Lipids

Lipids (Greek: lipos, means fat) - are heterogeneous class of

naturally occurring organic substances which are insoluble in
water and highly soluble in organic solvents like ether,
chloroform, benzene and acetone.
Chemically LIPIDS are various types of esters of different alcohols.
In addition to alcohol and fatty acids, some of the lipids may
contain phosphoric acid, nitrogenous base and carbohydrates.
Bloors Criteria
According to Bloor, lipids are compounds having the following
characteristics:
They are insoluble in water BUT soluble in organic solvents, such
as ether, chloroform, benzene, acetone, etc.
 Lipids
Lipids include fats, oils, waxes and related
compounds.

An oil is a lipid which is liquid at ordinary temperature.

Distinction between fats and oils is a purely physical

one.

Chemically they are all esters of glycerol with higher

fatty acids.
 Classification of lipids
1. Simple Lipids

Esters of fatty acids with various alcohols. They include:

(a)Neutral fats (Triacylglycerol, TG): These are triesters of fatty acids

with glycerol.

(b) Waxes are esters of fatty acids with higher alcohols.

2. Compound Lipids

()Esters of fatty acids containing groups, other than in addition, to an

alcohol and fatty acids.
 Classification of lipids
(a) Phospholipids: They are fats containing in addition
to fatty acid and glycerol, a phosphoric acid residue, a
nitrogenous base and other substituents. Examples:
phosphatidyl choline (Lecithin), phosphatidyl
ethanolamine (Cephalin) etc.
 Classification of lipids
(b) Glycolipids: Lipids containing carbohydrate moiety
are called glycolipids. These are of two types:
Cerebrosides, Gangliosides

(c) Sulpholipids: Lipids characterised by possessing

sulphate groups.

(d) Aminolipids (Proteolipids)

(e) Lipoproteins: Lipids as prosthetic group to

 Classification of lipids
3. Derived Lipids

These are obtained by hydrolysis of those given in group I and II,

which still possess the general characteristics of lipids.

(a) Fatty acids may be saturated, unsaturated or cyclic.

(b) Monoglycerides (Monoacylglycerol) and Diglycerides

(Diacylglycerol).

(c) Alcohols: Cholesterol and other steroids including Vit D.

 Fatty acids
Fatty acids are carboxylic acids with hydrocarbon chains ranging from
4 to 36 carbons long (C4 to C36).

Saturated FA: Those which contain no double bonds.

Unsaturated FA: Those which contain one or more double bonds.

(a) Saturated FA: Their general formula is CnH2n+1 COOH Examples:

Acetic acid CH3COOH, Propionic acid C2H5COOH and Butyric acid

C3H7COOH
 Fatty acids
(b) Unsaturated FA: They are classified further
according to degree of unsaturation.
(1) Mono unsaturated fatty acids: They contain one
double bond. Their general formula is Cn H2n1 COOH
Example: Oleic acid C17H33 COOH is found in nearly all
fats (formula 18 : 1; 9).
(2) Polyunsaturated fatty acids: There are three
polyunsaturated fatty acids of biological importance.
Linoleic acid , Linolenic acid, Arachidonic acid
 Fatty Acids
Stearic acid, an 18-carbon saturated fatty acid
 Fatty Acids

Oleic acid, an 18-carbon monounsaturated fatty acid

 Nomenclature of FA
According to standard nomenclature, Carbon atoms are numbered
from the COOH carbon (carbon No. 1).

The carbon adjacent to COOH gr. i.e. carbon number 2 is known as

-carbon, carbon atom 3 is -carbon and the end CH3 carbon is
known as the -carbon (Omega carbon).

A widely used convention is to express the fatty acids by a formula

to indicate the no. of carbon atoms, no. of double bonds and position
of double bond.
 Nomenclature of FA
The () sign is used for double bond, e.g. 9 denotes
double bond between 9 and 10 C.

For example oleic Acid (mol. formula C17H33 COOH)

has one double bond between C9 and C10, thus: 18: 1
9
 Nomenclature of FA
For polyunsaturated fatty acids (PUFAs), an alternative
convention is used.

The carbon of the methyl group is called the (omega)

carbon and is given the number 1.

