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LIPIDS
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Introduction

Lipids cannot be defined based on the chemical nature of the members

since they differ widely in structure and possess different chemical
groups. But they are commonly soluble in certain non polar organic
solvents. Based on this, lipids have been defined as compounds soluble in
ether, chloroform and benzene. Moreover almost of the lipids are soluble
in petroleum ether. Lipids are greasy substances present in both plants
and animals and constitute as main components of foods along with
proteins and carbohydrates.

Classification

Different authors adopt different systems for classification of lipids. We

are narrating a system of classification consisting of four classes such as
simple lipids, compound lipids, derived lipids and lipids
complexedto other compounds.

Structures of different lipids and some related narration

Before we are discussing about the structures of higher lipids,
we need to know the structures of fatty acids which are derived lipids.
Fatty acids are carboxylic acids which take part in the formation of
lipidous substances of organisms. Depending on the number of carbon
atoms they have, they may be even carbon and odd carbon acids. Even
carbon acids are generally found in natural fats. However, certain plants
and animals fats have odd carbon acids. Short chain, medium chain and
long chain fatty acids have 2-6, 8-14 and 16-24 carbon atoms
respectively. Very long chain fatty acids have more than 24 carbon atoms.
Moreover based on the nature of hydrocarbon chain, they may be
saturated, unsaturated, branched and hydroxyl derivatives.

Numbering of carbon atoms of fatty acids can be done starting from

carboxyl group carbon or from terminal methyl group carbon atom
denoting it as ω-1, next carbon atom as ω-2 and so on. In the former
case, the position of double bond is indicated by prefixing number in the
systematic name. In the latter case if the fatty acid is referred to as ω-3,
then it indicates this fatty acid has a double bond between ω-3 and ω-4
carbon atoms as one nearest to ω-1 carbon atom.

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Table 1.Saturated fatty acids.

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Common Systematic Formula I Occurrence

name name (lacks last
set)
Acetic acid n-Ethanoic CH 2:0 Tr i a c e t i n
(artificial)
Butyric acid n-Butanoic CH 4:0 Milk fats
H
Caproic acid n-Hexanoic CH 6:0 Plant fats
H
Caprylic acid n-Octanoic CH 8:0 Coconut oil
H
Caproic acid n-Decanoic CH 10:0 Plant fats
H
Lauric acid n-Dodecanoic CH 12:0 Laurel oil
H
Myristic acid n - CH 14:0 Nutmeg
Tetradecanoic H
Palmitic acid n - CH 16:0 Palm oil
Hexadecanoic H
Stearic acid n - CH 18:0 Animal and
Octadecanoic H plant fats
A r a c h i d i c n-Eicosanoic CH 20:0 Groundnut
acid H
Bohenic acid n-Docosanoic CH 22:0 Groundnut
H
Lignoseric n - CH 24:0 Groundnut &
acid Tetracosanoic H rapeseed
Cerotic acid n - CH 26:0 Wool fat
Hexacosanoic H

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Examples of saturated fatty acids are given in table 1. Their general
formula is CnH2n+1COOH. Their common names, systematic names,
formulae and occurrence have been displayed in the table.

Since the freedom of rotation of groups and atoms about the double
bond is prevented, the unsaturated fatty acids exhibit a type of
stereoisomerism known as geometrical isomerism. The basis is the
different arrangement of groups and atoms about the double bond. Two
isomeric forms cis and trans are produced when like groups and atoms
are on the same side and opposite sides of the double bond respectively.
Illustration is given with the isomers of of the formula C17H33COOH. The
cis isomer is oleic acid and trans isomer is elaidic acid. They have
different melting points and other physical constants. In this case oleic
acid is fatty acid.

