LIPIDS

Examples : fats, oils, steroids, waxes..etc.

Common properties Insoluble in water
Soluble in nonpolar solvents

Cellular
constituent
Important dietary
constituent

Transport
mediator

LIPIDS

Thermal and
electrical
insulator

Obesity,
Diabetes mellitus,
atherosclerosis,
nutrition and health

Fatty acids
-Carboxylic acids with variable R groups.
-Occur as esters in natural fats and oils.
-Free fatty acids in plasma.
-In natural fats straight chain derivatives
with even number of C atoms.
-Saturated or unsaturated.

Fatty acid nomenclature

- oic being substituted for the
final e in the name of the
hydrocarbon.
- Saturated acids end in -anoic,
and unsaturated acids
in
enoic.
Example : Octane (C8)
Octanoic
(18)

 C atoms are numbered

carboxyl carbon.
8

from
2

the

C C C C C = C C COOH

To indicate the position of the double

bonds,
eg: 3 double bond between C3 and
C4.
5
double bond on the 5th C
counting from the - carbon.

Palmitic acid, 16 : O
Oleic acid,
18: 1;9 or 9 18:1
18

10

CH3(CH2)7CH=CH(CH2)7COOH

or

9,C18:1 or n-9, 18:1

n

17
1

10

CH3CH2CH2CH2CH2CH2CH2CH2CH=CH(CH2)7CO
OH

 Additional double bonds are introduced only between

existing double bonds.
In animals,
-9 desaturase is present. So are able to
synthesise 9 family (microsomal chain
elongation and desaturase system) of
unsaturated fatty acids.
-but unable to synthesize linoleic (6) and
linolenic(3) acids because the required
desaturases are absent . Since 3 and 6
fatty acids are vital for maintenance of health
as well as growth and development, linoleic
and - linolenic fatty acids are known as
nutritionally essential fatty acids.
Three main series of fatty acids exist; 9 , 6
and 3 families.

 In saturated fatty acids,

chain is extended and flexible.
forms a zigzag pattern when
extended, as at low temperatures.
At high temperatures, some bonds
rotate, causing chain shortening.

 In an unsaturated fatty acid,

geometric
isomerism
occurs
depending on the orientation of atoms
around the double bonds - can either
be cis
or trans do not allow
rotation.
-If chains on the same side cis (Oleic
acid)
-Opposite trans (elaidic acid)
Most naturally occurring unsaturated
fatty acids are
cis,
and the
molecule being bent 120 degrees at
the double bond. So, Oleic is L shape

Unsaturated fatty
acids
9.18:1 cis & trans.

Saturated fatty
acid-Stearic acid
(18:0) in its
extended
conformation

 Increase in cis double bonds leads to various

spatial configurations
Eg: Arachidonic acids- 4 cis bonds- U shape.
Trans fatty acids in certain foods,
Catalytichydrogenation in the manufacture of
margarine results trans fats.
Ruminant fat, that contain trans fatty acids.

 Physical properties of the fatty

acids depends on,
-the length of the hydrocarbon
chain.
-the degree of unsaturation.
The non polar hydrocarbon chain
accounts for the poor solubility of
fatty acids in water.
Longer the fatty acyl chain and
fewer the double bonds, lower the
solubility in water.

 The melting points of even numbered

fatty acids increase with,
-the increases in length of the
hydrocarbon
chain.
-the decrease in the degree of
unsaturation.
The fatty acids with shorter chain
length and having double bonds
have lower melting points.
The difference in melting points is due
to different degree of packing of fatty

 A triacylglycerol with
-3 saturated fatty acids of 12 carbons is
more solid at body temperature.
-fatty acid residues of 18:2 are liquid to
below 0C.

 In practice,
-natural acylglycerols contain a mixture of fatty
acids tailored to suit their functional roles.
-Membrane lipids, which must be fluid at all
environmental temperatures, are more
unsaturated than the storage lipids.
-Lipids in tissues that are subject to cooling, eg.,
in hibernators or in the extremities of animals, are
more unsaturated.

Unsaturated fatty
acids

Polyunsaturated
fatty acids

Monounsaturated
fatty acids
Eicosanoids

Eicosonoids
Derivatives of eicosa (20-carbon) polyenoic fatty
acids.
Comprise prostanoids, leukotrienes, lipoxins.
Prostanoids include prostaglandins (PGs),
prostacyclins (PGIs) and thromboxanes (TXs).
PGs are synthesized by the cyclization of the
center of carbon chain to form a cyclopentane
ring.
TXs have the cyclopentane ring interrupted with
an oxygen atom.

