Lipids

What are lipids?

 A small water-insoluble biomolecule generally containing
fatty acids, sterols and isoprenoid compounds.
 The second major group of organic compounds found in
living matter
 Composed of carbon, hydrogen, oxygen
 All lipids are nonpolar
 Insoluble in water but dissolve readily in non polar solvents,
such as ether and chloroform
 Biological importance of lipids
 Fats and oils are the principal stored forms of energy in
many organisms.
 Phospholipids and sterols are major structural elements
of biological membranes.
 Protecting against desiccation (drying out)
 Insulating against cold
 Biological importance of lipids
 Other lipids, although present in relatively small amounts, play
crucial roles as :
 Enzyme cofactors
 Electron carriers
 Light absorbing pigments
 Hydrophobic anchors for proteins
 Chaperones to help membrane proteins fold
 Emulsifying agents in the digestive tract
 Hormones
 Intracellular messengers
 Classification of lipids

Broadly classified as

1. Simple lipids
2. Complex (or compound) lipids
3. Derived lipids
4. Miscellaneous lipids
 Simple lipids
 Esters of fatty acids with alcohols
Two types:
a) Fats & oils
b) Waxes
a) Fats & oils (triglycerols)
• Esters of fatty acids with glycerol
• Oil is liquid and fat is solid at room temperature
b) Waxes
• Esters of long chain fatty acids with long chain alcohol
 Complex ( or compound) lipids
 Esters of fatty acids with alcohols containing additional
groups, e.g. phosphate, nitrogenous base,
carbohydrate, protein etc.

 Further divided:

a) Phospholipids
b) Glycolipids
c) Lipoproteins
d) other complex lipids
Complex (or compound) lipids (contd.)
a) Phospholipids
 Lipids containing fatty acids, alcohol, phosphoric acid
and nitrogenous base.
 In contrast to the triacylglycerols, phospholipids have
a hydrophilic end that interacts with water.
Complex ( or compound) lipids (contd.)

i) Glycerophospholipids
 Contain glycerol as alcohol
 e.g. lecithin

ii) Sphingophospholipids
 Contain sphingosine as alcohol
 e.g. sphingomyelin
The principal classes of storage and
membrane lipids
Glycerophospholipids
Sphingophospholipids (sphigomyelin)
Thank you
 Complex ( or compound) lipids (contd.)

b) Glycolipids: Have a simple sugar or complex

oligosaccharide at their polar ends. e.g. gangliosides

c) Lipoproteins: Macromolecular complexes of lipids with

proteins.

d) Other complex lipids: Sulfolipids, lipopolysaccahrides

 Derived lipids
 These are derivatives obtained upon hydrolysis of
lipids.

 These include fatty acids, hydrocarbons, glycerol,

fat soluble vitamins, steroid hormone etc.
 Miscellaneous lipids
 These include large number of compounds
possessing the characteristics of lipids, e. g.
caroteniods.
 Fatty acids
 Simplest form of lipids
 Derived lipids
 Carboxylic acid with hydrocarbon side chain
 Carbon chain contain even or odd number of
carbon atoms
 Carbon chain contain either single bond
(saturated) or double bond (unsaturated)
 Present as esterified (major constituent of various
lipids) or unesterified (free) form
Simplified nomenclature for fatty acids
 The chain length and number of double bonds, separated
by a colon
 For example, the 16-carbon saturated palmitic acid- 16:0
 The 18-carbon oleic acid, with one double bond- 18:1
 The positions of any double bonds are specified by
superscript numbers following ∆ (delta)
 A 20-carbon fatty acid with one double bond between C-9
and C-10 and another between C-12 and C-13 is
designated 20:2 (∆ 9,12)
Simplified nomenclature for fatty acids
A common pattern in the location of double bonds
 In most monounsaturated fatty acids the double
bond is between C-9 and C-10 (∆ 9)
 In polyunsaturated fatty acids the other double
bonds are generally ∆ 12 and ∆ 15
 Almost never conjugated
 Separated by a methylene group: - CH=CH-CH 2-
CH=CH-
Some Naturally Occurring Fatty Acids
 Triacylglycerol/Triglycerides
 Esters of fatty acids & glycerols
 Fats & oils are chemically triglycerides
 Fats are usually fuel reserve of animals
 Oils are usually fuel reserve of plants
 Types: Simple and Mixed triglycerides
 Properties of Fats

 Contain only single C-C bond

 Strong interactions between chains
 Closely packed
 Solid at room temperature
 Properties of Oils
 Contain one or more double C=C bond
 Weak interaction between chains
 Nonlinear chains do not pack closely
 Liquid at room temperature
Thank You
 Reactions of Triglycerides

• Acid or Enzymatic Hydrolysis

• Alkali Hydrolysis (Saponification)
• Hydrogenation
• Rancidity
 Hydrolysis
 They are hydrolyzed into their constituents (fatty acids and
glycerol) by the action of super heated steam, acid, alkali or
enzyme (e.g., lipase of pancrease).
 During their enzymatic and acid hydrolysis glycerol and free
fatty acids are produced.

