3

LIPIDS

Definition LIPID
The lipids are heterogeneous group of com
pounds related to the fatty acids either actual or COMPOUND DERIVED
potential, insoluble in water, soluble in other so SIMPLE
vents such as ether, chloroform and benzene and of fatty (Esters of fatty (Substances
(Esterwith derived from
chemically are esters of fatty acid and some al acids acids contain-
cohols.
various nggroups in above group
alcohols) addition to an by hydrolysis)
Sources: The lipids occur widely in plant and alcohol anda
animal kingdom. fatty acid) Fatty acicds,
8ycerol, sterol,
Examples: The lipids include fats, oils, waxes steroid, fatty
and related compounds. Oils are liquids at 20°C but aldehyde, ketóne
fats are solid at 20°C. PHOSPHOLIPID
(Alcohol+ fatty acids
boides, lipid
soluble vitamins
+phosphoric acid+ and hormones
Biological Importance nitrogen containing
1. In the body, fat serve as an efficient sources base and other

of energy when stored in an adipose tissue. substituents)

The fat-soluble vitamins and the essential

GLYCOLIPIDS
(cerebrosides)
ite af
fatty acids are found with the fat of natural foods.
3. It serves as an insulating material in the (Fatty acidsS+ 5
amino alcohol+ g
subcutaneous tissues and around certain or carbohydrate)
gans.
SULPHOLIPID
4. The phosphatides of blood platelets are in-
volved in the production of thromboplastin activity AMINOLIPID 2/ at 2
in the early stages of blood clotting LIPOPROTEINS altbeg
5. Lipoproteins (combinations of fat and
protein) and glycolipids (combinations of fat and
carbohydrate) are essential for maintaining cellular
integrity. FAT WAX
6. Itprovides building blocks for different high (Esters of fatty acids (Esters of fatty acids
with glycerol) with higher alcohols
molecular weight substances, eg, acetic acid and can other than glycerol)
be used for the synthesis of cholesterol and certain
hormones. Glycerides (acylglycerols), cholesterol and
cholesteryl esters are neutral lipids because they are
7 .They produce metabolites through oxida uncharged.
tion in the tissues which are used in the interconver
1. SIMPLE LIPIDS
sion of substances
A. Fats
Classification
(a) They are esters of fatty acids with glycerol.
Bloor has proposed the following classification of b) They are found in nature in large quan
upids: tities.

9
 cONCEPTS OF BIOCHEMISTRY
material in 2. The products are gycerol and
are the best r e s e r v e of food the alkat
They of the fatty acids which are called ps. sa
the human body.
(a) They act as insulator for the loss of body 3. Fats, phospholipids, 8ycolipids and
heat. are called saponifiable lipid. waxes
(They act as a padding material for protect- 4. Steroids,
ing internal organs.
polyisoprenoids and
highes
coholsare grouped as unsaponifiable
The chemical structure of fat (trgiyc ride) con they cannot given rise to soap. lipids because
sists of
three different molecules of fatty acids with
one molecule of glycerol. The three different fatty ()Saponificationnumber:
acids (R, R R) are esterified with the three 1. The number of
milligrams
of KOH is
hydroxyl groups of glycerol. quired to saponity 1 gram of fat or oil. re

CH:OH HOOC-RI CH:0.CO.R1 2. The amount of alkali needed to

saponifya
CHOH+ HOOC-Ra
given quantity ot tat will be
depended upon
CH:O.COR number of -coOH group present. It is the
inversely
CH:OH HOOC-R3 CHO.CO.Rs proportional to the average molecular weight of the
Glycerol Fatty acids
Triglycende fatty acids in thewillfathave
1.e. the fats
containing short
chain fatty acids more-COOHgroups per
Fig. 3.1 gram than long chain fatty acids and this will take
Physical Properties of Fats: up more alkali and hence will have
saponification number. higher
(a) The fats are insoluble in water, but
soluble in ether, chloroform, benzene, carbon readily
tetrachloride
Example: Butter containing larger proportion
a

of short chain fatty acids such butyric and caproic

as
6) They are readily soluble in hot alcohol but acias, nas relatively high saponification number 220
slightly soluble in cold. to 230.

other
(C)They
fats,
themselves good solvents for
are
(a) Acd number
fatty acids, etc. 1. The number of milligrams of KOH is re
(d) They are tasteless,
odourless, colourless quired to neutralize the free
and neutral in
reaction tat.
fatty acids of 1 gram
of