Eicosatrienoic acid C 20:3

5,8,11
,Eicosatetraenoic acid or
Arachidonic acid C 20:45,8,11,14 and
Eicosapentaenoic acid, C 20:5,5,8,11,14,17
give rise to three groups of
eicosanoids (PG1, PG2 and PG3
series), by the number of double bonds
in the side chain.
Different groups attached to rings give rise to
series of PGs and TXs, labeled A, B
-Eg: PGE2 keto in position 9, PGF2

Prostaglandin E2 (PGE2)

Prostaglandin I2 (PGI2)/
Prostacyclins

Thromboxane A2 (TXA2)

Leukotriene A4 (LTA4)

Triacylglycerol
Esters of glycerol and fatty acids.
Non polar, hydrophobic.
Stored as fat droplets in fat
cells or adipocytes, also in plant
seeds.
Two advantages over
carbohydrates.
Fatty acids are more reduced,
therefore, yield more energy.
Unhydrated, therefore doesnt
need to carry extra weight of

 TGs under the skin provides insulation.

Fat reserves for hibernating animals.
Many foods contain triacylglycerols;
vegetable oils, dairy products, and
animal
fats
contain
complex
mixtures
of
simple
&
mixed
triacylglycerols.
Vegetable oils such as corn and
olive oil are composed largely of
triacylglycerols with unsaturated
fatty acids and are liquids at
normal temperature.

 Prolong exposure of lipid rich foods

to O2 in air,
- results spoiling & becoming rancid.
- Due to oxidative cleavage of the
double bonds in unsaturated fatty
acids to aldehydes and carboxylic
acids of short chain length.
- which are high volatile.
- unpleasant taste and odor.

Hydrolysis of triacylglycerol
Enzymatic hydrolysis of TGs
By a variety of lipases in
intestine, adipocytes,
germinating seeds.
Pancreatic lipase, Lipoprotein
lipase etc.

Release free fatty acids which

are used as fuel.

Soaps
Na or K salts of fatty acids.
Can solubilize water - insoluble
material by forming microscopic
aggregates.

Membrane lipids
Phospholipids, Glycolipids, Steroids
Phospholipids
Derivatives of phosphatidic acid
OH is esterified with a suitable alcohol
Phosphatidic acid is an intermediate in
the synthesis of TG and phospholipids

Phosphatidic
acid

 In general,
- Glycerophospholipids contain a
saturated fatty acid at C - 1
- and an unsaturated fatty acid at
C - 2 (16 - 18 carbons long)
- but there are exceptions.

Phosphatidylcholine (Lecithin)
Most abundant phospholipid in cell membrane
Represent a large proportion of the bodys store
of choline.
-Choline important in nervous transmission
Dipalmitoyl lecithin constituent of the
surfactant, in inner surface of lungs
-Absence in premature infants causes
respiratory distress syndrome.

Phosphatidylinositol
Important cell membrane constituent
Precursor of second messengers.
Cardiolipin
Major lipid in mitochondrial membrane
Plasmalogan
Constitute 10% of phospholipids in brain and
muscle.

 Resembles phosphatidylethanolamine
Ether link on C-1 instead of an ester link.

Sphingolipids

Composed of,
-one molecule of the long - chain amino alcohol
sphingosine or one of its derivatives ,
-one molecule of a long - chain fatty acid,
a polar head alcohol and sometimes
phosphoric acid at the polar head group.

 C-1, C -2, C-3 of sphingosine molecule bear

functional groups
-OH, -NH2, -OH.
When a fatty acid is attached in amide
linkage to the - NH2, the resulting compound
is a ceramide
similar to a diacylglycerol.
Ceramide is fundamental structural unit of
all sphingolipids.

 Three subclasses of sphingolipids.

All derivatives of ceramide but differing in
their head groups.
v
v
v

sphingomyelin
neutral glycolipids
Gangliosides

Sphingomyelins
Contain phosphocholine or phosphoethanolamine
as the polar head group.
Therefore classified as phospholipids together
with glycerophospholipids.
Present in plasma membranes & myeline sheath
surrounding & insulating the axons of
myelinated neurons.

Glycosphingolipids
One or more sugars connected directly to the
-OH at C-1 of ceramide moiety.
Sugar containing sphingolipids are called
glycosphingolipids.
Neutral glycolipids contain 1-6 sugar units of
D - glucose , D-galactose or N - acetyl - D galactosamine.
Glycosphingolipids occur largely in the outer
face of the plasma membrane.