In this convention, PUFAs with a double bond between C-3

and C-4 are called omega-3 fatty acids, and those with a
double bond between C-6 and C-7 are omega-6 fatty acids.
Nomenclature of FA
 Isomerism
Two types of isomers can occur in an unsaturated fatty acid.

(a) Geometric Isomers: They depend on the orientation of the

radicals around the axis of the double bonds. If the H are on the same
side of the bond, it is called as cis form. If the H are on the opposite
side, a trans form is produced. Cis form is comparatively unstable
and is more reactive.

Example: Oleic acid and elaidic acid both have same molecular
formula C17H33COOH.
Isomerism
Trans and cis-Fatty Acids
 Isomerism
(b) Positional Isomers: A variation in the location of
the double bonds along the unsaturated fatty acids chain
produces isomer of that compound.
Isomerism
 Physical Properties of FA
Melting point: MP of saturated fatty acids increases with increase in
the no. of carbon atoms in the chain. For example the MP of butyric
acid is 8C, Palmitic acid is 62C and that of Stearic acid it is 70C.

Higher the degree of saturation and higher the chain length, higher
will be the MP.

Solubility: Solubility of a fatty acid increases with increase in the

double bond.In contrast as the chain length increses, the solubility
decreses due to increase in no. of Methylene groups.
 Chemical properties of Fatty
acids
1. Formation of salts: Fatty acids form salts with alkali
and alkaline earth metals. Salts of Na, K, Ca and Mg are
soaps. Sodium and potassium salts are soluble while
calcium and magnesium salts are insoluble in water.
2. Formation of detergents: Reduction of COOH group
of fatty acids produces alkyl alcohols which can be
sulfated to form alkyl sulfates which act as detergents.
 Chemical properties of Fatty
acids
3. Formation of esters: Fatty acids in combination with
alcohol form esters. Mono, di and tri glycerides are
examples.
 Chemical properties of Fatty
acids
4. Formation of eicosanoids: Prostaglandins and related
compounds are called eicosanoids.

All eicosanoids are derived from arachidonic acid (20:4(

5,8,11,14)), the 20-carbon polyunsaturated fatty acid from
which they take their general name (Greek eikosi, twenty).

There are three classes of eicosanoids: prostaglandins,

thromboxanes, and leukotrienes.
 Chemical properties of Fatty
acids
The eicosanoids are considered paracrine or "local hormones."
They have specific effects on target cells close to their site of formation.

They are rapidly degraded, so they are not transported to distal sites within the
body.

Prostaglandins (PG) contain a five-carbon ring originating from the chain

of arachidonic acid.

Their name derives from the prostate gland, the tissue from which
they were first isolated by Bengt Samuelsson and Sune Bergstrm.
 O
PGE2
COOH
(prostaglandin E2)
is an example of a HO
OH
PGE2
prostaglandin,
produced from COOH

arachidonic acid.

Arachidonic acid
Biological Processes Regulated by Eicosanoids

1. Blood clotting
Thromboxane A2 stimulates constriction of blood vessels and
platelet aggregation
Prostacyclin dilates blood vessels and inhibits platelet aggregation

2. Inflammatory response
Prostaglandins mediate aspects of inflammatory response

3. Reproductive system
Stimulation of smooth muscle by PGE 2
Biological Processes Regulated by Eicosanoids

4. Gastrointestinal tract
Prostaglandins inhibit gastric secretion
Prostaglandins increase secretion of protective mucus
Inhibition of hormone-sensitive lipases

5. Kidneys
Prostaglandins dilate renal blood vessels
Results in increased water and electrolyte excretion

6. Respiratory tract
Leukotrienes promote the constriction of bronchi
Prostaglandins promote bronchodilation
Special reactions of unsaturated
fatty acids
Hydrogenation: It is the addition of hydrogen to
unsaturated double bonds present in oils.
Thus liquid fats( oils) are converted to solid fats(ghee).
This process is called as hardening of oils.
Halogenation: Halogens( F, I, Br) are readily added to
the double bonds of unsaturated fatty acids.
This property is used as an index of degree of
unsaturation of an oil or fat..(iodine number).
Iodine Number: The no. of grams of iodine required to
the double bonds in 100 grams of fat.
Special reactions of unsaturated
fatty acids
Oxidation: The double bonds in unsaturated fatty acids
are oxidizable.

