Chemistry of

Lipids
 Lipids are organic compounds formed mainly from
alcohol and fatty acids combined together by ester
linkage.

• insoluble in water
• soluble in nonpolar organic solvents like
benzene, chloroform, ether, acetone etc
 Biomedical Importances of Lipids

 Have a high-energy value

 Supply the essential fatty acids

 Supply the body with fat-soluble vitamins (A, D, E and K).

 A subcutaneous thermal insulator against loss of body heat.

 Lipoproteins serve as the means of transporting lipids in the
blood.

 Cholesterol is used for synthesis of steroid hormones,

vitamin D3 and bile acids.

 Knowledge of lipid biochemistry is necessary to understand

many important biomedical areas eg, obesity, diabetes
mellitus, atherosclerosis etc.
 Classification of Lipids
1. Simple lipids
2. Complex lipids
3. Derived lipids
4. Miscellaneous lipids
 Simple lipids

• Ester of fatty acids with various alcohols

 O O
HO C R1 CH2 OH H2C O C R1
O
O
R2 C O C H
HO C R2 + HO C H
O
O
CH2 OH 3 H 2O H2C O C R3
HO C R3
Glycerol Triglycerides
Fatty acids (Triacylglycerol)
 Types :
a. Fat and oils (triacylglycerols):
ester of fatty acids with glycerol
b. Waxes :
ester of fatty acids with higher MW
monohydric alcohols (eg, cetyl alcohol,
cholesterol)
 Complex lipids
• Ester of fatty acids with alcohols

• Also contain additional groups like phosphate,

bases, carbohydrate, protein etc.
 Types
a. Phospholipids :
• phosphate and frequently nitrogenous
base as additional group
• Alcohol : Glycerol or sphingosine

Eg. lecithin, cephalin, plasmalogens etc

b. Glycolipids :
contain fatty acids, sphingosine (C18), carbohydrates

eg, cerebrosides, gangliosides, sulfatids, globosides

c. Lipoproteins:
Macromolecular complex made up of lipids with proteins
eg, chylomicrons, VLDL, LDL, HDL etc

d. Other complex lipids :

sulfolipids, aminolipids
 Derived lipids
• Obtained by hydrolysis of simple or
complex lipids & having the features of lipids

eg, fatty acids, monoacyl glycerol,

diacylglycerol , steroids(cholesterol) etc
 Miscellaneous lipids
• Compounds with the features of lipids

eg, Squalene, Pentacosane etc.

 Fatty acids
 Fatty acids are carboxylic acids with hydrocarbon side
chains

General formula : R- COOH

where, R = hydrocarbon chain
COOH= carboxylic acid group

eg, CH3(CH2)14COOH
• Occurrences :
It is found in two forms:
a. Ester form : fatty acids are attached to
alcohol with ester bond
b. Free form of fatty acids
 Shorthand representation of fatty acids

CH3-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH=CH-CH2-CH2-CH2-CH2-

CH2-CH2-CH2-COOH

18:1;9 or ∆918:1 or ω9,C18:1

fig . Oleic acid (octadecaenoic acid)

CH3-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-CH2-

CH2-CH2-CH2-COOH

18 : 0

fig. stearic acid (octadecanoic acid)

 Classification of fatty acids

a. Depending upon total number of carbon atoms :

