1

Lipids

Lipids
Lipids are esters of long chain fatty acids
They are insoluble in water and soluble in
nonpolar solvents such as acetone, alcohol, ether
or chloroform.
Their low water solubility is due to a lack of
polarizing atoms such as N, S, and P

Lipids
Lipids are composed of C, H, O
long hydrocarbon chains (H-C)

Family groups
fats
phospholipids
steroids

Functions of lipids
Storage form of energy
Important dietary components because of their high
energy value and also because of the fat-soluble
vitamins and the essential fatty acids contained in
the fat of natural foods.
Structural components of biomembranes
Serve as thermal insulators in the subcutaneous
tissues and around certain organs
Nonpolar lipids act as electrical insulators, allowing
rapid propagation of depolarization waves along
myelinated nerves

Functions of lipids(Contd.)
Provide shape and contour to the body
Act as metabolic regulators
Combinations of lipid and protein (lipoproteins)
are important cellular constituents, occurring both
in the cell membrane and in the mitochondria,
and serving also as the means of transporting
lipids in the blood.

Biological roles of lipids:

Lipid functions
Lipids are used in
Fuel storage
Hormones
Signal transduction messenger
Membranes

Membrane lipids:
Phospholipid
Glycolipid
Cholesterol

Classification:

Classification
Bloor in 1925
I.

Simple: fats, oils, waxes, steroids.

II.

Compound:
A.

Phospholipids containing phosphoric acids:

1)

Nitrogen containing glycerophosphatides

2)

Non nitrogen containing glycerophosphatides

3)

Plasmalogens, containing long chain alcohol

4)

Phospho sphingosides, containing sphingosine.

B.

Non phosphorylated lipids:

1)

Glycosphingolipids(carbohydrates)

2)

Sulpholipids or sulfatides.

III. Derivatives: cholesterol and steroids

IV.

Lipids complexed to other compounds: lipoproteins

10

Types of Lipids
Lipids with fatty acids
Fats and oils (trigycerides)

Waxes
Phospholipids
Sphingolipids
Lipids without fatty acids
Steroids

Classification of Lipids

Fatty acids:
Fatty acids are
used as stored
forms of energy in
cells.
A fatty acid is a
carboxylic acid
with a long
unbranched non
polar hydrocarbon
tail.

Stearic

Oleic

Classification of fatty acids:

Depending up on the total number of carbon atom

Even chain: even number of carbons- most of the

naturally occurring
Odd chain : odd number of carbons- microbial cell walls,

in milk

Depending on the length of hydrocarbon chain:

Short chain: 2 to 6
Medium chain: 8 to 14
Long chain: 16-24

The Length of the Carbon Chain

Short-chain Fatty Acid
(less than 6 carbons)

Medium-chain Fatty Acid

(6-10 carbons)

Long-chain Fatty Acid

(12 or more carbons)

Classification of fatty acids:

Fatty acids

Saturated FA

Unsaturated FA

Saturated fatty acids:

Saturated fatty contains only single bonds.

Saturated indicates that the maximum
possible number of hydrogen atoms are
bonded to each carbon.
Considered as harmful.
It increases total cholesterol level and TGs
level.
Hypercholestrolemic SFAs are Myristic acid &
Lauric acid.

Saturated fatty acids:

All C bonded to H

No C=C double bonds

long, straight chain
most animal fats : palmitic and

stearic acid
High melting points
solid at room temp.
contributes to cardiovascular

disease (atherosclerosis)
= plaque deposits

Source:
Harper's
Illustrate
d
Biochem
istry by
Robert
K.
Murray,
Darryl K.
Granner,
Peter A.
Mayes,
Victor W

Unsaturated fatty acids:

Fatty acids contain one or more C=C double bonds.
The double bonded C prevent the molecules from
packing tightly together
Nonlinear chains do not allow molecules to pack
closely
UFA include oleic acid and linoleic acid.