The spontaneous oxidation forms thin, transparent

coating on the surfaces to which oils is applied. This is
called drying of oils and is used in the manufacturing of
paints and varnishes.
 Essential fatty acids
Three polyunsaturated fatty acids, linoleic acid, linolenic
acid and arachidonic acid are called essential fatty
acids (EFA).

They cannot be synthesized in the body and must be

provided in the diet.

Lack of EFA in the diet can produce growth retardation

and other deficiency manifestation symptoms.
 Docosahexaenoic acid (DHA)
Docosahexaenoic acid (DHA) is a polyunsaturated
fatty acid which is synthesized from -linolenic or
obtained directly from dietary fish oil.

This fatty acid is present in high concentrations in

retina, cerebral cortex, testes and sperms.

DHA is particularly needed for development of the brain

and retina and is supplied via the placenta and milk.
 Alcohols
Alcohols contained in the lipid molecule includes
glycerol, cholesterol and the higher alcohols, e.g.
cetylalcohol, C16H33COOH (usually found in waxes).
1. Glycerol: Glycerol is commonly called as glycerin
it is the simplest trihydric alcohol as it contains three
hydroxyl groups in the molecule.
 Steroids and sterols
Steroids are synthesized from the five
carbon isoprene unit.
Part of a diverse collection of lipids
called isoprenoids / terpenes
Contain the steroid carbon skeleton
A collection of 4 fused carbon rings
 Cholesterol
Cholesterol is the most important sterol in human body.
Its molecular formula is C27H45OH.
It possesses cyclopentanoperhydrophenanthrene
nucleus.
It has an OH group at C3.
Properties: The name cholesterol is derived from the
Greek word meaning solid bile.
Its melting point is 147 to 150o C.
 Steroids and sterols
Cholesterol
Cell membranes, precursor to bile salts, male and female sex
hormones, vitamin D, and the adrenocortical hormones
Have been linked to atherosclerosis

Bile salts
Important in the lipid digestion
 Steroid Examples
CH3 OH
CH CH2 CH2 CH2 CH(CH3)2 CH3
Cholesterol CH3
H

CH3 H CH3
H H

HO
H O
testosterone

CH3
C O
CH3
progesterone
CH3

O
 Other sterols of biological
importance
7-Dehydrocholesterol

It is an important sterol present in the skin.

This differs from cholesterol only in having a second double bond,

between C7 and C8.

Source: In man, 7-dehydrocholesterol may be obtained partly by

synthesis from cholesterol in skin and/or intestinal wall.

In the epidermis of skin, UV rays of sunshine change 7-

dehydrocholesterol (pre-cholecalciferol) to cholecalciferol (vitamin D3).
 Other sterols of biological
importance
Ergosterol: It is a plant sterol, first isolated from ergot,
a fungus of rye and later from yeast and certain
mushrooms. Ergosterol
 Vit D
Vitamin D3, also called cholecalciferol, is normally formed in the skin from 7-
dehydrocholesterol in a photochemical reaction driven by the UV component
of sunlight.

Vitamin D3 is not itself biologically active, but it is converted by enzymes in

the liver and kidney to 1,25-dihydroxyvitamin D3 (calcitriol), a hormone that
regulates calcium uptake in the intestine and calcium levels in kidney and
bone.

Deficiency of vitamin D leads to defective bone formation and the disease

rickets and osteomalacia.
 Vit D
Vitamin D2 (ergocalciferol) is a commercial product formed
by UV irradiation of the ergosterol of yeast.

Both have the same biological effects, and D2 is commonly

added to milk and butter as a dietary supplement.

Like steroid hormones, the product of vitamin D metabolism,

1,25-dihydroxyvitamin D3, regulates gene expression by
interacting with specific nuclear receptor proteins.
 Vitamin D3 production and
metabolism
Cholecalciferol (vitamin D3) is produced in the skin by UV irradiation
of 7-dehydrocholesterol, which breaks the bond shaded light red.

In the liver, a hydroxyl group is added at C-25; in the kidney, a

second hydroxylation at C-1 produces the active hormone, 1,25-
dihydroxyvitamin D3.