(e) Several neutral fats

eg beef, mutton.
are
readily crystallised, 2.
Significance: The acid number indicates the
degree of rancidity of the given fat.
(0 Their melting points are low e) lodine number:
() The
specific gravity of solid fats is about
086. So the fat .This is the amount (in grams) ot 1o
people float in water more orbed
than thin ones. readily by 100 grams of fat.
(h) They spread uniformly over the 2. This is
the of un-
measure of the degre
water s0the surface of saturation of a
spreading
;

etfect is to fat.
tension. lower surface
3. Significance: If the fat contains
ldentification of Fats and Oils hignees
Der of unsaturated fatty acids, it becomes l

for
(a) Hydrolysis the
protection of heart disease
saturated fatty acids being combine th the
Hydrolysis of triacylglycerol takes place
lipases producing
cholesterol are oxidized
in the liver
nbile
tatty acids and by acids, bile salts, vit. D, piormone
2. glycerol. gonadotrop
horm

phospholipids.
Phospholipases atack the ester They prevent atherosclerosis.
linkage of (0 Acetyl mumber:
6) Sapofiaation 2
1. The
L
number
of requir
metallic Boslng with an alcoholic solution
KOH
heutralize the millig
milligrams of

and fattyalkali hydrolyzes obtained by saponifnca

of
strong tion of 1 acid
acids is called triglycerides gram of fat after
saponificationintoglycerol acid
2. This
it has
is a measure of
the
pe
number
r o f h y d r a s y

groups in the fat.

 LIPDS 21

8) Polenske number : COMPOUND LIPIDS

1. The number of mililitersof 0.10) KOH A. Phospholipids (phosphatides)

required to neutralize the insoluble fatty acids from
5grams of fat. ) They are esters of fatty acids with glycerol
an esterified phosphoric acid and a
(h) Reichert-Miessl number: containing
r o g e n Dase.
1. Polenske number
This is the same as the
(i) They are present in large amounts in nerve
except that the soluble fatty acids are measured by
tissue, brain, liver, kidney, pancreas and heart.
titration of the
distillate obtained by steam distilla
tion of the saponification mixture.
Biological functions of phospholipids:
2. Significance: It measures the amount of
volatile soluble fatty acids, ) They increase the rate of fatty acid oxida-
tion.
() Halogenation
1. Chlorine, bromine and iodine atoms maye (ii) Theyact as carriers of inorganicions across
added to the double bonds of unsaturated fatty he membranes.
the
acids containing fats. (Gii) They help blood clotting
) Rancidity (iv) They act as prosthetic group to certain en
1. Nearly all natural fats are oxidized when e s(v) They form
exposed to air, light, moisture, particularly, ifwarm, the structures of membranes,
it an odour taste. The of
matrix cell wall, myelin sheath, microsomes and
zyme
develops unpleasant
lipase which in the presence of
and en-
moisture and mitochondria.
zyme lipase w
warm temperature bring about hydrolysis
rapidly.
2. This happens so due to the formation of Classification
peroxides at the double bonds of unsaturated fatty It is based on the type of alcohol present in the
acids. phospholipid.
3. Vitamin E is an important natural an There are three types.
tioxidant and prevents development of rancidity. (a) Glycerophosphatides-In this, glycerol is the
() Soaps: alcohol group
1. Soaps are metallic salts of fatty acids.
Example:
2. Soaps are formed by adding alkalis to fatty ) Phosphatidyl ethanolamine (cephalin).
acids. (Gi) Phosphatidyl choline (Lecithin).
3. Soaps of unsaturated fatty acids are softer
and more water soluble than those of saturated fatty (ii) Phosphatidyl serine.
acids. (iv) Plasmalogens.
4. Potassium soap of an acid is more water
(v) Phosphatidic acid.
soluble and softer than
the sodium soap, calcium
and magnesium soaps are far less soluble (b) Phosphoinositides In this, inositol is the
alcohol
B. Waxes
Example:Phosphatidyl inositol (Lipositol).
1. They are esters of fatty acids with higher
(c) PhosphosphuingosidesIn this, sphingosine
alcohols other than glycerol is an amino alcohol
2. In the human body, the commonest waxes
are esters of cholesterol.
Example: Sphingomyelin.
The phospholipids include the following
3. They are mainly three types such as
(a) True waxes are esters of higher fatty acids 8roups
alcohol or other higher straight chain
1. Phosphatidic acid and phosphatidyl glycerols
with acetyl
alcohols. Phosphatidic acid is important as an inter
mediate in the synthesis of triacylglycerols and
(b) Cholesterol esters are esters of fatty acid
with cholesterol. phospholipids.
(Vitamin Aand vitamin Destersare palmitic Cardiolipin
(a) It is formed from phosphatidyl glycerol.
or stearic acid esters of vitamin A (Retinol) or
vitamin D respectively. b) Chemically, it is diphosphatidyl glycerol.
 coNCEPTS OFBOOHEMSTRY
of Lecithin:
Physiological Functions
with
I t facilitate the combinations proteins
ot plasma and cells.
to from lipcoproteins
CH-O () Acetylcholine formed from choline has
mportant role in the transmission ot nervous im-
an

CHooH pulses across synapse

(1) Choline is the most important ipotropie
Phosphotidic acid
FoEmationh of fatty liver.
gent as it can prevent