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Oleic acid (cis), m.p. 13oC Elaidic acid

( trans), m.p. 45oC

In table 2, example of dienoic fatty acid is given with linoleic acid. Its
prefixing numbers are 9 and 12. These double bonds have cis
arrangement of groups and atoms. This table further shows that trienoic
fatty acids such as α-linolenic acid and ϒ-linolenic acid differ only in the
position of double bonds. Table 2 further displays the positions of double
bonds of polyenoic fatty acids. Again this table shows that α-linolenic acid,
timnodonic acid and cervonic acid are ω-3 fatty acids. It is very
interesting that ω-3 fatty acids reduce blood cholesterol , triglycerides
and blood pressure of human .

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Table-2.Unsaturated fatty acids

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a. Monoenoic (having only one double bond)

COOH
Common Systematic name Formula I Omega
name family
Myristoleic cis-9-Tetradecenoic C 13 14:1( w-5
acid H
P a l m i t o l e i c cis-9-Hexadecenoic C 15 16:1( w-7
acid H
Oleic acid cis-9-Octadecenoic C 17 18:1( w-9
H
Vaccenic acid cis-11-Octadecenoic C 17 18:1( w-7
H
Nervonic acid cis-15-Tetraeicosenoic C 23 24:1( w-9
H
b. Dienoic (having two double bonds).
Linoleic acid all c i s - 9 , 1 2 - C 17 18:2( w-6
Octadecadienoic H
c. Trienoic (having three double bonds).
α-Linolenic a l l c i s - 9 , 1 2 , 1 5 - C 17 16:3( w-3
acid Octadecatrienoic H
γ-Linolenic a l l c i s - 6 , 9 , 1 2 - C 17 16:3( w-6
acid Octadecatrienoic H

d. Polyenoic fatty acids (having more than three double bonds).

General formula: CnH2(n-x)O2 where x = no. of double bonds.
A ra c h i d o n i c all cis-5,8,11,14- C20 20:4(Δ w-6
acid Eicosatetraenoic

Timnodonic all cis-5,8,11,14,17- C20 20:5(Δ w-3

acid Eicosapentaenoic

Cervonic acid all cis-4,7,10,13,16,19- C22 22:6(Δ w-3

9
Docosahexanoic )

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I: Distinguishing three sets of number. These sets such as 18:3(Δ9,12,15)
and 20:5(Δ5,8,11,14,17) can be alternatively written as 18:3;9,12,15 and
20:5;5,8,11,14,17 respectively.
Moreover tables 1&2 indicate that fatty acids have been distinguished by
three sets of number. The first set indicates the total number of carbon
atoms. The second number separated from the first number by colon
indicates the number of double bond. Then delta follows it. Superscripts
on delta indicate the numbers of carbon atoms preceding double bonds.
Alternatively, instead of delta semicolon is used. It is then followed by
preceding numbers of double bonds.

Saturated fatty acids are solid at room temperature. This is due to

parallel arrangement of their alipathic chains. However cis double bonds
disturb this regular packing and thus unsaturated fatty acids are liquids at
room temperature. Melting point of fatty acids lowers with increasing
degree of unsaturation.

Linoleic acid and linolenic acid are essential fatty acids. Arachidonic
acid becomes essential when its precursor linoleic acid is not sufficiently
obtained from the diets.

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Simple lipids

They are esters of alcohols and fatty acids. If alcohol is glycerol,

and it is esterified by three fatty acid molecules, they are triglycerides.
Fats and oils are triglycerides. On the other hand, esters formed by long
chain alcohols comprising 16 to 30 carbon atoms and long chain saturated
and unsaturated fatty acids comprising 14 to 36 carbon atoms are waxes.
Examples of waxes are beeswax, lanolin of lamb’s wool and spermaceti oil
of whales etc. Waxes are used in the preparation of candles, cosmetics,
lubricants, ointments, polishes .

Triglycerides are simple when they formed with identical fatty acid
molecules. Example is tristearin present in beef fat. Mixed triglyceride is
formed with at least two different fatty acid molecules.

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Triglycerides with higher composition of unsaturated fatty acids exist as

liquid at room temperature and therefore they are oils. The terms fats
and oils cannot be implied for distinct triglycerides since a triglyceride
may be solid ei fat at low temperature and liquid ei oil higher
temperature. For example ghee is solid at room temperature and oil at
higher temperature.