1. Even chain fatty acids : they have even number of
carbon atoms in their structure(2,4,6….)
eg, acetic acid (C- 2)
palmitic acid (C-16)
stearic acid (C-18)
2. Odd chain fatty acids: They have odd number of carbon
atoms (3,5,7….) in their structure
eg, propionic acid (C-3), valeric acid (C-5)
b. Depending upon length of hydrocarbon chains:
1. Short chain fatty acids : they have 2 to 6 carbon atoms
in their structure
eg, butyric acid (c-4), caproic acid (C-6)
2. Medium chain fatty acids : they have 8 to 14 carbon
atoms in their structure
eg, capric acid (C-10), myristic acid (C-14)
3. Long chain fatty acids: they have 16-24 carbon atoms
in their structure
eg, palmitic acid (C-16)
cervonic acid (C-22)
c. Depending upon the nature of hydrocarbon
chain :
1. Saturated fatty acids: they have only single
bond in their hydrocarbon chain
eg, acetic acid CH3 – COOH
palmitic acid CH3- (CH2)14-COOH
stearic acid CH3-(CH2)16-COOH
2. Unsaturated fatty acids : they have at least
one double bond in their hydrocarbon chain
Types of unsaturated fatty acids :
a. Monounsaturated fatty acids : they have one
double bond in their hydrocarbon chain
eg, oleic acid (18:1;9)
palmitoleic acid (16:1;9)
nervonic acid (24:1;15)
b. Polyunsaturated fatty acids(PUFA): they have
two or more double bond in their
hydrocarbon chain
eg,
Linoleic acid (18:2;9,12)
α-Linolenic acid (18:3;9,12,15)
Arachidonic acid (20:4;5,8,11,14)
D. On the basis of nutritional requirments, fatty acids are classified as:
1. Essential fatty acids:
 They are not synthesised by the body and should be supplied in the
diet
They are :
 Linoleic acid (18:2;9,12)
 α-Linolenic acid (18:3;9,12,15)
 Arachidonic acid (20:4;5,8,11,14)

Occurrences of EFA : Corn, peanut, cottonseed, soybean, linseed oil,

sunflower seeds and many plant oils.
The functions of essential fatty acids are:
• Arachidonic acid synthesizes eicosanoids such
as prostaglandins, leukotrienes, lipoxins
• They decrease cholesterol level
(antiatherogenic effect)
• Alpha linolenic acid plays role in vision. It
shows action at retinal photoreceptor
• They prevent from fatty liver
2. Nonessential fatty acids : these can be
synthesized in body and therefore, need not
be supplied in the diet.
Eg, Palmitic acid, stearic acid
 Importances of fatty acids
• They are the components of various lipids
• Fatty acids undergo oxidation to provide
energy to human body
• They are the component of membranes
• PUFAs lower cholesterol level.
Isomerism in unsaturated fatty acids
 ω- family of unsaturated FA
• ω3 family - a-linolenic acid (18:3;9,12,15)

• ω6 family - linoleic acid (18:2;9,12)

• ω9 family - oleic acid (18:1;9)

Significances of PUFAs:
 helps in excretion of cholesterol
(Antiatherogenic effect)

Arachidonic acid forms prostaglandins,

thromboxanes

α-Linolenic acid helps in vision (shows action

at retinal photoreceptor)
 Steroids
• Cyclopentanoperhyd-
rophenanthere (CPPP)
ring

• Eg, cholesterol, bile

acids, vitaminD , sex
hormones, ergosterol,
sitosterol etc.
 cholesterol

MW : C27H45OH
• Cholesterol is the major animal steroid (sterol)
• It consists of CPPP (cyclopentanoperhydro
phenanthrene) ring, one –OH group at C3 ,
double bond between C5 & C6 and eight
carbon containing side chain at C17.
 Sources of cholesterol
• Endogenous source : acetyl coA

• Exogenous sources : meat , egg , butter , milk

etc.
 Functions of cholesterol
• It is Component of membranes (mainly
nervous tissue)
• Synthesize bile acids, vitaminD, sex
hormones, hormones of adrenal cortex.
• It is an insulating cover of nerve fibers
• It constitutes the structure of various
lipoproteins
 Clinical correlation: Cholesterol
• High plasma cholesterol : risk for
cardiovascular disorders

• Cholesterol, if not solubilized in bile, may form

cholesterol rich gall stones
 TRIACYLGLYCEROL
(triglycerides/ fat)

They are made up of three fatty acids attached to one glycerol by

ester bond.
They are stored in the adipocytes of adipose tissue in the
subcutaneous tissue and in the abdominal region.
• OCCURRENCES : meat, egg, ghee, butter,
fish, oil etc
 Types of TAG
• Simple TAG : they have same type of fatty
acids in their structure