Fig. 32 (iv) Lecithin lowens the surtace

B a
tension ot

constituemt
lung
of
in inner membrane of alveoli. Dipalmityl lecithin major
C)t 1s
tound adherence
lung surfactant which prevents the
of

mutochondria and bacterial wall

the inner surtace ot the alveouOthe ung (preven
2 Lecithins (Phosphatidylchsline) the alveol) by its surtace
tension

The lecithins contain giycerol and tatty acids,

ing the collapse ot the alveolar
tn
1he absence ot this
phosphoric a c i d and choline (nit
lowering effect.
membrane o f some premature i n t a n s causes the

Lecithins 8enerayc aistress syndrome in them.

tttty acd at B posi-
acid at
proy

Ption.
They can exist in d
(v) It lowers the surface tension of water
in the emulsification of fat.
oF P molecule and helps
Difference of Lecithin and Cephalin

acHocR Cadmiunm chloride compound

ot oephalin is
iecithin
p CH-O-C- Solubiebutcadmium chlotidecompound ot
is insolupe
a CHo-t0-HCHNCH, 3. Cephalins (Phosphatidyl etthanolamine)

Lecithin holine

Fig 33
cH-o-
Physical Properties: CH00-C,HNH
substances but
0) Lecithins are waxy, white
become brown soon when
exPosed to ai.

(3) They are soluble in ordinary fat solvents

eptacetone

in) They decompose when heated. They always occur in

the
tissues in association fne
with lecithins and are very similarin properties.
iv) They constitute valuabie gen only difference is the nitrogenous base.
emulsithications of tats and oils
4 Phosphatidyl Serine
Chemical Properties of Lecithin:

) When aqueous solution of lecithins are

shaken with HsOy choline is split ott, torming

Phosphatidic acid.
CB-
( )When lecithins are boiled with alkalis or
mineral acids, not only choline is pit of. phos
phatidic acid is further hydrolyzed to gycerophos-
CHlofo-CHH-COO
OF
of fatty acids. Photphatidy serine
phoric acid and 2 molecules

Lecithin Phosphatidic acid +choline. Fig. 3.5

Phosphatidic a c i d - G y c e r o p h o s p h o r i c acid + Acephaline like phospholipid is found in h s

fatty acids (2 mol)

 LIPIDS
5. Phosphatidyl inositol (Lipositol or Phos- a CH-0-CH-CH-R
phoinositides)
BCH-O--R
Y
CH,-0-C-R aCH 0-j-oCH CH-NH,
DH
CH-O--R Ethanolamine
9 OH Plasmalogen (Phosphatidal ethanolamine)
CH-0-P-0 H
HO/OH
OH
Fig.33.8
(ii) They possess an ether link in a position
Phosphatidyl
inositol Inositol
instead of ester link. The alkyl radical is an un-
saturated alcohol.
Fig. 3.6 8. Sphingomyelins:
9It acts as second messenger in Ca de-
pendent hormone actid
Sphingosine
(1i) Some
OH
signals must provide
communica CH (CHuCH-CH-CH-CH-N-ÖR
tion between the hormone on the plasma
receptor
membrane and intracellular Ca" reservoirs.
H Fatty acid

iii) They are more acidic than the other phos Phosphoric acid OP-OH
pholipids o-CHCH-N(CH,),
phingomyelin Choline)
6. Lysophospholipids:

Fig. 3.9
H-o-,
) These are found in large quantities in brain
OH and nerve tissue.
CH
CH,-0-0-CH,
OH
CH NCH
CH
i) The concentrations of these phospholipids

Lysolecithin Choline are increased in Niemann-Pick disease in the liver

and spleen.

.3.7 (ii) These contain sphingosine (18 carbon)