Saponification number

Previously it has discussed that fatty acids composed in fats vary widely
in chain length. Thus the molecular weights of different fats are to vary.
We can have an idea on this by determining their saponification number.
Saponification number is defined as the amount KOH in milligram required
to saponify 1 g of fat. We know that a molecule of fat is saponified by
three molecules of KOH. Since a gram of fat composed by low molecular
weight fatty acids has more of its molecules, requires more amount of
KOH for complete saponification. Thus saponification number is an index
of average molecular size of fatty acids of fat. It can be experimentally
found out.
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Iodine number

Halogens can be added to the double bonds of unsaturated fatty

acids of fats. Iodine number expresses the amount of iodine in g added to
100g of fat. This can be experimentally found out. It expresses the
degree of unsaturation of fats.

-CH=HC- + I2 → -CIH-HIC-

Rancidity of fats

During storage in presence of lipases, fats undergo slow

hydrolysis with the liberation of free fatty acids. Short chain fatty acids
have bad smell. Such development of unpleasant taste and odour is
known as rancidity and fat is said to be rancid. Another cause of rancidity
is the reaction between unsaturated fatty acids of fat and atmospheric
oxygen. As done by free unsaturated fatty acids, unsaturated fatty acids
of fats combine with oxygen to form peroxides. The peroxides then
undergo scission to form aldehydes of objectionable odour. Addition of
antioxidants such as vitamin E prevents oxidation by atmospheric oxygen.

Acid number

It expresses the amount of KOH in mg required to neutralize the free

fatty acids present in 1 g of fat. It indicates the degree of rancidity of fat.

Compound lipids

Compound lipids occur in phosphorylated and non phosphorylated

forms. Phosphorylated lipids or phospholipids are the derivatives of
glycerol phosphate and sphingosine phosphate.

Glycerol phosphate derivatives

Glycerol phosphate derivatives are lecithins which are

chemically phosphatidyl choline, cephalins which are chemically
phosphatidyl ethanolamine and phosphatidyl serine. Other examples are
phophatidyl inositol and phosphatidyl inositol phosphate etc. All these are
derivatives of L-α-phosphatadic acid in which two hydroxyl groups of α│
and β carbon atoms of glycerol are esterified to two fatty acid molecules
while hydroxyl group of α carbon atom is esterified to phosphoric acid.
Its β carbon atom is assymmetric and it exists in L-form. Therefore it is
known as L-α-phosphatidic acid.

In case of plasmalogens αɪ carbon atom is ether linked with long

chain aliphatic aldehyde. Aliphatic aldehyde changes to its enol form
before formation of ether bond.

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PlasmalogenEnol form of aliphatic aldehyde

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Sphingosine phosphate derivatives

They are known as phosphosphingosides or sphingomyelins. One

molecule of sphingomyelin is composed by one molecule for each of
sphingosine or dihydrosphingosine, phosphoric acid, choline and fatty
acid. They are found in nerve tissues.
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Non phosphorylated derivatives

Non phosphorylated lipids include glycolipids and sulpholipids

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Glycolipids

Glycolipids are also known as glycosphingolipids. Cerebrosides,

globosides and gangliosides belong to glycolipids. One molecule of
cerebroside is composed by one molecule for each of sphingosine, fatty
acid, glucose or galactose. Its sphingosine and fatty acid portion is
known as ceramide. Globosides are ceramide oligosaccharides. Their
oligosaccharides are made up of glucose and galactose and other
combinations of hexoses and hexoseamine. Gangliosides are derived
forms of globosides with attachment of N-acetyl neuraminic acid.
Cerebrosides and gangliosides are found in brain.

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Globoside

Sulpholipids

Lipids having sulphate groups are known as sulpholipids or

sulphatides.

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Sulfolipid

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Derived lipids

Fatty acids

Fatty acids are examples of derived lipids because they can be obtained
from other lipids. Their structures, certain physical and chemical
properties have been discussed preiviosly.