• Mixed TAG : they have usually saturated

fatty acid at C-1, unsaturated fatty acid at C-2
and either saturated or unsaturated fatty acid
at C-3.
 Properties of TAG
1. Melting point :
- TAG containing saturated fatty acid is solid at room
temperature and
-TAG containing unsaturated fatty acid is liquid at room
temp.
2. Hydrolysis : TAG undergoes hydrolysis by
- lipase
- strong acids
- strong alkali (NaOH, KOH)
3. Saponification :
hydrolysis of TAG by alkali is called
saponification
4. Rancidity :
The deterioration of fats and oils to give
unpleasant taste and odour is called rancidity.
 Functions of TAG
• It is the storage form of energy
• It provides energy to human beings (9kcal/gm)
 Clinical correlation : TAG

• Accumulation of fat leads to : OBESITY

• High plasma TAG : risk for cardiovascular

disorder
Tests to check the purity of fats/oil
1. Iodine number:
The number of grams of iodine absorpbed by 100gm of
fats/oil

Importance:
Determines the content of unsaturated fatty acids
present in fat
Example: Iodine number of : butter 25-28 and
sunflower oil : 125-135
2. Saponification number:
The number of mg of KOH required to saponify one
gram of fat/oil.
Importance:
It is a measure of average molecular size of fatty acids.
Example: saponification number of –
Human fat : 195-200
Butter : 230-240
coconut oil : 250-260
3. Reichert- Meissel (RM) number:
The number of mL of 0.1 N KOH required to
completely neutralise soluble volatile fatty acids
distilled from 5gm fat/oil

Importance :
Useful to check the adulteration of fats/oil
Example : RM number of –
Edible oil : <1 ; Butter : 25-30
4. Acid number :
The number of mg of KOH reuired to completely
neutralise free fatty acids present in one gram of
fat or oil
Importance : It helps to assess whether fat/oil is
safe for human consumption or not
 LIPOPROTEINS

 they are macromolecular complexes of lipids & proteins

 They help in the transport of lipids

 Types of lipoproteins
1. Chylomicrons:
 Carries TAG(triacylglycerol) from small intestine

2. VLDL (very low density lipoprotein) :

 Carries TAG from liver to other tissues

3. LDL (low density lipoprotein) :

 It carries cholesterol to liver & extrahepatic tissue
 It is called bad cholesterol because its high concentration may cause
cardiovascular disease

4. HDL (high density lipopotein) :

 It carries cholesterol from extrahepatic tissue to liver for degradation
 It is called good cholesterol because its high concentration prevents from
cardiovascular disease
 Phospholipids
• They contain fatty acids and
alcohol along with phosphate
& frequently nitrogenous
bases as additional group

• It is an amphipathic molecule
 Types of phospholipids
two types :
1. Glycerophospholipids : they contain glycerol
as alcohol

2. Sphingophospholipids : they contain

sphingosine as alcohol
 1. Glycerophospholipids
examples :
a. Phosphatidic acid
(phosphatidate):
 It is the simplest
phospholipid
 It is made up of glycerol,
two fatty acids, phosphate

Importance:
 It acts as an intermediate
compound in phospholipid
biosynthesis
b. Phosphatidyl choline (lecithin)

It consists of glycerol, two fatty

acids, phosphate and choline

Importances of lecithin:
• It is the most abundant
phospholipid of cell membrane

• Dipalmitoyl lecithin : - it is the

component of surfactant in
lungs alveoli and prevents from
the collapse of lugs alveoli
c. Phosphatidyl ethanolamine(cephalin)

• It consists of glycerol, two

fatty acids, phosphate,
ethanolamine

Importances:

• It is the Component of
biomembranes
d. Phosphatidyl serine

• It consists of glycerol,
two fatty acids ,
phosphate, serine

Importances:
• It is the component of
biomembranes
e. Phosphatidyl inositol
• It consists of glycerol, two fatty
acids, phosphate, myoinositol
Importances:

• Phosphatdyl inositol 4,5 –

bisphosphate is an important
component of cell membrane

• Phosphatdyl inositol 4,5 –

bisphophate is cleaved into
Diacylglycerol and Inositol
triphosphate which help in the
action of some hormone
f. Plasmalogens

• It consists of glycerol, fatty

acid, Unsaturated fatty
alcohol, phosphate and
X(choline or etahanolamine
or serine or inositol)
Importances:
• It constitutes as much as
10% phospholipids of brain
and also a major
component of heart muscle
 g. Cardiolipin (diphosphatidyl glycerol)

O OH
• It consists of glycerol and
O
CH2 O C R1 CH2 O P O
O
CH2
two phosphatidate
R2 C O C H H C OH H C O C R3
O
O
CH2 O P O CH2 R4 C O CH2
OH O
Cardiolipin

Importance :
• It constitutes a major lipid
of mitochondrial membrane
 2. Sphingophospholipids
Sphingomyelins :
Ceramide

Sphingosine
Fatty acid
OH O
CH3 (CH2)12 CH CH CH CH NH C R1

CH2 Choline
O CH3
O P O CH2 CH2 N
+ CH3

OH CH3
Phosphate
Sphingomyelin

It consists of sphingosine, fatty acid,

phosphate, choline.

Importance:
It constitutes the myelin sheath of
neurons
 Clinical correlation : phospholipids
 Lecithine: sphingomyelin (L:S ratio) :
 determined in amniotic fluid
 Prediction of fetal lungs maturity

 L:S ratio : 2 or more (indicates proper fetal lungs maturity)

 L:S ratio : 1.5-1.9 (40% risk for respiratory distress syndrome)

 L:S ratio : <1.5 (75% risk for respiratory distress syndrome)

 GLYCOLIPIDS
• It is made up of Sphingosine (alcohol) , fatty
acid and carbohydrate
 Types of glycolipids
1. Cerebrosides
(sphingosine +Fatty acid + glucose/galactose)

2. Sulfatids
(sphingosine + FA + sulfated galactose)
3. Globosides
(sphingosine+FA + two or more sugars)
4. Gangliosides

sphingosine +FA + { two or more sugars +

N-acetyl neuraminic
acid(NANA)}
 Functions of glycolipids
• It is a major component of nervous tissue
• It helps in cell-cell interaction
• It is highly antigenic & found in tumor
antigens, blood group antigens
• It acts as receptor for toxic agents & some
pathogens
 EICOSANOIDS
• Types
1. Prostanoids :
prostaglandins (PGs)
prostacyclins (PGIs)
thromboxanes (TXs)
2. Leukotrienes (LTs)
3. Lipoxins (LXs)
 Biosynthesis of Eicosanoids

Arachidonic acid
Lipoxygenase cycloxygenase

Leukotrienes prostaglandins
Lipoxins prostacyclin
thromboxanes
PROSTAGLANDINS(PGs)
TYPES OF PGs:
PGA ; PGB; PGD; PGE ; PGF; PGG; PGH; PGI

Series of PGs:

• Series I : C13=C14 eg, PGE1

• Series II : C13=C14 C5=C6 eg, PGE2
• Series III : C13=C14 C5=C6 C17=C18 eg, PGE3
 FUNCTIONS OF PROSTANOIDS(PROSTAGLANDINS)

1. Effect on CVS :
• Prostacyclin (PGI2) :
vasodilator & inhibit platelet aggregation

• TXA2 : vasoconstrictor & stimulate

platelet aggregation
2. Effect on uterus :
PGE2 & PGF2 : stimulate uterine muscle
contraction
3. Effect on GI tract :
PGE2 : inhibits gastric acid secretion & stimulates
intestinal motility
4. Metabolic effects :
- inhibits lipolysis
- stimulates calcium mobilization
- stimulate glycogen synthesis
5. Effect on respiratory tract :
• PGF is bronchoconstrictor
• PGE is bronchodilator

6. Effect on immunity & inflammation :

• PGE2 & PGD2 produce inflammation by increasing capillary
permeability
• PGE2 reduces both T & B cell functions.