(amino alcohol) fatty acid, phosphoric acid and
) These are
phosphoacylglycerols
contain- choline. Noglycerol is present.
ing only one acyl radical in a position eg, iv) In sphingosine molecule -NH2 group
Lysolecithin. binds a
fatty acid by an amide linkage to produce
(11) Formation: ceramide. When phosphate
group is attached to
ceramide it is called ceramide phosphate.
(a) By the action of phospholipase A
(v) When choline is split off from sphin-
(b) By interaction of lecithin and cholesterol in gomyelin, ceramide phosphate is left.
presence of the enzyme lecithin cholesterol acyl
so lysolecithin and cholesterol ester are
transferase,
tormed CLINICALASPECT
I n Niermann-Pick disease excess amount of
Lecithin + cholesterol sphin
gomyelin are deposited in brain, liver, spleen.
LCAT
I t is a lipid storage disease (lipidoses) and
Lysolecithin+ cholesterol ester
7. Plasmalogens: hereditary. It is caused by the deficlency of enzyme
sphingomyelinase.
(0 These are the contents of brain and muscle. The clinical findings are:
(1) Structurally, these resemble lecithins and (a) Enlarged liver and spleen.
cephalins but give a positive reaction when tested
(b) Mental retardation.
for aldehydes with Schiffs
reagent (fuchsin-sul (c) Nervous system is affected.
phurous acid) after pretreatment of the phos-
pholipid with mercuric chloride. (d) Anemia and leukocytosis.
 CONCEPTS OF BIOCHEMISTRY
Action of Phospholipase
Oxynervon-Containing hydroxynervonic
(a) Phospholipase A attacks the ester bond in acd cH CHa}y-CH CH-(CH)
CH(OH)COOH]. 12
position 1 of phospholipid.
(6) Phospholipase A attacks B position and (d) Stearic acid is a
major component of the
of rat brain cerebrosides.
form
fattyacids
Lysolecithin +one mol. fatty acid. (e) Cerebrosides, specially cerebronic acid, in-
() Phospholipase B lysophospholipase) at creases in Gauchers disease and the Kerasin char-
acks ysolecithin and hydrolyzes ester bond in acterized by Eucose replacing galactose
position and forms glyceryl phosphoryl choline + 1 ( The cerebrosides are in much higher
con
mol. tatty acid.
centration in medullated than in nonmedullated
(d) Phospholipase C hydrolyzes phosphate nerve nbers,
ester bond and
produces a,
diacyl glycerol+
phosphoryl choline. CLINICAL ASPECT OF CEREBROSIDE
() Phospholipase D-splits off choline and Gaucher's disease
phosphatidic acid is formed
The cerebroside content of the reticuloendothelial
cell (spleen) is very nign.
Phospholipase A
Oco-R, In cerebroside molecule, the kerasin is
charac
tenised by glucose replacing galactose
R-Co-c-H Phospholipase D The
disease is caused by the deficiency of enzyme
Phospholipase CHoiPjo N-base glucocerebrosidase.
OH (Choline)
Phospholipase C Symptom
Spleen is increased, signs of leucopenia.
B. Glycolipids Liver is enlarged.
These contain an amino Eyes show a yellow brown
alcohol (sphingosineor
iso-sphingosine) attached with an amide linkage to tion.
wedge shaped eleva
a
tatty acid and gycosidically to a carbohydrate
moiety (sugans, amino sugar, sialic acid). (i) Gangliosides:
These are
further classified into ) (a) These are glycolipids occurring in the
Cerebrosides, (Gi) Gangliosides. brain.
9 Cerebrosides: (6) Gangliosides contain ceramide (sphin-
(a) Cerebrosides contain galactose, a high netatty acids), glucose, galactose, N-acetyl
molecular weight fatty acid and sphingosine.There- 8alactosamine and sialic acid.
fore, they may also be classified as sphingolipids (c) Some gangliosides also contain
dihydros
(o) They are the chief constituent of myelin Phingosine or Gangliosine in place of sphin
sheath.
8osine
(c) They may be differentiated by the type of (d) Most of the gangliosides contain a
two
glucose,
fatty acid in the molecule molecules of galactose, one
N-acetylgalac-
tosamine and upto three molecules of sialic acid.
These are
Types of Ganglioside
Kerasin-Containing lignocericacid [CH3
(CH)22COOH]. GM, ganglioside :
Cerebron-Containing a hydroxylignoceric Gal->Gal NAC
Gal ->Glucose-Ceramide
acid (cerebronic acid).
NANA
CH-CHh-CH(OH)-coOH) GM, ganglioside :
NervonContaining an nervonic
unsaturated Gal
NACGal Glucose Ceramide
homologue of lignoceric acid called acid.
ICH-(CH,-CH=CH-(CHhs-COOH NANA
LIPIDS

GMg ganglioside: ii) The density of lipoproteins increases as the

GalGlucoseCeramide anqy
protein content rises and the lipid content falls and
the size of the particle becomes smaller.
NANA (iv) Lipoproteins may be separated on the
G=Ganglioside, M = Monosialo variety.
basis of their electrophoretic properties and may be
1,2,3= Position in chromatography. identified more accurately by means of immuno-

GMgangliosidosis: This is due to deficiency of lectrophoresis.

have
enzyme -galactosidase.
o groups lipoproteins
of
hoon
been identified which are important physiologically
Tay Sach's disease (GMa gangliosidosis): and in clinical diagnosis in some metabolic disor
ders of fat metabolism.
This disease is characterised by increased
ac
cumulation of GM2 ganglioside in brain and spleen. These are: OV
is (a) Chylomicrons.
It caused by
nexosaminidase A.
deficiency of enzyme
b)Very low density lipoproteins (VLDL or
Pre-p-lipoproteins).
Symptom: (Low density lipoproteins (LDL or p
lipoproteins).
Mental retardation, blindness, muscular
weakness. d High density lipoproteins (HDL or a -