 Cerebrosides have a single sugar linked to

ceramide .
Those with galactose are found in the
plasma membranes of cells in neural tissue
and those with glucose in the plasma
membrane of cells in non neural tissue.

Gangliosides
Polar head made up of several sugar units.
One or more of the sugar
units is N Acetylneuraminic acid (sialic acid) at the termini
- -gives it a negative charge at pH 7.
-found in the grey matter.
Lesser amounts in non neural tissue membrane.

Sphingolipids are sites of biological

recognition
Glycosphingolip
ids are the
determinants
of the human
blood groups
A, B and O

 Ganglioside, GM 3, is the point of

attachment of cholera toxin.
Derangements in the metabolism of
cerebrosides & gangliosides underlie
the devastating effects of several
human genetic diseases. Eg. Tay Sachs and Niemann - Pick diseases.
Tay-Sachs disease is due to acculumation of gangliosides due to the
absence of an enzyme that breaks it
down
Neiman pick disease is due to absence of an enzyme that breaks down

Phospholipids and sphingolipids are degraded in

the lysosomes.

phosphotidylinositol
Phospholipase C
(hormone activation)

Diacylglycerol
(DAG)

Phospholipase A2

Inositol
phosphates
(IP3)

Arachidonic acid
from membrane
lipids

Gangliosides are degraded by a set of

enzymes that catalyze the stepwise removal of
sugar units finally yielding a ceramide.
A genetic defect in any of these hydrolytic
enzymes leads to the accumulation of
gangliosides in the cell with severe clinical
consequences.

Functions of Phospholipids and Sphyngolipids

Membrane structure
Important components of lipoproteins
Enzyme activator
Cholesterol solubilization
Lung surfactant - Dipalmitoyl phosphatidylcholine
(DPPC) is a very active surface active agent
(maintains alveolar stability during expiration
thereby preventing lung collapse). Inadequate
surfactant function , superimposed on a immature
lung leads to respiratory failure in the premature
infant - Hyaline membrane disease (HMD)
Hormone & neurotransmitter action (via production
of DAG, IP3)
Synthesis of eicosonoids

Sterols
-Are structural lipids.
-In the membranes of most eukaryotic cells.
-Cholesterol - major sterol in animal tissues,
Stigmasterol in plants
Ergosterol in fungi
-Cholesterol - amphipathic with a polar head
group (-OH group at C-3) and a nonpolar
hydrocarbon body.

Forms an ester
with fatty acids
for storage and
transport

-Precursors for bile acids

-side chain at C - 17
is hydrophilic,
-emulsifying dietary
fat
-Produce hormones from cholesterol by
oxidation of the side chain at C - 17.
-7-dehydrocholesterol is the precursor of
vitamin D3.

Micelle

bilayer

liposome

Cell membrane
Lipids form the matrix and proteins are anchored
Major lipid phosphoglycerides. Shpyngolipids and
cholesterol to lesser extent.
Tails made up of fatty acids; heads of PO4 and
nitrogenous bases, sugars and OH in cholesterol
Proteins are mainly glycoproteins; ionic groups
clustered at aqueous phase and non-ionic region in
hydrophobic lipid matrix.

 Lipid bilayer is in a dynamic and fluid state:

-the lipids & most proteins being
free
to diffuse laterally within the
membrane.
Hydrophobic tails consist of an appropriate
mixture of saturated and unsaturated fatty
acids
-that is fluid at the normal
temperature of the cell.
The degree of fluidity of the membrane
-depends on the temperature &
character the fatty acyl tails
The temperature at which the structure melts is

 More unsaturation, more fluid the membrane.

Saturated long aliphatic chains harden the
membrane and restrict lateral motion of protein
molecules.
cholesterol modifies the fluidity. At temperatures
below Tm it increases fluidity by interfering with
the interaction of hydrocarbon chains of fatty
acids and at temperatures above Tm it limits
fluidity by limiting the disorder.
As membrane fluidity increases, so does the
permeability to water and other small
hydrophilic molecules.

Major functions of the cellular membrane

1.
Membrane form a barrier between the cell and
the external environment and divide cells into discrete
compartments.
2.
Their highly selective permeability varies.
(permeable to non polar / impermeable to polar charged
molecules).
3. Contain specific receptors for external stimuli.
4.
The locus of cell specific antigens: characteristic
of both cell type and mammalian tissues.
5. They organize complex reaction sequences.
6. They regulate cell growth and multiplication.