LIPIDS

Introduction, Sources, Nomenclature and Classification

Definition: The lipids are a heterogenous group of compounds related to fatty acids and include fats, oils,
waxes and other related substances.
 They are oily or greasy organic substances, insoluble in water and soluble in organic solvents
like ether, chloroform and benzene.
 They are thus hydrophobic in nature.
 These are variously called as lipins or lipoids.
 The term “lipid” was first used by German biochemist BLOOR in 1943 for a major class of
tissue components and food stuffs.

Occurrence (or) Sources:

Fats are widely distributed in plants and animal tissues from which they can be extracted by fat
solvent. In plants they are particularly present in nuts, seed, fruits etc. In animals they are stored in
adipose tissue, nervous tissue and bone marrow. Nervous system is rich in lipids like cholesterol,
phospholipids and glycolipids. Blood contains lipoproteins. In the cells, lipids are present in cytoplasm
as well as the plasma membrane. Food sources rich in fats are
Plant source – nuts, seed, iols etc.
Animal source – milk, meat, liver etc.

Functions of lipids:
1. Food material: Lipids provide food, highly rich in calorific value. One gram lipid produces 9.3
kilocalories of heat. But the same amount of carbohydrate releases 4.5 kilocalories only.
2. Food reserve: Lipids are insoluble in aqueous solutions and hence can be stored readily in the
body as food reserve.
3. Structural component: Lipids are important constituent of cell membrane.
4. Heat insulation: The fats are characterized for high insulating capacity. Great quantities of fat
are deposited in the subcutaneous layers in aquatic mammals such as whales and in animals
living in cold climates.
5. Fatty acid absorption: Phospholipids play an important role in the absorption of and transport
of fatty acids.
6. Hormone synthesis: The sex hormones, adrenocorticoids, are synthesized from cholesterol.
7. Lipids acts as carriers of fat soluble vitamins such as A, D, E and K.
8. Function of dietary lipids is to supply the essential fatty acids.
9. Some lipids act as surfactants by reducing surface tension.

Classification of lipids
Bloor (1943) has proposed the following classification of lipids based on their chemical composition.

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 1. Simple lipids: These are esters of fatty acids with alcohols.
These are mainly of two types:
 Fats and Oils (Triglycerides TG, Triacylglycerols TAG): These are esters of fatty acids with
glycerol.

The difference between fat and oil is only physical. Oil is a liquid while fat is a solid at room
temperature.

Note: Fats and Oils (storage forms of energy) are derivatives of fatty acids.
Monoacylglycerides, diacylglycerides and triacylglycerides, consist respectively of one, two or three molecules
of fatty acid esterified to a molecule of glycerol.

Triacylglycerols or Triacylglycerides or Neutral Fat

These are tri-esters of fatty acids with glycerol.
 Triacylglycerols containing the same kind of fatty acid in all three postions are called simple
triacylglycerols. E.g.,simple triacylglycerols of palmitic acid is called tripalmitin.
 Mixed triacylglycerols contain two or more different fatty acids. The fatty acid on carbon-1 is usually
saturated. That on carbon-2 is usually unsaturated and that on carbon-3 can be either.

 

 Waxes: These are esters of long chain fatty acids with long chain mono hydroxy aliphatic alcohols other
than glycerol such as Cetyl alcohol, CH3 (CH2)14 CH2OH which is most commonly found in waxes.
(The term “wax” is originated from English word “weax” meaning the material of honey comb).
Waxes are seen all over in nature. The leaves and fruits of many plants have waxy coatings which protect them
from dehydration and small predators. Feathers of birds ans some other animals have similar coatings which
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 serve as water repellant.
Sources of Waxes; they can be of plant or animal origin. Examples of waxes from animal sources include:
Spermaceti- found in the head of sperm whales and helps them in their buoyancy and warmth . It is made up of
palmitic and cetyl alcohol, making it cetyl palmitate.
Sebum waxy substance secreted by sebaceous gland in the skin of mammals help to keep the skin soft and prevent
dehydration.

Bees wax- which is found in the structural material of bee hives is an important wax that is used to make several
substances including cosmetics, candles, ointments, protective polishes. Beeswax contains myricyl palmitate
obtained from esterification reaction between palmitic acid and Myricyl alcohol.