Red spot appears in the muscular region of eye in lipoproteins)

first year of life. (vi) Chylomicrons and VLDL

Predominant lipid triacylglyceraolof(50%) and

is
cholesterol (23%). The concentrations these are
C. Other compound lipids increased in atherosclerosis and coronary throm-
bosis etc.
Lipoproteins
LDL: Predominant lipid is cholesterol
) Triacylglycerol (45%), phospholipids (46%) and phospholipids (23%). In
(35%%), cholesterol and cholesteryl esters (15%), free crease in atherosclerosis and
fatty acids (less than 5%6) and also protein combine coronary thrombosis, etc.
to form a hydrophilic lipoprotein complex. HDL: Predominant lipid is phospholipid
i) Since pure fat is less dense than water, the (27%) and proteins(45%)
proportion of lipid to protein in lipoproteins in plas- (vii) The protein moiety lipoprotein is known
ma is by ultracentrifugation.
as an apoprotein which constitute nearly 60% of
HDL and 19% of
some
chylomicrons. Many
lipoproteins contain more than one type of
DENSITY
rOrigin apoprotein polypeptide.
<0.96 (vii) The larger lipoproteins (such as
Chylomicrons
chylomicrons and VLDL consistof a lipid core of
nonpolar triacylglycerol and cholesteryl ester sur-
1.006-1.063 3-Lipoproteins rounded by more polar phospholipid, cholesterol
(LDL) and apoproteins.

(v L)
Pre-p-Lipoproteins Importance:
) To transport and deliver the lipids to tis-
sues.
(ii) Tomaintain structural integrity of cell sur
1.063-1 face and subcellular particles like mitochondria and
a-Lipoproteins
(HDL) microsomes.
(ii) The -lipoprotein fraction increases in
severe diabetes mellitus, atherosclerosis etc. Hlence
determination of the relative concentrations of a-
teparation of plasma lipoproteins by paper) and P-lipoproteins and pre-p- lipoproteins are of
Fig. 3.10 diagnostic importance
 cONCEPTS OF BIOCHEMISTRY
2. Aminolipids Types
Phosphatidyl ethanolamine and serines are 1. Straight chain.
aminolipids and sphingomyelins and gangliosides 2. Branched chain.
contain substituted amino
groups 3. Substituted (methyl substituted-cerebronic
acid)
3. Sulpholipids (Sulphatides)
4. Cyclic (chaulmoogric acid) used in leprosy.
) These have been isolated from brain and 1. Straight chain :
other animal tissuesS.
(a) Saturated ( odd than (less 10 carbon atom)
(ii) These are sulphate derivativesof the galac & even (greater than 10 carbon atom)).
tosyl residue in cerebrosides. (b) Unsaturated (odd & even).
DERIVED LIPIDS (Straight chain even number fatty acid is com-
mon)
1. Fatty acids
A. Saturated fatty acids
() These are obtained by the hydrolysis of
fats. General formula for saturated fatty acids is
CH2n+1 COO. Other higher fatty acids occur in
(ii)
FattyFatty acids
acids occurring
occurring in
in natural
natural fats usual waxes. A tew branched-chain fatty acids have also
ly contain an even number of carbon atoms tats usual been isolated from both plant and
because
Prostanoids include Prostaglandins (PG),
animal
sourcesand
they are
synthesized from 2-carbon units and are
straight chain derivatives. thromboxanes (TX).
General characteristics of
i) The straight chain may be saturated (con- prostanoid
taining no double bonds) (a) All are 20 carbon compound.
unsaturated (contain-
or
ing one or more double
bonds). (b) Trans double bond at 13 position.
(iv) Carbon atoms of fatty acids are numbered -OH group at 15 position.
from the
carboxyl carbon (carbon No.1). The carbon Prostaglandins (PG)
atom adjacent to the carboxyl carbon
is also known
(Carbon No. 2) (a) They virtually exist
the a-carbon. Carbon atom No. 3
as in every mammalian
is the tissue and act as local hormones.
-carbon and the end methyl carbon is known
as the y-carbon. (b) They have important
pharmacologic activities. physiologic and
(v) Various conventions are used for
indicat-
ing the number and position of the double ()They are synthesized in vivo by
eg. A indicates a double bond between bonds,
of the center of the
carbon chain of 20-Ccyclization
atorms 9 and 10 of the
fatty acid.
carbon saturated fatty acids (e-g. arachidonic acid) polyun-
a cyclopentane ring8 to form

Saturated fatty acids

Acd Formula
Carbon atoms
ources
Acetic CHCOOH
Product of
CaHscoOH carbohydrate fermentation by rumen organisms.
CsHCOOH do
CsHaCOOH Product of
Butter.
CHisCOOH 8 carbohydrate fermentation by rumen
CaHaCOOH Butter. organisms.
Butter.
CuHsCOOH
CuHaCOOH
2
4 onut oils.
CisHaCOOH Coconut oils.
CpHsCOOH 18 Animal and plant fats.
rechidice Cis Hos COOH
0 do
CnHoCOOH Peanut oil.
Dgnocen CaHeCOOH Seeds
Peanut oil, crebrosides.
LIPIDS

