CHEMISTRY OF LIPID-I

(Introduction, fatty acids)

Manoj Sigdel
Asst. professor
Department of biochemistry
MCOMS, Pokhara
Lipids
• Heterogenous group of organic molecules including
fats, oils, steroids and related compounds which are
relatively insoluble in water and soluble in organic
solvents such as ether, chloroform, benzene, acetone
etc.
Bloor’s Criteria
Lipids are compounds having the following
characteristics:
Insoluble in water
Solubility in one or more organic solvents, such as
ether, chloroform, benzene, acetone etc.
Some relationship to the fatty acids as esters either
actual or potential
Possibility of utilization by living organisms
 Classification Lipids

Simple lipids Compound lipids Derived lipids

Fatty acids

Mono &
Diacylglycerols
Waxes Fat & Oils
(Triacyglycerols) Alcohols

Miscellaneous
Phospholipids Lipoproteins
Hydrocarbons

Other complex lipids Carotenoids

Glycolipids
Squalene
Simple lipids
Esters of fatty acids with various alcohols

• Fats and oils : Esters of fatty acids with glycerol

Oil is a liquid while fat is a solid at room temp
Waxes:
• Esters of fatty acids (usually long chain) with alcohols
other than glycerol.
• Example: Cetyl alcohol : is a fatty alcohol with the
formula CH3(CH2)15OH
Complex lipids
Esters of fatty acids with alcohols containing additional
groups such as phosphate, nitrogenous base
carbohydrate, protein

i. Phospholipids : Lipids containing, in addition to fatty

acids and an alcohol, a phosphoric acid residue. Usually
have nitrogen containing bases and other substituents,
Examples:
a. glycerophospholipids : the alcohol is glycerol eg;
lecithin, cephalin and
b. sphingophospholipids: the alcohol is sphingosine eg;
sphingomyelin
II) Glycolipids (glycosphingolipids) : Lipids containing a
fatty acid, sphingosine, and carbohydrate
Example: Cerebrosides, Gangliosides

III) Other complex lipids: Lipids such as sulfolipids ,

lipopolysaccharides , aminolipids, Lipoproteins
Precursor and derived lipids:
• Include - fatty acids, glycerol, steroids, other alcohols,
fatty aldehydes, and ketone bodies, hydrocarbons,
lipid-soluble vitamins, and hormones

• Acylglycerols (glycerides), cholesterol, and cholesteryl

esters are uncharged, so they are termed as neutral
lipids
 Function of lipids
Storage form of energy (Triacylglycerol)

Constituents of membrane structure and regulate

the membrane permeability (phospholipids and
cholesterol)
Are important as cellular metabolic regulators
(steroid hormones and prostaglandins)
Act as surfactants, detergents & emulsifying agents
• Provide insulation against changes in external
temperature
• Protect the internal organs, serve as insulating
materials and give shape and smooth appearance to
the body
• Help in absorption of fat soluble vitamins.
• Improve taste & palatability of food

• Lipoproteins, which are complexes of lipids and

proteins are involved in the transport of lipids in
the blood and are also components of cell
membrane
• Lipids present in myelinated nerves act as insulators
for propagation of depolarization wave
• A knowledge of lipid biochemistry is important in
understanding many current biomedical areas of
interest, eg;
– obesity
– Atherosclerosis
– Myocardial infarction (heart attack)
– role of various polyunsaturated fatty
acids in nutrition and health
 Fatty Acids
Aliphatic carboxylic acids,

General formula, R-CO-OH

Depending on the R group (hydrocarbon chain), the

physical properties of fatty acid may vary
Occurrence: esterified & free (unesterified) form

Animal origin are much simpler in structure in

contrast of plant origin which often contain groups
like keto, hydroxy, cyclopentane rings
 Classification of fatty acids
I. Depending on total number of carbon atoms

1. Even chain fatty acids:

 having carbon atoms 2,4,6 & series
Example: Acetic acid (CH3COOH)
Butyric acid (C3H7COOH)
Caproic acid (C5H11COOH)
Palmitic acid (C15H31COOH)
2. Odd chain fatty acids:
 having carbon atoms 3,5,7 etc
Seen in microbial cell walls & also present in milk
Example: Propanoic (C2H5COOH)
II. Depending on the length of hydrocarbon chain

• Short chain = 2-6 carbons

• Medium chain = 8-14 carbons

• Long chain = 16-22 carbons,

• Very long chain fatty acids: 24 & above carbons

III. Depending on the nature of hydrocarbon
chain
Saturated fatty acids

Unsaturated fatty acids

Branched chain fatty acids (e.g. isovaleric acid)

Hydroxy fatty acids (e.g. cerebronic acid)

 Saturated Fatty Acid
• Contain single bond, no double bond

• General formula: CH3-(CH2)n-COOH

Example: acetic acid : CH3-COOH

butyric acid: CH3-(CH2)2-COOH
palmitic acid: CH3-(CH2)14-COOH
stearic acid: CH3-(CH2)16-COOH
Important metabolic intermediates: Acetic acid & butyric
acid
Most abundant in body fat: palmitic acid & stearic acid