This hormone regulates the metabolism of Ca in kidney, intestine,

and bone.
Vit D3
 Simple lipids(glycerides)
Glycerides are lipid esters
Alcohol group of glycerol form an ester with a fatty acid
Esterification may occur at one, two, or all three alcohol positions
producing:

Monoglyceride
Diglyceride
Triglyceride
A neutral triacylglycerol or a triglyceride
Triglycerides are nonionic and nonpolar
Triglycerides serve as energy storage in adipose cells
 Triglycerides
Glycerides are lipid esters
A triglyceride places fatty acid chains at each alcohol group
of the glycerol
 Physical Properties
1. Neutral fats(Triglycerides) are colourless, odourless and
tasteless substances. The colour and taste of some of the
naturally occurring fats is due to extraneous substances.

2. Solubility: They are insoluble in water but soluble in

organic fat solvents.

3. Specific gravity: The specific gravity of all fats is less

than 1.0, consequently all fats float in water
 Physical Properties
4. Emulsification: Emulsions of fat may be made by shaking
vigorously in water and by emulsifying agents such as gums, soaps
and proteins which produce more stable emulsions(bile salts).

5. Melting point and consistency: The hardness or consistency

of fats is related to their MP. Glycerides of lower FA melt at lower
temperature than those of the higher fatty acids, and the
unsaturated fatty acids glycerides at still lower temperature.
 Chemical Properties
1. Hydrolysis: The fats may be hydrolysed with Super heated steam, By
acids, or alkalies, or By the specific fat spliting enzymes lipases.
Saponification: Hydrolysis of a fat by an alkali is called saponification.
The resultant products are glycerol and the alkali salts of the fatty acids,
which are called soaps.
2. Additive Reactions: The unsaturated fatty acids present in neutral fat
exhibits all the additive reactions, i.e. hydrogenation, halogenation, etc.
Oils which are liquid at ordinary room temperature, on hydrogenation
become solidified.
This is the basis of vanaspati (Dalda) manufacture, where inedible and
cheap oils like cotton seed oil are hydrogenated and converted to edible
solid fat.
 Chemical Properties
3. Oxidation: Fats very rich in unsaturated fatty acids
such as linseed oil undergo spontaneous oxidation at the
double bond forming aldehydes, ketones and resins
which form transparent coating on the surfaces to which
the oil is applied. These are called drying oils and are
used in the manufacture of paints and varnishes.
 Chemical Properties
4. Rancidity: When lipid-rich foods are exposed too long to the
oxygen in air, they may spoil and become rancid.

The unpleasant taste and smell associated with rancidity result

from the oxidative cleavage of double bonds in unsaturated
fatty acids, which produces aldehydes and carboxylic acids of
shorter chain length and therefore higher volatility; these
compounds pass readily through the air to your nose.
 Chemical Properties
To improve the shelf life of vegetable oils used in cooking, and to
increase their stability at the high temperatures used in deep
frying, commercial vegetable oils are prepared by partial
hydrogenation.

This process converts many of the cis double bonds in the fatty
acids to single bonds and increases the melting temperature of the
oils so that they are more nearly solid at room temperature
(margarine is produced from vegetable oil in this way).
 Chemical Properties
Partial hydrogenation has another, undesirable, effect: some
cis double bonds are converted to trans double bonds.

Dietary trans fatty acids raise the level of triacylglycerols and

of LDL (bad) cholesterol in the blood, and lower the level of
HDL (good) cholesterol, and these changes alone are
enough to increase the risk of coronary heart disease.
Lipids as pigments in plants and
bird feathers
Compounds with long conjugated systems absorb light
in the visible region of the spectrum.
Birds acquire the pigments that color their feathers red
or yellow by eating plant materials that contain
carotenoid pigments, such as canthaxanthin and
zeaxanthin.
The differences in pigmentation between male and
female birds are the result of differences in intestinal
uptake and processing of carotenoids.
 Compound lipids
Compound(conjugated) lipoids are lipids conjugated with other
substances. They include:

1. Phospholipids formed of lipid, phosphoric acid and

nitrogenous base

2. Glycolipids formed of lipid and carbohydrate

3. Sulpholipids, lipids containing sulphate.

4. Lipoproteins formed of lipid part and protein part.

 Phosphoglycerides

Phospholipid is a more general G

term l
Any lipid containing phosphorus
y Fatty Acid
Phosphoglycerides contain:
c
Glycerol Fatty Acid
e
Fatty acid
r
Phosphoric acid with an amino Phosphoric Acid
alcohol o
Replace an end fatty acid of a l
Alcohol
triglyceride with a phosphoric
acid linked to an amino alcohol
 Phosphoglycerides
Have hydrophobic and hydrophilic domains

Structural components of membranes

Emulsifying agents

Suspended in water, they spontaneously rearrange into ordered

structures
Hydrophobic group to center

Hydrophilic group to water

Basis of membrane structure

 Types of
Phosphoglycerides
The phospho-amino-alcohol is highly hydrophilic

They are used in:

Cell membranes

Emulsifying

Micelle-forming agents in the blood

Two types
Ones made with choline are called lecithin

Those made with either ethanolamine or serine are called cephalins

 Non-glyceride Lipids
Sphingolipids
These lipids are based on sphingosine
Long-chain
Nitrogen-containing
Alcohol
Amphipathic, like phospholipids
Polar head group
Two nonpolar fatty acid tail
Structural component of cellular membranes
Major categories
Sphingomyelins
Glycosphingolipids
 Types of Sphingolipids
Sphingomyelins
Structural lipid of nerve cell
membranes
Myelin sheath feature
Glycosphingolipids
Built on a ceramide
Cerebrosides have a single
monosaccharide head group
Glucocerebroside
Galactocerebroside
 Sphingolipid Storage Diseases

Disease Symptom Sph. Lip Enzyme

Tay-Sachs Blindness, Ganglioside -hexose-
muscles weak GM2 aminidase A
Gauchers Liver & spleen Gluco- -glucosidase
enlarge, MR cerebroside
Krabbes demyelation, Galacto- -galactosidase
MR cerebroside

Nieman- MR Sphingomyelin Sphingomyelinase

Pick
 Phosphoglycerides
Phosphoglycerides include phosphatidic acid, lecithins,
cephalins, phosphatidyl inositol, plasmalogen and
cardiolipin.

1. phosphatidic acid: It is phosphoric acid ester of

diglycerides.It is formed of Glycerol

Saturated FA attached to alpha carbon of glycerol by

ester bond
 Lipoproteins
A lipoprotein is a biochemical assembly that contains both proteins and lipids.

The lipids or their derivatives may be covalently or non-covalently bound to the

proteins.

Many enzymes, transporters, structural proteins, antigens, adhesins and toxins

are lipoproteins.

Examples include the high density and low density lipoproteins of the blood,
the transmembrane proteins of the mitochondrion and the chloroplast, and
bacterial lipoproteins.
 Classification

General categories of lipoproteins, listed in order from larger and less dense (more fat than
protein) to smaller and more dense (more protein, less fat):
Chylomicrons - carry triacylglycerol (fat) from the intestines to the liver, skeletal muscle, and to
adipose tissue.
Very low density lipoproteins (VLDL) - carry (newly synthesised) triacylglycerol from the liver to
adipose tissue.
Intermediate density lipoproteins (IDL) - are intermediate between VLDL and LDL. They are not
usually detectable in the blood.
Low density lipoproteins (LDL) - carry cholesterol from the liver to cells of the body. Sometimes
referred to as the "bad cholesterol" lipoprotein.
High density lipoproteins (HDL) - collects cholesterol from the body's tissues, and brings it back to
the liver. Sometimes referred to as the "good cholesterol" lipoprotein.
 Biological Functions of Lipids
As an energy source, lipids provide 9 kcal of energy per
gram
Triglycerides provide energy storage in adipocytes
Phosphoglycerides, sphingolipids, and steroids are
structural components of cell membranes
Steroid hormones are critical intercellular messengers
Lipid-soluble vitamins (A, E, D, K)
Dietary fat acts as a carrier of lipid-soluble vitamins into
cells of small intestine
Provide shock absorption and insulation
Lipoprotein &
Phospholipids Acts as fuel Insulating
(cell wall & in the body effect
mitochondrion
constituents)

Padding &
protection of
internal organs
Vitamin
A,D,E,K
fat Building
soluble Materials
vitamins (hormone
s)
Supply
Nervous essential fatty
system: Rich acids
in lipids
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