Unsaturated Fatty Acids

Low melting points

liquid at room temperature

Plant & fish fats

Vegetable oils

Saturated and Unsaturated Fatty

Acids
Saturated = CC bonds
Unsaturated = one or more C=C bonds
COOH
palmitic acid, a saturated acid
COOH
palmitoleic acid, an unsaturated fatty acid

Fatty Acids
Carbon Atoms: Common
Double Bonds Name
Saturated Fatty Acids

Higher mp

12:0
14:0
16:0
18:0
20:0

Melting Point
(C)

Lauric acid
Myristic acid
Palmitic acid
Stearic acid
Arachidic acid

44
58
63
70
77

Unsaturated Fatty Acids

Lower mp

16:1
18:1
18:2
18:3
20:4

Palmitoleic acid
1
Oleic acid
16
Linoleic acid
-5
Linolenic acid
-11
Arachidonic acid -49

Classification based on unsaturation:

Monoethenoid acids: one double bond
eg: oleic acid
Diethenoid acids: Two double bonds
eg: Linoleic acid
Triethenoid acids: Three double bonds
eg: Linolenic acid
Tetraethenoid acids: Four double bonds
eg: Arachidonic acid

Saturated Vs. unsaturated

saturated
unsaturated

Divisions of unsaturated fatty acids:

Monounsaturated Fatty
Acid
(MUFA)
One carbon-carbon double bond

Found mostly in vegetable oils such as olive,

canola, and peanut.
They are considered as beneficial for human
health.

Monounsaturated fatty acids:

Cis FA

Trans FA

Cis fats
Naturally
occurring

Yes

Trans Fats
hydrogenation, or
hardening, of natural
oils

Health Effect

Decreases total cholesterol Detrimental lowers

and TGs level.
good cholesterol and
increases the level of
Increases HDL level.
bad cholesterol in the
body. Harmful to heart
health could cause
cardiac death.

Arrangement of
atoms

The chains of carbon atoms

are on the same side of the
double bond, resulting in a
kink

Hydrogen atoms are on

the opposite side of the
double bonds of the
carbon chain, making
the fat molecule
straight

Hydrogenation of Fatty acids:

Hydrogenation of oils leads to solidification and saturation

e.g. Vanaspathi

Cis-fatty acid:

Hs on same side of the double bond; fold into

a U-like formation; naturally occurring;

Trans-fatty acid:

Hs on opposite side of double bond; more

linear; occur in partially hydrogenated foods;

Tra
n sfat
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liste t be
Foo d on
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Lab
By
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Jan
1, 2 uary
006

Polyunsaturated Fatty Acid

(PUFA)

More than one carbon-carbon double bond

PUFA are identified by position of the double bond nearest
the methyl end (CH3) of the carbon chain; this is described
as a omega number
If PUFA has first double bond 3 carbons away from the
methyl end=omega 3 FA
6 carbons from methyl end=omega 6 FA

Omega-3

Omega-6

Eicosanoids:

Derived from long chain

polyenoic fatty acids (Eicosa- 20
Carbon arachidonic acid).
considered "local hormones
participating in intercellular
signaling,
Examples:
Prostaglandins (PGs)
Prostacyclins (PGIs)
Thromboxanes (TXs).
Leukotrienes
lipoxins

Effects in different
cells:
cause muscles to
contract and muscles
to relax
help regulate blood
pressure, blood clot
formation
Participate in immune
response to injury
and infection producing fever,
inflammation, and
pain.

Essential fatty acids

Essential fatty acids

Burr and Burr in 1930

Fatty acids that have to be supplied in the diet

All these are polyunsaturated fatty acids

The C 20 fatty acid Arachidonic acid (20:4;5,8,11,14)

The two C18 acids

Linoleic acid (18:2; 9,12) Also called Vitamin F
Linolenic acid (18:3; 9,12,15).