B. Unsaturated fatty acids:

General formula CnHan-1 COOH
Type of acid Acid Formula Unsaturation at Number of Sources
carbon atoms double bonds
Mono-unsaturated Palmitoleic CisHasCOOH
Near all fats
Oleic Ci7HasCOOH 4 do
Poly-unsaturated Linoleic CipHsiCOOOH A,A Animal and plant fat
Linolenic CiHasCoOH
do
Arachidonic C19Hs1coOH
Eicosanoids
D,A, A",A Peanut oil

Prostanoids & Timnoionic CioHssCOOH

Leukotrienes A,A,A", a",a7 Fish oils, eg, cod
lver oil
Clupanodonic CpH:COOH ,AD,a, al, a° Fish oils, phos
pholipids in brain

Cervonic Ca1Hs1COOH A',A,A,A,AA Fish oils, phos-

pholipids in brain
Classification
Linolenic acid Arachidonic acid

Eicosanoic acid

Eicosanoid

Prostanoid Leukotriene
Via (LIA4
LTB4
Prostaglandin Thromboxane lypooxygenase LTC4
(PGI2 PGE2, PGD2) (TXA2)
pathway ETD4
LTEA
Via
Aspirin Cyclooxygenas
pathway
d) Three different eicosanoic fatty acids give Prostacyclins (PGI)
rise to three groups of eicosanoids characterized by (a) They are formed in vascular endothelium
the number of double bonds in the side chains, eg and continually formed in heart. They are also
PG,PG PG. Variations in the substituent groups formed in kidneys.
attached to the rings give rise to different types in (6) They are formed from cyclic endoperoxide
eachseries of prostaglandins, as for example,EPGH,by the action of microsomal Prostacyclin syn-
ype of Prostaglandin has a keto grOup in position thetase.
9, whereas the "F" type has a hydroxyl group in this (c) They inhibit platelet aggregation and
position, gastric secretion from the pyloric mucosa.
 cONCEPTS OF BIOCHEMISTRY

coo
c0
Leukotriene A, (LTA)
OH
OH
Prostaglandin E, PGE;) Fig. 3.13

(c) They are characterized by the

Fig.3.11 three
conugated double bonds. presence of
(d) They decrease blood (d) They are
coronary arteries. pressure and protect and
stimulators of mucus
secretion
are
. ( They increase renal blood responsible
bronchial muscles.
for
vasoconstriction of
late renin production. flow and stimu-
(e) They are inhibited
() They are aspirin. by prolonged use of
inhibited
deticiency and radiation. by hyperlipemia, vit. E
The
groupof compounds known as
Thromboxanes dins are
synthesized from arachidonic
prostaglan
acid
body. They have in the
(a)
They contract smooth muscles activity. pharmacologic and biochemical
essels, Gl tract, on blood
uterus, bronchioles. Example: Prostaglandin
E, (PGE,)
COO
coOH

OH

Thromboxane A, (TXA, Prostaglandin E, (PGE,

Fig3.12 Fig. 3.14
C. Many Other Fatty Acids:
the
6) They are discavered in
cyclopentane platelets, and have
atom (Oxane ring).ring interrupted with an ) These have
oxygen material. been detected in
(c) The substituent biologic
rings being varied groups attached to the
give rise to different
Example: Fish oil contain 5 and 6
tatty acids
series of
thromboxanes labelled A, B, etc.types in each having carbon atoms
22.
unsaturated
(d) They (ii) Various other
produce vasoconstriction and
crease blood pressure. groups (ricinoleic structures with
(e) They cause
in- found in nature. acid) or cyclic hydroxy
groups have been
release of serotonin
ion
(Ca ) from platelet and calcium Example of
cyclic groups is
(9 Imidazoles granules which was used
many years ago chaulmoogric acia
inhibit their leprosy. in the
synthesis. treatment of
Leukotrienes
(a)
They are
derivatives formed thevia third group
H,C -HH-CH) COOH
of
rather than the eicosanoid
cyclization
b) They are first
of thelipoxygenase
fatty acid pathway
chain.
described in Chaulmoogric acid
leukocytes
Fig. 3.15
LIPIDS
General formula No. of double itructure Sources
Chemical name
Essentialfatty
bonds
actds CHa-(CHa Corn, Peanut
Linoleic ,12-Octadecadi- CaHanaCOOH 2(AA)
(CH-CH-CHE)h Cotton seed,
enoic acid oil.
(CHa)% COOH Soyabean

6,9,12-Octadeca CaHan-5 COOH 34A"A") CH-(CHa4 Found frequently

Linolenic (CH=CH-CHa)s with linoleic acid
trienoic acid
(CHas COOH but particularly
in inseed oil.

