1

DEPARTMENT OF BIOCHEMISTRY AND MOLECULAR BIOLOGY

FACULTY OF LIFE SCIENCE
FEDERAL UNIVERSITY OF DUTSIN-MA, KATSINA STATE

Lecture notes on BCH 201

Course Lecturer: Dr. M. Osibemhe
E-mail: mosibemhe@fudutsinma.edu.ng

TOPIC: CHEMISTRY AND STRUCTURES OF FATTY ACIDS AND LIPIDS

INTRODUCTION

Lipids

Lipids are heterogeneous group of compounds that may be defined as relatively insoluble in
water, but freely soluble in organic solvents such as acetone, chloroform, benzene, ether, e.t.c.
they are of great importance to the body as they serve several functions such as:

• Storage form of energy(triglycerides)

• Structural components of biological membranes (Phospholipids and Cholesterol)

• Metabolic regulators (steroid hormones and prostaglandins)

• Provides insulation against changes in external temperature (subcutaneous fat)

• Acts as detergents and emulsifying agents (amphipathic lipids)

• Protect internal organs by providing a cushioning effect (pads of fat)

• Help in absorption of fat soluble vitamins.(Vitamins A,D,E and K)

• Give shape and smooth appearance to the body

• Improve taste and palatability of food

 2

Classification of Lipids

Lipids can be classified on the basis of their chemical nature into four groups: Simple lipids,
Compound or Complex lipids, Derived lipids, and other complex lipids. They could also be
classified on the basis of their functions into different categories such as: Storage lipids,
Structural lipids, and other lipids that perform other diverse functions.

Simple lipids: they are esters of fatty acids with alcohols. The alcohol could be glycerol or other
higher alcohols. They are of two main types;

• Fats and Oils (triacylglycerol): fats are ester of fatty acids with glycerol. Oil is
fat in the liquid state.
• Waxes: esters of fatty acids with long-chain alcohol other than glycerol

Compound or Complex lipids: they are esters of fatty acids with alcohol containing other
groups. Depending on these extra groups, they are sub-classified as:

(A) Phospholipids: they contain phosphoric acid in addition to fatty acid and alcohols. They
are subdivided into:

(i) Glycerophospholipid: this group contains glycerol as its back bone

(ii) Sphingophospholipids: this group contains sphingosine as its back bone

(iii) Plasmalogens: these are phospholipids which have an aliphatic long chain unsaturated
alcohol in ether linkage with the first hydroxyl group of glycerol. The second OH group is
esterified to fatty acid. The phosphoric acid is attached to choline or ethanolamine

(B) Glycolipid: they belong to a general class of sphingolipids; containing fatty acid, simple
sugar or complex oligosaccharide. Sphingosine is the back bone in this group. They lack
phosphate group and glycerol. They are called glycosphingolipids. e.g cerebrosides,
globosides and gangliosides.
 3

(C) Lipoproteins: Lipoproteins are formed by combination of lipid with protein

Derived lipids: they are compounds which are derived from lipids. E.g: Fatty acids, steroids,
eicosanoids , terpenes etc.

Other complex lipids: Lipids such as sulfolipids and aminolipids

Fatty Acids

They are carboxylic acids with hydrocarbon chain. They are the simplest form of lipid (derived
lipid) and are generally found in ester linkage in the different classes of lipids. They have general
formula R-COOH. Fatty acids that occur in natural fats are usually straight-chain derivatives,
containing even numbers of carbon atoms. The chain may be saturated or unsaturated.

• Saturated fatty acids: contain no double bond

• Unsaturated: contains one or more double bonds

Unsaturated fatty acids may further be divided into:

• Monounsaturated: fatty acids with one double bond

• Polyunsaturated: contains two or more double bonds

The double bonds in polyunsaturated fatty acids are separated by at least a methylene group –
CH2 and are never conjugated (alternation of double and single bond). The configuration of the
double bond of all naturally occurring fatty acids are usually in cis-form. Trans fatty acids are
produced by fermentation in the rumen of dairy animals and are obtain from dairy products and
meat. They are generally considered to be injurious to health.