Waxes from plant sources include:

Carnuba Wax: which is obtained from palm tree, is valued for its toughness and water resistance. It is used to
make protective coating for furniture, cars, floors, etc.

Lanolin which a mixture of waxes obtained from wool is used in hand and facial lotions to aid water retention.

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2. Complex (or compound) lipids or Hetero lipids: These are esters of fatty acids with alcohols
containing additional groups such as phosphate, nitrogenous base, carbohydrate, protein etc. Based on the
additional groups they are classified as:

(a) Phospholipids: They contain phosphoric acid and frequently a nitrogenous base in addition to alcohol and
fatty acids. e.g., lecithin, cephalin.
(b) Glycolipids: These lipids contain a fatty acid, carbohydrate and nitrogenous base. The alcohol is
sphingosine and hence they are also called as glycosphingolipids. Glycerol and phosphate are absent e.g.,
cerebrosides, gangliosides.
(c) Sulpholipids: These are esters containing Sulphate groups.
(d) Lipoproteins: These are lipids attached to proteins. Eg., HDL (high density lipoprotein) , LDL (low
density lipoprotein).

3. Derived lipids: These are the derivatives obtained on the hydrolysis of group1 and group2 lipids which
possess the characteristics of lipids. These include glycerol and other alcohols, fatty acids, mono- and
diacylglycerols, cholesterol, steroid hormones, terpenes.

FATTY ACIDS
Fatty acids are aliphatic carboxylic acids with hydrocarbon side chain. They are simplest form of lipids. They
have the general formula RCOOH where COOH represents functional group and R represents hydrocarbon. If
we desscribe fatty acids based on their bio-synthesis, they are compounds synthesized in nature by the
condensation of malonyl CoA units by the fatty acid synthase complex enzyme.
Fatty acids usually contain even number of carbon atoms in straight chains. Fatty acids have 2 ends or 2 parts.
The carboxyl end (also called the carboxylic head) which is polar and the methyl end also called the
(hydrocarbon chain or tail) which hydrophobic and non-polar.

Occurrence: Fatty acids mainly occur as major constituents of various lipids. But their most abundant source is
triglycerides.

Functions of fatty acids include: They are the building block for other lipids phospholipids, glycolipids etc
-They provide and store energy
-They are modifying agents when attached covalently to proteins and other molecules for specific functions
-Fatty acid derivatives serve as inteacellular second messengers

Classification of fatty acids:

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  Depending upon the total number of carbon atoms fatty acids are classified into 2 types: Even
and odd carbon fatty acids
• Even chain fatty acids: Most of the naturally occurring lipids contain even chain fatty
acids(usually 14C-20C). Eg. Palmitic acid (C16) and Stearic acid (C18) are the most
common.
• Odd chain fatty acids: These are seen in microbial cell walls.
 Depending upon the length of hydrocarbon chain, fatty acids are classified into 3 types:
 Short chain fatty acids: with 2 to 6 C atoms.
 Medium chain fatty acids: with 8 to 14 C atoms.
 Long chain fatty acids:-with 16 and above usually up to 24 C atoms.
Chain length affects some important characteristic of fatty acids such as solubility, transport, melting
point etc
 Depending upon the nature of hydrocarbon chain, fatty acids are classified into 5 Types:
a. Saturated fatty acids: These are fatty acids which do not contain double bonds.
See table in next page for examples.
b. Unsaturated fatty acids: They 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).
c. Branched chain fatty acids: These are fatty acids having branched structure. Eg. Isovaleric, Isocaproic
acid.
d. Hydroxy fatty acids: These are fatty acids containing hydroxyl group in its structure.
e. Cyclic fatty acids: These are fatty acids containing cyclic ring structure.

Common name Systematic No. of Structure Common

name Carbon Source
atoms
Branched chain 3-methyl 5 Metabolic
fatty acids: butanoic acid Intermediate
Isovaleric acid

Hydroxy Fatty 12-hydorxy, 18 Castor Oil

Acids: Ricinoleic ∆9
Acid octadecenoic
acid
Cyclic fatty Cyclopentenyl 18 Chaulmoogra

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 The prefix n- indicates the “normal” unbranched structure. In biological fatty acids, the configuration is
almost always Cis.