Carbon atoms of fatty acids are numbered as C1,C2,

….starting from the COOH group

Starting from the methyl end, the carbon atoms may be

numbered as omega-1,2,3….
 Unsaturated Fatty Acid
• contains one or more double bonds

• One double bond = monounsaturated fatty acid

• Two or more double bonds = poly- unsaturated

fatty acid
• Monounsaturated and polyunsaturated fatty
acids don’t stack compactly and are liquid at
room temperature
Example: Oleic acid (C17H33OOH)

Example: Linoleic acid (18:2;9,12)

Linolenic acid (18:3;9,12,15)
Arachidonic acid (20:4;5,8,11,14)
• Omega 3

• Omega 6

• Omega 9
 Nomenclature of Unsaturated Fatty Acids

5 3 1COOH
17 15 13 11 9 7

18 16 14 12 10 8 6 4 2

Number of Double Bonds

Carbon Chain Length Position of Double Bonds

18:3 ( 9, 12, 15)

The most commonly occurring fatty acids have even number of

carbon atoms in an un-branched chain of12-24 carbons
 General Patterns of Double Bonds
• The most common positions for double bonds are
Δ9, Δ12, and Δ15.
• The double bonds of polyunsaturated fatty acids are
separated by methyl group:
-CH=CH-CH2-CH=CH-
• In almost all the naturally occurring unsaturated
fatty acids, the double bonds are in Cis- configuration
 Two types of bond formation
• CIS: hydrogens on the carbons joined by a double
bond are on the same side = the carbon chain is bent
• TRANS: hydrogens on the carbons joined by a
double bond are on the opposite side = the carbon
chain is straighter
 Isomerism
Two types of isomers can occur in an unsaturated fatty acid

1. Geometrical isomers: cis and trans

Cis isomers have a curved configuration.

Trans isomers have a linear configuration.

Due to curve configuration cis unsaturated fatty acids

have a lower melting point as compared to their trans
counterpart.
Most of the natural unsaturated fatty acids have cis double
bonds
Example: Oleic acid & Elaidic acid [ C17H33COOH]
2. Positional isomers:
• variation in the location of the double bond
along the unsaturated fatty acids chain produces
isomer of that compound
• Oleic acid have 15 different positional isomers
The Packing of Fatty Acids
 Essential fatty acids
The fatty acids that can not be synthesized by the
body, & therefore, should be supplied in the diet
is known as essential fatty acids
Chemically, they are polyunsaturated

Example:
- Linoleic acid (18:2,9,12)
- Linolenic acid (18:3,9,12,15)
- Arachidonic acid (20:4,5,8,11,14)
Functions of EFA
– Maintain membrane structure and function
– Transport of cholesterol
– Formation of lipoproteins
– Prevention of fatty liver
– Synthesis of eicosanoids

Deficiency of EFA results in phrynoderma or toad skin

Properties of fatty acids
1. Hydrogenation
2. Halogenation
3. Melting point
4. Salt formation
5. Ester formation
6. Oxidation of fatty acids
Hydrogenation
• Unsaturated fatty acids may be converted to the
corresponding saturated fatty acids by
hydrogenation of double bonds
• Eg:
+2H +2H +2H
Linolenic Lenoleic Oleic stearic

• Hydrogenation of oils can lead to solidification and

saturation eg: Vanaspathi
Halogenation
• When treated with halogens under mild conditions,
the unsaturated fatty acids can take up two halogen
atoms, at each double bond to form the
halogenated derivative of the fatty acid

• Eg:
Oleic acid + I2 Di-iodo oleic acid

• The number of halogen atoms taken up will depend

on the number of double bonds and is an index of
the degree of unsaturation.
Melting point
• The short and medium chain fatty acids are liquids
where as long chain fatty acids are solids at 25oC
• The solubility in water decreases, while melting and
boiling points increase, with increase in chain
length
• The unsaturtaed fatty acids have lower melting
point compared with saturated fatty acids with the
same chain length
• Eg: stearic acid (C18, no double bond) has the
melting pont 69oC
- Oleic acid (c18, 1 double bond) has 13oC
- Lenoleic (C18, 2 double bond) has -5oC
- Lenolenic (C18, 3 double bond) has -10oC
Salt formation
• Saturated and unsaturated fatty acids form salts
with alkali
• Sodium and potassium salts of long chain fatty acids
are called soaps
• Calcium and magnesium soaps are insoluble and
Calcium soaps are used in grease
• Akyl sulfonate and akyl sulfate are used as
detergents
Ester formation
• Both saturated and unsaturated fatty acids form
esters with alcohols, especially with glycerol

• Fatty acids can form mono, di, or tri esters with

alcohol groups of glycerol
Oxidation of fatty acids
• All the fatty acids undergo oxidation in the body to
give energy
• Beta oxidation is the major process by which acids
are oxidized
• However, the unsaturated fatty acids can undergo
auto oxidation, due to the presence of the highly
reactive double bonds.