Nomenclature of Fatty Acids

The systematic name for a fatty acid is derived from the name of the parent hydrocarbon. The
saturated fatty acids end with the suffix -anoic (E.g the C18 saturated fatty acids is called
octadecanoic acid because the parent hydrocarbon is octadecane) while the unsaturated fatty
 4

acids end with the suffix-enoic (the C18 with one double bond is called octadecenoic acid and
that which contains two double bonds is called octadecadienoic acid and those with three double
bonds are named octadecatrienoic acid. The notation 18:0 denotes a C18 fatty acid with no
double bonds whereas 18:2 signifies 18-carbon fatty acid containing two double bonds. Carbon
atoms are numbered from the carboxyl carbon as number 1. The carbon atoms adjacent to the
carboxyl carbon (Nos. 2, 3, and 4) are also known as the α, β, and γ carbons, respectively, and
the terminal methyl carbon is known as the  or n-carbon. The position of a double bond is
represented by the symbol delta(∆), followed by a superscript number. E.g. C18 containing two
double bonds at position nine and twelve is written as; 18:2∆9,12 or 18:2;9,12.

Properties of Fatty Acid

• Melting point increases with increasing carbon number

• Melting point of a saturated fatty acid is higher than an unsaturated fatty acid with the
same number of carbon.

• Double bonds lower melting point relative to saturated fatty acid

• The fluidity of fatty acids and their derivatives is enhanced by short chain length and
unsaturation. i.e the shorter the chain and more degree of unsaturation the lower the
melting point.
 5

TABLE 1

Adapted from Garrett and Grisham, 1999

Simple Lipids

Fats and Oils (triacylglyceride): they are esters of glycerol with fatty acid. They are also called
triglycerides or neutral fats. Mono- and Diacylglycerol, wherein one or two fatty acids are
esterified with glycerol, are also found in tissues. Triacylglycerol could be simple or mixed;

1. Simple triglyceride: contains the same type of fatty acids in all the OH group of the
glycerol. For example, when the fatty acid in the three position is 18:0; it will be named
tristearin.
 6

2. Mixed triglycerides: contains different fatty acid on the OH group of glycerol. Usually,
the OH group at position two is esterified to a polyunsaturated fatty acid. In the naming
of mixed triglyceride, the position and name of each of the fatty acid must be stated.

Formation of Triacylglycerol

Properties of Triglyceride

• Hydrolysis: Triacylglycerols undergo hydrolysis by acid catalyst or broken down by

lipase, a digestive enzyme to liberate free fatty acids and glycerol.
Triacylglycerol
 7

• Saponification: hydrolysis of triglycerides by alkali (NaOH or KOH) to produce

glycerol and soap.

• Rancidity: the deterioration of fats and oils resulting in an unpleasant taste and smell.

Hydrolytic rancidity: occur as a result of partial hydrolysis of triacylglycerol by

enzymes.
 8

Oxidative rancidity: occur as a result of the oxidation of unsaturated fatty acids

with the resultant formation of unpleasant products such as dicarboxylic acids,
aldehydes, ketones etc.

• Lipid peroxidation: triacylglycerols can also undergo oxidation in vivo-lipid

peroxidation in living cells, to produce peroxides and free radicals that can damage the
tissue. These free radicals are believed to be implicated in various kinds of diseases,
ranging from inflammation, ageing, cancer, and atherosclerosis.

Antioxidants are usually added to food (as preservatives) to prevent oxidative rancidity.
Butylated hydroxyanisole (BHA) and Butylated hydroxytoluene (BHT) are synthetic
antioxidants use in food preservation. Other natural antioxidants such as vitamin E (tocopherols)
could also be used. The natural antioxidants present in the body helps to prevent the effects of
free radicals in living cell.

Test for the Purity of Fats and Oil

• Saponification number: number of mg of KOH required to saponify the free and

combined fatty acids in 1 g of a given fat. It is a measure of the molecular weight of fat.
The value is higher for fats containing short chain fatty acids.

• Iodine number: number of grams of iodine absorbed by 100 g of fat or oil. It is a

measure of the degree of unsaturation present in the fat.

• Acid number: number of mg of KOH required to neutralize the fatty acids in a gram of
fat. In normal circumstances, refined oils should be free from any free fatty acids.
Presence of free fatty in such oil is an indication of rancidity. It is a measure of the degree
of rancidity.

• Reichert-meissl number: number of ml of 0.1N KOH required to neutralize the soluble

volatile fatty acids distilled from 5 g of fat. It is a measure of the amount of soluble
volatile fatty acids present in a given fat. The test is used to measure the purity of butter.
 9

Butter contains high amount of volatile soluble fatty acids. E.g butyric acid, caproic acid
etc.

