydrocarbon or alcohol). They are naturally occur in
most plants, animals, microorganisms and are used as cell membrane components, energy stor-
age molecules, insulation, and hormones.

Lipids obtained from animal sources are usually solids whereas oils are generally of plant origin.
Therefore, we commonly speak of animal fats and vegetable oils.

The role of lipids in the diet has received a great deal of attention because of the apparent con-
nection between saturated fats and blood cholesterol with arterial disease. Lipids are the most
important energy storage compounds in the animal kingdom

In addition, lipids provide insulation for the vital organs, protecting them from mechanical shock
and maintaining optimum body temperature. Lipids are integral components of cell membrane
structure and, as such, are associated with transportation across cellular membranes.

BIOLOGICAL SIGNIFICANCE OF LIPIDS

1. Rich source of energy: fats provide food of high calorific value (1g fat produces about 9.3 kilo

calories of heat).

2. As food reserve: Fats are stored in body as reserve food material, because these could be

readily stored in the body on account of insoluble character sticks. Triglycerides stored in

adipocytes (fat cells) of adipose tissue are the principal fat reserve.

3. As heat insulators: Fats deposited in the subcutaneous tissues act as insulators conserving body

heat.

4. Solvent: Lipids act as a solvent for fat soluble vitamins like vitamin A, D and E.
5. Structural constituents: Phospholipids, glycolipids and sterols are structural components of all

the membrane system of cell (i.e. cell membrane, nuclear membrane, membranes of the

endoplasmic reticulum etc.)

6. Fat transport: Phospholipids play an important role in the absorption and transportation of
fatty acids.

7. Hormone synthesis: Adrenocorticoids, sex hormones, vitamin D and cholic acids are

synthesized from cholesterol.

8. As shock absorber: The fat deposited around the visceral organs and underneath the skin acts

as cushion and absorbs mechanical shocks.

9. As electric insulators: Myelin sheath around medullated nerve fibres forms an electric

insulation.

10. Prostaglandins: They control local activities in the body.

11. Protective layers: Lipids form a protective waxy covering on the aerial parts of plants to
check loss of water by evaporation.

12. Thrombokinase: helps blood clotting.

13. Leukotrienes: a group of eicosanoid helps in respiration.

14. Some isoprenoids form insect hormones.

15. Some insoprenoids form volatile oil and pigments. Natural rubber is also an isoprenoid.

16. Glycolipids help in cell recognition.

17. Complex lipids form phospholipid bilayer of plasma membrane.

18. Steroid act as hormones and neurotransmitters in mammals

2. Physical properties of Lipids

 Lipids may be either liquids or non-crystalline solids at room temperature.

  Pure fats and oils are colourless, odorless, and tasteless.
 They are energy rich organic molecules
 Insoluble in water
 Soluble in organic solvents like alcohol, chloroform, acetone, benzene etc.
 No ionic charges
 Solid triglycerols (Fats) have high proportions of saturated fatty acids.
 Liquid triglycerols (Oils) have high proportions of unsaturated fatty acids.

3. Structure of Lipids

 Basically, they are made from two molecules: Glycerol and Fatty Acids.
 A glycerol molecule is made up from three carbon atoms with a hydroxyl group attached
to it and hydrogen atoms occupying the remaining positions.
 They may be saturated or unsaturated.

Structure of Triglycerides

 Triglycerides are lipids consisting of one glycerol molecule bonded with three fatty acid
molecules.
 The bonds between the molecules are covalent and are called Ester bonds.
 They are formed during a condensation reaction.
 The charges are evenly distributed around the molecule so hydrogen bonds to not form
with water molecules making them insoluble in water.

4. Classification of Lipids:

Unlike polysaccharides and proteins, lipids are not polymers. However, like carbohydrates, they
can be classified according to their hydrolysis products and according to similarities in their
molecular structures. Three major subclasses are recognized:
i. Simple lipids:

(a) Fats and oils which yield fatty acids and glycerol upon hydrolysis. Fats and oils are the most
abundant lipids found in nature. Both types of compounds are called triacylglycerols because
they are esters composed of three fatty acids joined to glycerol, a trihydroxy alcohol.

Further classification of triacylglycerols is made on the basis of their physical states at room tem-
perature. It is customary to call a lipid a fat if it is solid at 25°C and oil if it is a liquid at the same
temperature. (These differences in melting points reflect differences in the degree of unsaturation
of the constituent fatty acids.)

(b) Waxes.

A wax is an ester of a long-chain alcohol (usually mono-hydroxy) and a fatty acid. The acids and
alcohols normally found in waxes have chains of the order of 12-34 carbon atoms in length.
Waxes are easily melted solids that are widely distributed in nature and are found in both plant
and animal matters. They are not as easily hydrolysed as the triacylglycerols and therefore are
useful as protective coatings.

(c) Fatty acids

A fatty acid can be defined as an organic acid that occurs in a natural triglyceride and is a mono-
carboxylic acid ranging in chain length from C4 to about 24 carbon atoms.