Arachidonic 5,8,11,14-eicosatetra- CnHan-7 COOH 4(4AA"A") CH-(CHa)a(CH

CH-CHa4
Found in small
quantities with
enoic acidd and
(CHa2 COOH linoleic
linolenic acids

but particularly
in peanut ol

ISOMERISM IN UNSATURATED
ESSENTIAL FATTY ACIDS
FATTYACIDS
Burr and Burr (1930) introduced the term "Es-
Variations in the locations of the double
bond
sential Fatty Acids (EFA) on the pas1S tnat tney are in unsaturated fatty acid chains produce 150mers.
essential for the growth and health of young albino
ec acid has 15 difterent positional isomers.
which
1hese polyunsaturated fatty
rats. acids are
from
not synthesized in the body but are taken HOOC
natural sources are called essential fatty acids. They
HOOC
are (mentioned above): H COOH
HOOC H
Linolenic and arachidonic acids are formed
Cis form Trans form
Fumaric acid)
from linoleic acids provided linoleic acids are avail- (Maleic acid)
able in the body in sufficient quantities.
Fig.3.16
Properties: Geometric isomerism depends on the orienta
) The essential fatty acids of vegetable oils tion of radicals around the axis of double bonds. If
have low melting points and iodine number. the radicals which are being considered are on the
side of the bond, the compound is called "cis"
(i) They become saturated fatty acids on same
if on opposite side, trans" This can be illustrated
hydrogenation and the oils become solid fats. with maleic acid and fumaric acid.

Functions : There are more geometric isomers in case of

(1) The essential fatty acids in high concentra acids with greater degree of unsaturation. 1The un-
tion along with the lipids constitute the structural
Saturated
long chain of fatty acids occurring in na-
ture are nearly all if the'cis' form and the molecules
elements of the tissues are "bent" at the position of the double bond. Thus,
(2) The lipids of gonads also contain a high
arachidonic acid is U-shaped.
concentration of polyunsaturated fatty acids which
suggestthe importance of reproductive function. REFINED AND
(3) They effect the prolongation of clotting HYDROGENATED OILs
time and increase the fibrinolytic activity. Refined oil : It is prepared in the following
(4) They retard atherosclerosis being esterified manner:
and emulsified with cholesterol and are incor
) Free fatty acids are removed by alkali treat
porated into lipoproteins for transport to the liver ment.
for further oxidation.
5) They cure skin lesions. (i) Colouring matter is removed by activated
acids in the diet ofaD
o The deficiency of these (ii) Odour is removed by superheated steam.
babies causes eczema.
 cONCEPTS OF BIOCHEMISTRY
Hydrogenated oils: The refined
oils are Steroids may be divided in the
following man-
hydrogemated under optimum
temperature and
pressure with hydrogen in the presence of nickel ner
catalyst. Unsaturated fatty acids are converted into Sterols -cholesterol, ergosterol, coprosterol.
Bile acids-Glycocholic acid and
saturated fatty acids taurocholic
acid.

Sex hormones-Testosterone, Estradiol.

Hydrogenation
Oleic acid Stearic acid. Vitamin D-Vit. D, and Dg
Adrenocortical hormones-Corticosterone.
The
liquid oil becomes solid fat and the un- Cardiac glycosides-Stropanthin.
saturated fatty acid content decreases.
Vanaspati is
Saponins -Digitonin.
hydrogenated refined groundnut oil.
Cholesterol
2. ALCOHOLS It is widely distributed in all cells of the body
animal but not in plant fats. Its
Alcohols found in lipid molecules include
t occurs in fats
structure is given below. The metabolism of
Bycerol, cholesterol and higher alcohols (cetyl a- cholesterol is discused in the chapter of lipid meta-
cohol), usually found in the waxes. bolism.
The unsaturated alcohols are important
pig
ments. Phytyl alcohol is a constituent of chlorophyll
and lycophyll (C4ois6O2); a polyunsaturated
dihydroxy alcohol occurs in tomatoes as a purple
P1gment.

3. STEROIDS
(Cholestero)
The steroids are often found in association with Fig.3
3.18

fat. They have similar cyclic nucleus

a
resembling Erogesrol
phenanthrene (rings A, B, C) to which a cyclopen-
) It occurs in ergot and yeast.
tane ring (D) is attached. Ihe
better
substanceparent ) It is the
precursor of vitamin D.
designated as
cyclopentano-per (ii) Tt acquires antirachitic properties with the
hydrophenanthrene.The position on the steroid
Opening ot ring B when irradiated with ultraviolet
nucleus are numbered as shown in the 4.14.
fig8ure light.
Methyl side chains occur typically atpositions
and 13
10 (constituting C
atoms 19 and
chain at position 17 is usual (as in cholesterol). If the
18). A side
has more hydroxylgroups and no
compound one or
carbonyl or carboxyl groups, it is a sterol, and the
name terminates
in OL.
HO

Ergostero)