Waxes

Biological waxes are ester of long-chain fatty acids with long-chain alcohols other than glycerol.
Their melting point is generally higher than those of triacylglycerol. Waxes also serve a diversity
of other functions related to their water-repellent properties and their firm consistency. Birds,
particularly waterfowl, secrete waxes from their preen glands to keep their feathers water-
repellent. Biological waxes find a variety of applications in the pharmaceutical, cosmetic, and
other industries. Lanolin (from lamb’s wool), beeswax, carnauba wax (from a Brazilian palm
tree), and wax extracted from spermaceti oil are widely used in the manufacture of lotions,
ointments, and polishes.

Compound Lipids

Compound lipids are esters of fatty acids with alcohol and in addition contain other groups.
Depending on these extra groups, they are sub-classified as

(A) Phospholipids: they are lipids that contain in addition to fatty acids and glycerol or
other alcohol, a phosphoric acid. They are subdivided into
(i) Glycerophospholipids or phosphoglycerides: is a 1,2-diacylglycerol that has a
phosphate group esterified at carbon atom 3 of the glycerol back bone. They contain
glycerol as their back bone, two fatty acids esters and a phosphoric acid esterified
with an alcohol.
 10

They are amphipathic molecules containing a polar head (phosphoric acid end) and a
hydrophobic portion (fatty acids end). The most common is phosphatidic acid. Other examples
are:

• Phosphatidylcholine(Lecithin)
• Phosphatidylethanolamine(Cephalin)
• Phosphatidylserine
• Phosphatidylinositol
• Plasmalogen
• Lysophospholipid(Lysolecithin)
• Phosphatidyl glycerol
• Diphosphatidyl glycerol(Cardiolipin)
11
 12

(ii) Sphingophospholipid: this group of lipid contains a sphingosine as the back bone, a fatty
acid esterified in an amine linkage to form a ceramide, and an alcohol usually choline or
ethanolamine attached to a phosphate group. They belong to a class of sphingolipids. An
example is sphingomyelin.
 13

(iii)Plasmalogens: these are phospholipids which have an aliphatic long chain alcohol in
ether linkage with the first hydroxyl group of glycerol. The second OH group is
esterified to fatty acid. The phosphoric acid is attached to choline or ethanolamine

Plasmalogen containing a phosphoethanolamin

(B) Glycolipids (glycosphingolipids): Lipids containing a fatty acid, sphingosine, and

carbohydrate. They lack phosphate and are uncharged. They are divided into three subgroups:
Cerebrosides, Globosides and Gangliosides.
l
➢ Cerebrosides have a single sugar linked to ceramide; those that contain galactose sugar
on the OH at the C1 of ceramide are called galactocerebrosides whereas those with
glucose attached to the OH at the C1 of ceramide are called glucocerebrosides.
 14

Structure of galactosylceramide (galactocerebroside, R = H), and sulfogalactosylceramide

(a sulfatide, R = SO42–).

➢ Globosides are neutral (uncharged) glycosphingolipids with two or more

sugars(oligosaccharides), usually D-glucose, D-galactose, or N-acetyl-D-galactosamine.

Lactosylceramide

➢ Gangliosides are the most complex sphingolipids which have oligosaccharides as their
polar head groups and one or more residues of N-acetylneuraminic acid (NANA), a sialic
acid.
 15

( C ) Lipoproteins-They are lipids complex with proteins. They serve as means of transporting
lipids in blood. Four major types are identified, namely chylomicrons, very low density
lipoprotein (VLDL), low density lipoprotein (LDL), and high density lipoprotein (HDL).
Free fatty acids-albumin complex is also a type of lipoprotein for the transport of free fatty acids.

Text Books:

1. Nelso D.L, Cox. M. M. (2009). Lehninger’s .Principle of Biochemistry. 6th ed. Freeman.
2. Satyanarayana U. and Chakrapanin U. (2007). Biochemistry. 3rd ed. Arunabha Sen, Kolkata.
3. Naik, P & Pawar, V. (2012). Essentials of Biochemistry (1st ed) India:Jaypee Brothers Medical
Publishers.
4. Garrett R. H. and Grisham C.M. (1999). Biochemistry. 2nd ed. Thomson Brooks/Cole
5. Voet and Voet (2010) Biochemistry.4th ed, John Wiley.