On the basis of presence or absence of double bonds, fatty acids may be classified into two main
classes-

i. Saturated fatty acids (saturated with hydrogen)

The fatty acids which do not contain any double bond are called saturated fatty acids. The gen-

eral formula is Cn H2n+1 COOH e.g. Butyric acid C3 (CH2)2 COOH. The most abundant satu-
rated fatty acids in nature are palmitic acid (C18) and stearic acid (C16). The saturated fatty
acids are straight chain acids. In addition to these straight chain acids, there are some branched
chain acids, with odd or even number of carbon [Link]. Isopalmitic acid, anti-isopalmitic acid
and tuberculostearic acid

2. Unsaturated fatty acids

The fatty acids which contain one or more double bonds are called unsaturated fatty acids. On
the basis of number of double bonds, the unsaturated fatty acids may be divided into two groups-

Mono unsaturated fatty acids: - having one double bond e.g. crotonic acid, oleic acid, palmitoleic
acid, nervonic acid etc.

Polyunsaturated fatty acids:-having more than one double bonds e.g. linoliec acid, eleostearic
acid etc.

In most of the monosaturated fatty acids there is a single bond lying between carbon atoms 9 and
9
10. This is designated as ∆ . The symbol ∆ with the superscript number nine (9) indicates the po-
sitions of the double bond. When there are more than one double bond (polyunsaturated fatty
9
acids), the additional bonds occur between the ∆ double bond and the methyl terminal end of
the chain. The symbol 18:3 signifies that there are three double bonds and symbol ∆9,12,15 sig-
nifies that the position of double bonds are between carbon atom 9 and 10, 12 and 13 and 15 and
16.

Presences of double bonds in the fatty acids lower their melting point considerably. Most plant
fats contain unsaturated fatty acids as oleic acid and linoleic acid and hence they are liquid at
room temperature. Contrary to this animal fats have more of saturated fatty acids and hence solid
at room temperature.

Essential Fatty Acids

The fatty acids which cannot be synthesized by human body but are essential for the normal
maintenance of the body are called essential fatty acids .These fatty acids must be included in
our diet. Three polyunsaturated fatty acids, linoleic acid, linolenic acid and arachidonic acid are
the essential fatty acids.
Non essential fatty acid

These are the fatty acids which can be synthesized by our body. Thus they need not be included
in our diet. They are unsaturated fatty acids and are synthesized from their corresponding satu-
rated fatty acids by introducing a single bond .e.g. palmitoleic acid and oleic acid.

ii. Compound lipids:

Compound lipids contain some additional groups or elements besides fatty acids are alcohol. The
addition group may contain phosphorus, nitrogen, sulpher or it may be a protein. Compound
lipids canbe categorized into the following: Phospholipids, Glycolipids,

Phospholipids

Phospholipids are those compound lipids which contain a phosphorus atom. In addition to phos-
phorus, phospholipids may also contain nitrogen as a key component.

Simply, Phospholipids are compound which yield fatty acids, glycerol, phosphoric acid and a ni-
trogen-containing alcohol upon hydrolysis.

Phospholipids are wide spread in bacteria, animal and plant tissues and their general structures
are quiet similar.

They may be glycerophospholipids or sphingophospholipid depending upon the attaching

group present (glycerol or sphingosine).
Glycolipids

Glycolipids, which yield fatty acids, glycerol, and a carbohydrate upon hydrolysis.
iii. Derived lipids:

Steroids

Terpenes
Chemical Properties of Lipids:

a. Saponification:

Triacylglycerols may be hydrolysed by several procedures, the most common of which utilizes
alkali or enzymes called lipases. Alkaline hydrolysis is termed saponification because one of the
products of the hydrolysis is a soap, generally sodium or potassium salts of fatty acids.

This hydrolysis reaction also provides a useful analytical method for the determination of a con-
stant, the saponification number, which is characteristic of the simple lipids.

The saponification number of a lipid is defined as the number of milligrams of potassium hy-
droxide required to saponify 1 gm. of a fat or oil. It gives an indication of the average molar
mass of the lipid.

A lipid that contains long-chain fatty acids will have fewer molecules of acid per unit mass than
one containing the short- chain fatty acids. In other words, a small saponification number for a
fat or oil indicates a high molar mass.

b. Halogenation:

Unsaturated fatty acids, whether they are free or combined as esters in fats and oils, react with
halogens by addition at the double bond(s). The reaction (halogenation) results in the decolouri-
sation of the halogen solution.

Since the degree of absorption by a fat or oil is proportional to the number of double bonds in the
fatty acid moieties, the amount of halogen absorbed by a lipid can be used as an index of the de-
gree of unsaturation.

The index value is called the Iodine number and is defined as the number of grams of iodine (or
iodine equivalent) that will add to 100 grams of fat or oil. As a general rule, a high iodine num-
ber indicates a high degree of unsaturation. Natural fats of saturated fatty acids have iodine num-
bers of about 10-50; those that contain an abundance of polyunsaturated fatty acids have iodine
numbers of 120-150.
c. Hydrolysis of triglycerols

Triglycerols like any other esters react with water to form their carboxylic acid and alcohol– a
process known as hydrolysis.

d. Hydrogenation

The carbon-carbon double bonds in unsaturated fatty acids can be hydrogenated by reacting with
hydrogen to produce saturated fatty acids.

e. Rancidity:

The term rancid is applied to any fat or oil that develops a disagreeable odour. Hydrolysis and
oxidation reactions are responsible for causing rancidity. Oxidative rancidity occurs in triacyl-
glycerols containing unsaturated fatty acids.