Omega-3

Omega-6

(ebook - medicine) Biochemistry Garrett

and Grisham 2nd ed

Source: Biochemistry by Garrett and Grisham 2nd ed

Triglycerides

Triglycerides(TG):
The simplest lipids constructed from fatty
acids are the triacylglycerols.
Also referred to as Triglycerides, Fats, or
Neutral fats.
A significant number of the fatty acids in
plants and animals exist in the form of
triacylglycerols.
It is composed of three fatty acids each in
ester linkage with a single glycerol

Triacylglycerols are
nonpolar.
Structure:
glycerol (3C alcohol) + fatty acid
Triacylglycerols are nonpolar: Polar hydroxyls of
glycerol and the polar carboxylates of the fatty acids are
bound in ester linkages

H2O
dehydration synthesis

Triglycerides(TG):
Ester linkage = between OH & COOH
Lipids have lower specific gravities than water-so
floats on the aqueous phase

Fatty acid composition of

three food fats.

Types of triacylglycerol
Simple triacylglycerol: same kind of fatty acid in all
three positions
Examples:
Tristearoylglycerol (tristearin)-derived from
three units ofstearic acid
Trioleoylglycerol (triolein)- three units of the
unsaturated fatty acid oleic acid
Mixed triacylglycerols : contain two or three
different fatty acids. e g: 1-paimitoyl-2,3-distearin.
Most of natural plant and animal fat is composed of
mixtures of simple and mixed triacylglycerols.

Example of triglycerides
Triglyceride derived from one molecule each of palmitic
acid, oleic acid, and stearic acid, the three most abundant
fatty acids in the biological world.
palmitate (16:0)
O
oleate (18:1)
O CH2OC(CH2) 14CH3
stearate (18:0)
CH3(CH2)7 CH=CH(CH2 )7COCH O
CH2OC(CH2) 16CH3

Triglycerides
Functions
Energy source
1 g yields about 38 kJ.
Form of stored energy in
adipose tissue
Insulation and protection
Carrier of fat-soluble vitamins
Sensory properties in food

Saponification and Soap

Hydrolysis with alkali is called saponification
Triglycerides split into glycerol and the salts of
fatty acids
The salts of fatty acids are soaps
KOH gives softer soaps

Saponification
O
CH2 O

(CH2)16CH3

O
CH

CH2

C (CH2)16CH3 + 3 NaOH
O
C

(CH2)16CH3

CH2 OH
CH
CH2

+OH + 3 Na O C (CH2)14CH3
salts of fatty acids (soaps)
OH

Triglyceride Reactions
Triglycerides undergo three basic reactions
These reactions are identical to those studied in
carboxylic acids

Triglyceride
H2O, H+
Glycerol
Fatty Acids

H2, Ni
NaOH
Glycerol
Fatty Acid Salts

More saturated
triglyceride

Hydrolysis

Saponification

Hydrogenation

Lipoproteins:
PLASMA LIPIDS:

Plasma lipids:
Total plasma lipid is 400-

600mg/dl
Since lipids are insoluble
in water , they need a
carriers in plasma.
Lipids are complexed with
protein- lipoproteins.
The protein part of lipid is
called apolipoprotein.

Lipoproteins:

61

Lipoproteins:
Lipids absorbed from the diet and synthesized by the liver
and adipose tissue must be transported between various
cells and organs for utilization and storage.
Lipids are insoluble in water, the problem of transportation in
the aqueous plasma is solved by associating nonpolar lipids
(triacylglycerols and cholesteryl esters) with amphipathic
lipids (phospholipids and cholesterol) and proteins to make
water-miscible lipoproteins.

General Structure of Lipo proteins

Some apolipoproteins are integral and cannot be removed, whereas others

can be freely transferred to other lipoproteins.

Lipoproteins(Lp)

Various combinations of lipid and protein produce particles

of different densities.

Depending on the density ( ultra centrifuge) or

electrophoretic mobility- 5 Types:
1. Chylomicron
2. Very low density lipoprotein ( VLDL)
3. Intermediate density lipoprotein (IDL)
4. Low density lipoprotein (LDL)
5. High density lipoprotein (HDL)

Classification of Lipoproteins

Lipoproteins with high lipid content will have low density, larger size and

so float on centrifugation.
Those with high protein content sediment easily, have compact size and
have a high density.