Nomenclature of fatty acids

 The naming of a fatty acid (systematic name) is based on the hydrocarbon from which it is derived.

 The saturated fatty acids end with a suffix –anoic . For e.g., the C18 saturated FA octadecanoic acid,
because the parent hydrocarbon is octadecane.
 The unsaturated fatty acids end with a suffix –enoic (e.g.,octadecenoic acid).
One double bond – monoenoic acid
Two double bond – dienoic
Three double bond - trienoic
Four double bond - tetraenoic
Ex: With one double bond  octa decenoic acid
With two double bond  octa deca di-enoic acid

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Numbering of carbon atoms: Two conventions for naming fatty acids:
Fatty acids are often named with the in which
1. Alpha system of fatty acid nomenclature or Standard Nomenclature: the counting of carbon atoms
proceed from the carboxyl end towards the methyl end. It assigns the no.1 to the carboxyl carbon (C-1),
and „α‟ to the carbon next to it. The position of any double bond(s) is indicated by ∆ followed by a
superscript number indicating the lower numbered C in the double bond.

2. Omega system of fatty acid nomenclature: : the counting of carbon atoms proceed from the methyl end
towards the carboxyl end. For poly unsaturated fatty acids (PUFAs) , an alternating convention numbers
the carbon in the opposite direction, assigning the number 1 to the methyl „C‟ at the other end of the chain;
this „C‟ is also designated as „ω‟(omega; the last letter in the greek alphabet). The position of „=‟ bonds
indicated relative to the ω carbon.
Shorthand representation of fatty acids
 Instead of writing the full structures, biochemists employ shorthand notations (by numbers) to represent
fatty acids.
 The general rule is that the total number of carbon atoms are written first followed by the number of
double bonds and finally position of double bonds, starting from the carboxyl end.

 Thus, saturated fatty acid,

o palmitic acid is written as 16:0,
o oleic acid as 18:1; 9,
There are other conventions of representing the double bonds ∆9 indicates that the double bond is between 9
and 10 of the fatty acid.ω9 represents the double bond position (9 and 10) fatty acids belong to ω9, ω6 and ω3
series.
ω 3 series: Linolenic acid(18:3; 9,12,15)
ω 6 series: Linoleic acid (18:2; 9,12) and arachidonic acid(20:4; 5,8,11,14)
ω 9 series: oleic acid (18:1; 9)

Isomerism of double bond of fatty acid

A double bond in an alkyl side chain (hydrocarbon chain) can occur in the Cis or Trans configuration.
 Nearly all double bonds in naturally occurring FA in humans, plants and bacteria are of the Cis
configurations.

 „Trans‟ double bonds, however, are formed during the catalytic hydrogenation of vegetable oils to make
margarine. The purpose of hydrogenation is to change the physical properties of oils into solid products
which are easier to manipulate. The solid fats are used in the manufacture of candles

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 Chemical properties of Fatty Acids and Triglycerides
Reactions of Triglycerides involving COOH group
1. Hydrolysis: The fats are hydrolyzed by lipases to yield FA and glycerol. It occurs in a step – wise
manner.

2. Saponification: The hydrolysis of fats by alkali is called saponification. This reaction results in
the formation of glycerol and salts of FA which are called soaps.

Soaps are important cleansing agents. Their cleansing property is due to their emulsifying action.

3. Rancidity: When butter or fats are stored, they become rancid (sour or rotten) and hence unpalatable
(not able to use). Rancidity is caused by growth of microorganisms which secrete lipases. These split
the fats into glycerol and FA. The FA gives unpleasant odour and flavour to the fat. This rancidity
can be prevented by refrigeration or by exclusion of water (using air- tight containers).

Reactions involving double bond:

1. Hydrogenation: Unsaturated FA can combine with gaseous hydrogen under the influence of a
suitable catalyst such as platinum, palladium or nickel to give saturated FA. The addition of hydrogen
takes place at the C-C double bond.

2. Halogenation: Unsaturated FA and their esters can take up halogens like Br2 and I2 at their double
bonds at room temperature in acetic acid or methanol solution.
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 3. Oxidative rancidity: The unpleasant odour and taste developed by natural fats upon aging is referred
to as “rancidity”. Rancidity may be due to hydrolysis or oxidation of fats.
Oils containing highly unsaturated fatty acids are spontaneously oxidized by atmospheric oxygen at
ordinary temperatures. This may form short chain fatty acids, peroxides, which then decompose to
form aldehydes of unpleasant odour and taste.