O O
CH2 O C R1 H2C OH R1 C OH
O Lipase or Acid O
R2 C O C H HO C H + R C OH
2
O
O
CH2 O C R3 3 H2O H2C OH
R3 C OH
Triacylglycerol Glycerol Free fatty acids
 Saponification.
 Alkaline hydrolysis produces glycerol and salts of
fatty acids (soaps).

O O
CH2 O C R1 H2C OH R1 C ONa
O O
R2 C O C H HO C H + R C ONa
2
O
O
CH2 O C R3 3 NaOH H2C OH
R3 C ONa
Triacylglycerol Glycerol Sodium salts of
fatty acids (soap)
 Hydrogenation
 It is a type of addition reactions accepting hydrogen
at the double bonds of unsaturated fatty acids.
 The hydrogenation is done under high pressure of
hydrogen and is catalyzed by finely divided nickel or
copper and heat.
 It is the basis of hardening of oils, e.g., change of
oleic acid of fats (liquid) into stearic acid (solid).

Oils Hydrogen, high pressure, nickel Hard fat

(liquid) (margarine, solid)
(with unsaturated (with saturated
fatty acids, e.g., oleic) fatty acids, e.g., stearic)
 Reactions of Triglycerides

 Rancidity: Changes in odor and flavor are due to

the deterioration of fats or oils. Fats containing
unsaturated fatty acids are more susceptible to
rancidity.

 Causes of rancidity:
Endogenous enzymes
Microbial enzymes
Chemical transformation
 Tests of checking purity of fats & oils

 Iodine number
 Saponification number
 Reichert-Meissl (RM) number
 Acid number
 Tests of checking purity of fats & oils

 Iodine number: The number of grams of iodine

absorbed by 100 g of fat or oil.

 The lower is the iodine number the less is the

degree of unsaturation.
 Butter= 25-28
 Sunflower oil=125- 135
 Tests of checking purity of fats & oils

 Saponification number: The number milligrams of

KOH required to hydrolyze/saponify 1 g of fat or
oil.

 The value is higher for fats with short chain fatty

acids.

 Butter=230-240 Coconut oil=250-260

 Tests of checking purity of fats & oils
 Reichert-Meissl (RM) number: The number of ml
0.1 N KOH required to completely neutralize the
soluble volatile fatty acids distilled from 5 g of fat.

 Adulteration of butter is tested by this number.

 Butter has RM number in the range of 25-30 while

it is less than 1 for most other edible oils.
 Tests of checking purity of fats & oils

 Acid number: The number of milligrams of KOH

required to completely neutralize free fatty acids.

 Oils on decomposition yield free fatty acids.

 Oils with increased acid number are unsafe for

consumption.
 Amphipathic Lipids
 Lipids that contain both hydrophilic region and
hydrophobic region are called amphipathic lipids.

 They cluster together with their hydrophobic

moiety in contact with each other and their
hydrophilic groups interacting with surrounding
water.
 Amphipathic Lipids
 Three types of lipid aggregates are found when
amphipathic lipids are mixed with water.
 Micelles
 Relatively small, spherical structures
 Involving a few dozen to a few thousand molecules
 Their hydrophobic regions aggregate in the interior, excluding
water
 Hydrophilic head groups are at the surface in contact with
water.
 Micelles formation facilitated by bile salts is very important for
lipid digestion and absorption.
 Bilayer
 Two lipid monolayers combine to form a two-
dimensional sheet.
 The hydrophobic portions in each monolayer interact
excluding water.
 The hydrophilic head groups interact with water at the
two surfaces of the bilayer
 Liposome
 Formed when a lipid bilayer folds back on itself to form a hollow
sphere called a liposome or vesicle.
 By forming vesicles, bilayer sheets lose their hydrophobic edge
regions, achieving maximal stability in the aqueous
environment.
 These vesicles enclose water, creating a separate aqueous
compartment.
 Liposome in combination with tissue specific antigens are used
as carrier of drugs to target tissue.
 Isoprenoids
 Isoprenoids in living organisms range in function from
pigments and fragrances to vitamins (A, D, E, K) and
precursors of sex hormones. The five-carbon unit that
constitutes the basic building block of isoprenoids is a called
isoprene. Isoprenoids contain from two to many thousands of
isoprene units and are synthesized by the condensation of
isoprene units.

 One of the most familiar natural substances, rubber, is a

polyisoprene.
 Steroids

• Compounds containing a cyclic steroid nucleus

consisting of 4 fused rings, 3 with 6 carbons and 1 with 5
carbons.

Steroid nucleus
• Steroids, sterols are derived from isoprenoid building blocks via
biosynthetic pathways.
 Steroids in biological system
 Cholesterol
 Bile salts
 Male and female hormones (testosterone, estradiol)
 Vitamin D
 Ergosterol (structural constituent of cytoplasmic
membrane in fungi)
Thank You