Steroids

They are compounds derived from basic structure of four fused

rings- three of cyclohexane and one of cyclopentane. Such fused ring
system is known as perhydrocyclophentanophenanthrene. If such
structure has one hydroxyl group at carbon atom no. 3 and a chain of
8-10 carbon atoms at carbon atom no. 17, then it is known as sterol.
Examples of sterols are lanosterol, ergosterol, cholesterol, 7-
dehydrocholesterol etc. Other forms of steroids are bile acids, sex
hormones, adrenocorticoids and insect hormone etc.

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Lanosterol 7-Dehydrocholesterol

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Vitamin D is formed by cleaving ring B of ergosterol upon

irradiation with UV. Hence it is member of the class derived lipids.

Terpenes

Terpenes are hydrocarbons formed by polymerisation of repeating unit of

isoprene. An isoprene has five carbon atoms and eight hydrogen atoms.
Some authors use the word terpenoids for terpenes whose methyl groups
are eliminated, moved or containing oxygen. However, organic chemists
use both words interchangeably. A monoterpene is composed by two
isoprene units and it has ten carbon atoms. Examples are geraniol,
limonene, menthol. A sesquiterpene has three isoprene units and thus it
has 15 carbon atoms. Example is farnesol. Diterpenes, triterpenes and
tetraterpenes are composed by 4,6 and 8 isoprene units respectively.
Table 3 displays their numbers of carbon atoms and examples. The table
also shows that rubber is a polyterpene composed by 500-5000 isoprene
units.

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Table 3.Terpenes

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Terpenes No. of No. of carbon Terpenoids

repeating units atoms
Monoterpenes 2 10 Geraniol,
limonene,
menthol
Sesquiterpenes 3 15 Farnesol

Diterpenes 4 20 Abietic acid,

sapeitic acid
Triterpenes 6 30 Lanosterol
Tetraterpenes 8 40 Carotenoids
Polyterpenes 500-5000 2500 - 2500 Rubber

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Isoprene units combine to form terpenes following special rule. In
accordance to this rule, isoprene units combine with the formation of
head to tail linkage. No. 1 and no. 4 carbon atoms of isoprene are known
as head and tail respectively. However, this rule is not always followed.
For example cryptone has nine carbon atoms instead of ten carbon
atoms. Moreover isoprene units are not head to tail linked in lavandulol.
Again in carotenoids two isoprene units in the centre of the chain are tail
to tail linked.
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Isoprene

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FarnesolGeraniol

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Menthol
Limonene

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LavandulolCryptone

It has ascertained from table 3 that carotenoids are tetraterpenes.

Members of carotenoids are more than 600 and they are divided into
carotenes and xanthophylls. Carotenes are hydrocarbons and they are in
the subclass of unsaturated hydrocarbons. Examples are α-carotene and β
carotene and lycopene. Xanthophylls are oxygen containing carotenoids.
Examples are lutein and zeaxanthin.

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α-carotene β-
carotene

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β-cryptoxanthin

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α- Carotene, β- carotene and β- cryptoxanthin serve as precursors of
vitamin A for human. Therefore vitamin A is regarded as lipid under the
class derived lipids. On the other hand, vitamins E and K have isoprenoids
side chain. Therefore they are also members of the class derived lipids.

Eicosanoids

Arachidonic acid is the dominant precursor of eicosanoids. It can be

noted that all eiconoids have twenty carbon atoms. Eicosanoids include
prostaglandins, thromboxanes, leukotrienes and lipoxins etc. In our body
prostaglandins function as local hormones, Leukotrienes bring about
contraction of smooth muscles. Thromboxanes participate in the
formation of blood clot. Lipoxins exert immunoregulatory function.