This process is increased by exposure to light or heat. Many natural vegetable fats and oils, may
contain antioxidants like vitamin E which prevent onset of rancidity. Therefore, vegetable fats can
be preserved for a longer time than animal fats. Overheating and repeated heating of oil (is an
unhealthy practice) leads to peroxide formation.

Reactions involving OH groups:

1. Dehydration (Acrolein test) – Fats when heated in the presence of a dehydrating agent, NaHSO4 or
KHSO4 produce an unsaturated aldehyde called acrolein from the glycerol moiety. Acrolein is easily
recognized by its pungent odour and thus forms the basis of test for the presence of glycerol in fat
molecule.

Quantitative test or characterization of fat:

Composition, quality and purity of a given fat or oil is determined by means of a no. of physical and
chemical test. The usual physical test includes determination of MP, Specific gravity, viscosity etc.,
while chemical tests includes determination of
(i) Acid number (ii) Saponification number (iii.) Iodine number
(iv) Reichert-Meissl Number

1. Saponification number: It is the number of mgs of KOH required to saponify 1 gm of fat. This
number provides information on the average chain length of the FA in the fat. It varies inversely with
the chain length of the FA. The shorter the average chain length of the FA, the higher is the
saponification number.

2. Iodine number: It is the number of grams of iodine absorbed by 100 gm of fat. This number is a
measure of degree of unsaturation of FA in fat. Higher iodine no., indicates presence of higher amount
of unsaturated FA. Oils like soyabean, corn, cotton seed oil have high iodine value than the solid fat
such as beef fat.

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 Essential fatty acids
 The fatty acids that cannot be synthesized by the body and therefore, should be supplied in the diet are
known as essential fatty acids (EFA).

 Chemically, they are polyunsaturated fatty acids, namely
 linoleic acids (18:2,9,12)
 linolenic acid (18:3; 9,12,15).

Conditionally essential
 Arachidonic acid (20:4; 5, 8, 11, 14) becomes essential, if its precursor linolenic acid is
not provided in the diet in sufficient amounts.

Biochemical basis for essentiality: Linoleic acid and linolenic are essential since humans lack the enzymes that
can introduce double bonds beyond carbons 9 and 10.

Functions of Essential Fatty Acids (EFA)

(a) EFA‟s are constituent of structural lipids of the cell and are concerned with the structural integrity of the
mitochondrial membrane. Arachidonic acid is present in membranes and accounts for 5% to 15% of the fatty acids
in phospholipids.
(b) Essential fatty acids are required for transport of cholesterol, formation of lipoproteins, prevention of fatty
liver etc.
(c) They are also needed for the synthesis of eicosanoids - Formation of regulatory compounds like
prostaglandins and leukotrienes.
(d) Docosa-hexaenoic acid (DHA:ω-3) (cervonic acid),which is synthesized from linolenic acid or obtained
directly from fish oils, is present in high conc in retina, cerebral cortex,testis and sperm. DHA is particularly
needed for development of the brain and retina during the neonatal period and is supplied via the placenta and
milk.Therefore,a small daily intake of EFA is now recommended.This may be especially important when the
nervous system is developing.
It has been found that animal fat contain more saturated FA whereas vegetable fat contains more of unsaturated FA
and the latter are rich in EFA. The unsaturated and EFA tend to lower the serum cholesterol. This property of EFA
is important in the management of hypercholesterolemia associated with atherosclerosis (or thickening of arteries).
Diet rich in EFA are
1. Vegetable oils rich in EFA are
i. Safflower oil contains 75% EFA
ii. Corn oil contains 50% EFA
iii. Cotton seed oil contains 45% EFA.
2. Animal fat are poor sources of EFA.
i. Egg contains 9% EFA
ii. Lard contains 9% EFAs

Essential Fatty Acid Deficiency

A disease state known as essential fatty acid deficiency occurs if EFA‟s are excluded from the diet for long periods.
The syndrome in the humans is characterized by:
• Dermatitis and
• Poor wound healing
These problems clear up when the patients are fed diet containing EFA

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