Apolipoproteins:
Apolipoproteins are lipid-binding

proteins in the blood.

responsible for the transport of
Triacylglycerols
phospholipids
cholesterol and
cholesteryl esters between
organs.
It combine with lipids to form
several classes of lipoprotein
particles.
Mainly synthesized in liver; small
quantities in almost all organs.

Functions of Apolipoproteins:
Structural role:B48 is an important

component.
Activation of enzymes:
Apo C-II is activator of lipoprotein
lipase.
Apo A-1 activates lecitin
cholesterol acetyl
transferase(LCAT)
Receptor binding:
Apo A-1 is the ligand for HDL
receptor.

Chylomicrons
Formed in the intestinal mucosal cells- contain apoB-

48 and apo-A but apo-C and apo-E are added from

serum.
Absorbed into: the lymph vessels, then -->
moves into the blood
Rich in: TGs
Half life about 1 hour.
Function: Deliver TGs to

Adipose tissue for storage

heart and muscle cells to be used as fuel

Metabolism of chylomicron:

LpL

VLDL (Very Low Density

Lipoprotein)
Synthesized

in: the liver from glycerol and fatty

acids
Contains apo B100, C-II and E
Secreted into: the bloodstream
Half life: 1 to 3 hours
Rich in: TGs
Function: Deliver TGs to body cells
Similar to Chylomicrons, but made by different
tissues

Metabolism of chylomicron:

LpL: Lipoprotein
Lipase enzyme,
located at endothelial
layer of capillaries of
adipose tissue,
muscles and heart.

VLDL & Lipoprotein cascade pathway:

VLDL major carriers of
endogenous TGs(synthesized in
liver) to peripheral tissues.
VLDL contain hepatic
cholesterol, apo B-100, C-II and E
Half life is 1-3 hours
In peripheral tissues apo C-II
activates LpL , which liberates FA
The remnant is called
IDL( intermediate density
lipoprotein)
IDL contains less TAG & more
cholesterol.
Small part of IDL is taken up by
liver and major fraction is
converted to LDL

LDL (Low Density

Lipoprotein)
Made in: the Liver as VLDL
Rich in cholesterol & contains apo B-100
Arise from: VLDL once it has lost a lot of its

TGs & apo E

Secreted into: the bloodstream
Hal life: 2 days.
Contain 75% of plasma cholesterol.
Function: Deliver cholesterol to all body
cells
Bad cholesterol:
Oxidized LDL creates pro-coagulants
surface on the endothelium, causing
blood clot formation.

 LDL concentration in blood has a positive correlation with

incidence of cardiovascular disease.

HDL(High Density Lipoprotein)

Pick up cholesterol from body cells and take it back

to the liver = reverse cholesterol transport

Latter excreted through bile
Potential to help reverse heart disease
HDL level below 35mg/dl increases the risk
HDL level above 60mg/dl protect persons from

coronary artery diseases.

Metabolism of HDL
Role of LCAT
LCAT( Lecithin Cholesterol Acyl Transferase)
enzyme catalyzes the esterification of cholesterol to
form Cholesteryl ester.
The reaction can be represented as followsLecithin + Cholesterol
Lysolecithin +
Cholesteryl Ester

Metabolism of HDL
LCAT and the LCAT activator apo A-Ibind to

the discoidal particles, and the surface

phospholipid and free cholesterol are
converted into cholesterol esters and
lysolecithin .
The nonpolar cholesteryl esters move into the
hydrophobic interior of the bilayer, whereas
lysolecithin is transferred to plasma albumin.
Thus, a nonpolar core is generated, forming a
spherical, pseudomicellar HDL covered by a
surface film of polar lipids and apolipoproteins.
This aids the removal of excess unesterified
cholesterol from lipoproteins and tissues .

References:
1. Lehninger Principles of Biochemistry Fourth Edition by

David L. Nelson and Michael M. Cox

2. Text book of biochemistry by DM Vasudevan and

Sreekumari S
3. Medicine Biochemistry 2nd edition by Garrett and Grisham
4. Color Atlas of Biochemistry Second edition,by Jan Koolman

and Klaus-Heinrich Roehm

5. Biochemistry the chemical reactions of living cells by David

E. Metzler.