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Lipids complexed to other compounds

Lipoproteins

Certain lipoproteins occur in blood as transport form of lipids. They are

complexes of proteins, phospholipids, triglycerides and cholesterol. Based
on fraction migration in density gradient separation, they are classified
into very low density lipoproteins (VLDL), low density lipoproteins (LDL),
high density lipoproteins (HDL). VLDL is mainly synthesized in liver, but in
intestine it is also synthesized in small amount with absorbed lipids. LDL
is largely derived from VLDL. HDL is the transport form of cholesterol
from peripheral cells to liver where it is excreted in bile as bile acids.
These lipoproteins have different half life periods.

Proteolipids

They are complexes of protein, phosphoglycerides and cerebrosides, and

occur in brain tissue.

Lipopolysaccharides

These lipids occur in the outer layer of the cell wall of gram negative
bacteria. Permeability barrier exhibited by outer layer is due to presence
of these lipids.

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Polar and non polar lipids

Lipids such as phophatidyl choline, phosphatidyl ethanolamine

etc. have charged groups. Such polar groups are hydrophilic. But their
hydrocarbon chains are hydrophobic. Therefore they are amphipathic
molecules. Other lipids such as monoglyceride, diglyceride and sterols
have polar hydroxyl groups and they are also amphipathic molecules. The
hydrophilic and hydrophobic parts of such amphipathic molecules are
known as head and acyl chain respectively.
 When cross sectional area of the head is larger than that of acyl
chain, amphipathic molecules form micelles when mixed with water.
Examples are soap molecules. A micelle has few dozen to few thousand of
molecules. In a micelle hydrophobic side chains aggregate inside
excluding water while their hydrophilic heads are in contact with water.
On the other hand when their head and acyl chain have equal cross
sectional

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Micelle Lipid bilayer

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area, they organise into lipid bilayer when mixed with water. In lipid
bilayer, acyl chains of each monolayer occupy inner portion due to their
hydrophobic interaction and Van der Waals' force and thus they exclude
water. The hydrophilic heads of each monolayer interact with water
molecules forming hydrogen bonds. Examples are phosphatidyl choline,
phosphatidyl ethanolamine etc.

Biological importance
Biological roles of lipids in plants and animals are several and some
important biological roles are discussing below.
Fats serve as chief energy reservoir of plants and animals.
Fats prevent loss of heat from the body. They also support and protect
internal organs by serving as padding substance.
Glycolipids, phospholipids, cholesterol and other steroids are the major
structural components of mitochondrial and other cellular membranes.
Lipoproteins are the transport forms of lipids in blood. They involve in the
absorption of free fatty acids from intestine.
Glycolipids, phospholipids and steroids play essential roles in the
functions of mitochondria.
Cerebrosides, gangliosides and sulpholipids play specific roles in the brain
functions.
Cholesterol gives rise to bile acids.
Cholesterol insulates impulse generating and transmitting units of brain
and nerve.
Waxes of animals’ skins and furs serve as protective lipids. Plant waxes
protect leaves and fruits. Ear wax is also an example of protective lipid.
Vitamins A,E,D and K are also members of lipids. These vitamins play
magnificent roles in the vital processes.
Eicosanoids such as protaglandins serve as local hormones. Functions of
other eicosanoids are causing contraction of smooth muscles, formation of
blood clot and regulation of blood pressure etc.
Conclusion

From the above narration, it can be concluded that many organic

molecules widely differed in structure and function include as members of
lipids. The structure of a lipid may be as simple as that of acetic acid and
complex one as that of a lipoprotein. Fats and oils are neutral lipids
whereas phospholipids are polar lipids. The functions of lipids are
diversified as fats and oils are storage lipids of plants and animals;
phospholipids, glycolipids and steroids serve as structural components of
cell membranes; fats prevent loss of heat the body as well as serve as
padding substance of tissues and organs; some other lipids serve as
vitamins ei vitamins A,E,D,K and moreover lipoproteins serve as transport
form of cholesterol etc.Ceretain lipids such as prostaglandins serve as
local hormones. In foods lipids present as one of the main components.
The essential fatty acids such as linoleic acid and linolenicacid are to be
regularly obtained from the lipids of diets with their required amounts.
Arachidonic acid becomes essential when its precursor linoleic acid is not
sufficiently obtained from the diets.