Fig. 3.19

Coprosterol
opcntanopertiydropbcnanthrene
nacleus
Tt occurs in feces as a result of the reduction by
bacteria in the intestine of the double band between
Fg3.17 Cs and Cgof cholesterol.
LIPIDS
CLINICALIMPORTANCE
Important tests
The high concentration of polyunsaturated fatty
important in
(1) Greese spot test: A drop of oil placed over acids in the lipids of gonads
are

translucent spot is
ordinary paper. A
reproductive function.
a piece ot
of fat. causes sweling
visible. This indicates the presence The essential fatty acid deficiency reduc-
taken in membrane resulting in the
(2) Emulsification test: 2 ml water is of mitochondrial
oxidative phosphorylation
and 2 ml of diluted bile salt solution in tion in efficiency of
one test tube producing increased heat.
of the given oil to
another test tube. Add 3 drops
Note the Docosahexenoic acid formed from dietary linolenic
each test tube and shake vigorously. of the
emulsification formed. acids enhances the electrical response
stability of the photoreceptors to
illumination. Therefore,
linolenic

test Take 10 drops of tor opimal vision.

(3) Saponification acid of the diet is essential

oil in test tube. Add 20 drops of 40%

a
coconut
it. Gently boil for The deficiency of essential fatty acids causes skin
NaOH and 2 ml of glycerol to and lactation in adult
oc- lesions, abnormal pregnancy
about 3 minutes until complete saponification
are visible, boiling must be con-
females, fatty liver, kidney damage.
curs. If oil globules cholesterol acyl
the The genetic deficiency of lecithin Disease.
tinued. Divide
the solution into3 parts to carry transferase (LCAT) causes Norum's

following experiments in test tube 1, 2,3. intestinal absorption of

Sitosterol decreases the
To test tube No. 1 add saturated solution of and endogenous
cholesteroland there
exogenous
floats to
NaCl. Note that the soap separates out and by lowers the blood cholesterol level.
the surface (salting out process). The deficiency of the enzyme sphingomyelinase
HCI. causes the large accumulations of sphingomyelins
To test tube No. 2 add a few drops of conc. in the
and spleen of children resulting
An oily layer of the fatty acids rises to the
surface. in brain, ihver of en-
Niemann-Pick disease with the symptoms
To test tube No. 3 add a few drops of CaCh spleen and mental deteriora-
larged abdomen, liver,
solution. The insoluble calcium soap is precipitated. tion.

Unsaturation test: Add 10 drops of Huble's Absence of dipalmityl lecithin (DPL) in

premature
foetus produces respiratory distress syndrome
to 10 ml of chlorotorm. The
iodine reagent (Hyaline-membrane disease).
chloroform pink colour due to the free
assumes a
The inherited Gaucher's Disease in infancy and
iodine. The solution is divided equally into three test childhood is caused by the deficiency of the enzyme
and (C) and three of oil are
tubes as (a), (6) types glucocerebrosidase involving the large accumula-
tions of glucocerebrosides (usually Kerasin) in the
added.
brain with the
Add the oil No. 1 to the test tube (a) drop by liver, spleen, bone marrow, and
manifestations weight loss,
of failure in growth, and
after each addi-
drop shaking the tube vigorously progressive mental retardation.
tion till the pink colour of the solution just disap-
noted.
The autosomal recessive Tay-Sach's Disease
pears. The number of oil drops required are
(GM2 Gangliosidosis) results in the accumulation of
The experiment is repeated by oil 2 and 3 adding to large amounts of gangliosides in the brain and
test tubes (6) and (©), respectively. The more
the nervous tissues due to the absence of the enzyme
number of drops required to discharge the pink hexosaminidase A with the assocation of progres
sive development of idiocy and blindness in infants
colour, the less is the unsaturation.
soon after birth.
Colour Reactions to Detect Sterols The inherited disorder Metachromatic
Leukodystrophy (MLD) happens on the salfatide,
Liebermann-Burchard Reaction: A formed from galactocerebroside, accumulation in
chloroform solution of a sterol when treated with various tissues owing to the deficiency of the en
zyme sulfatase (Aryl salfatase) with the symptoms
acetic anhydride and sulphuric acid gives a green of weakness, ataxia, defectsin inchildren
locomotion,
colour. This reaction is the basis of a colorimetric in before
estimation of blood cholesterol. paralysis, difficultes speech
three years of age and psychiatric manifestation
Salkowski test: A red to purple colour appears including progressive dementa in adults.

when a chloroform solution of the sterol is treated Obesity and atherosclerosis are distinctly related to
with an equal volume of concentrated sulphuric the concentrations of cholesterol and polyun-
acid.
saturated fatty acids in the body.
 CONCEPTs OF BIOCHEMISTRY
DIAGRAMMATIC COMPENDIUM

LIPIDS

(Insoluble in water but soluble in nonpolar solvent)

Simple Compound ul
(Fats & Wax) Derived
ogse
hospholipids Glycolipids Lipoproteins Fatty Acids Cholestrol

Saturated
Unsaturated Vitamin D Bile Acids

Adrenocortical & Sex Hormones

Polyunsaturated Monounsaturated
Eicosanoids

Prostaglandins ThrombOxanes Leukotrienes ld

Prostacycins

losoli d ol niolao