STRUCTURE FUNCTION

AND
CLASSIFICATION OF LIPIDS

BAS 121 Unit 4

CHEMISTRY OF LIPIDS
Definition:
 Lipids are organic compounds formed mainly
from alcohol and fatty acids combined
together by ester linkage.

O
H2O O
R CH2 OH HO C R R CH2 O C R
+
Fatty alcohol Fatty acid Esterase (lipase) ester (lipid)
 Lipids are insoluble in water, but
soluble in fat or organic solvents (ether,
chloroform, benzene, acetone).
 Lipids include fats, oils, waxes and
related compounds.
 They are widely distributed in nature
both in plants and in animals.
Biological Importance of Lipids:

1. They are more palatable and storable to unlimited

amount compared to carbohydrates.
2. They have a high-energy value (25% of body
needs) and they provide more energy per gram
than carbohydrates and proteins but
carbohydrates are the preferable source of energy.
3. Supply the essential fatty acids that cannot be
synthesized by the body.
4. Supply the body with fat-soluble vitamins (A, D, E
and K).
5. Tissue fat is an essential constituent of cell
membrane and nervous system.
It is mainly phospholipids in nature that are not
affected by starvation.
7- Stored lipids “depot fat” is stored in all human
cells acts as:
 A store of energy.
 A pad for the internal organs to protect them from
outside shocks.
 A subcutaneous thermal insulator against loss of
body heat.
8- Lipoproteins, which are complex of lipids and
proteins, are important cellular constituents that
present both in the cellular and subcellular
membranes.
9- Cholesterol enters in membrane structure and is
used for synthesis of adrenal cortical hormones,
vitamin D3 and bile acids.
 CLASSIFICATION OF LIPIDS

1. Simple lipids (Fats & Waxes)

2. Compound or conjugated lipids
3. Derived Lipids
4. Lipid-associating substances
FATTY ALCOHOLS
1-Glycerol:
 It is a trihydric alcohol (i.e., containing three
OH groups) and has the popular name
glycerin.
CH2 OH 2 H 2O
HO CH
Heating, KHSO
CH2 OH
Glycerol

 It is synthesized in the body from glucose.

1. Colorless viscous oily liquid with sweet
taste.
2. On esterification with fatty acids it gives:
 Monoglyceride or monoacyl-glycerol: one
fatty acid + glycerol.
 Diglyceride or diacyl-glycerol: two fatty
acids + glycerol.
 Triglyceride or triacyl-glycerol: three fatty
acids + glycerol.
 Esterification
glycerol three fatty acids triacylglycerol
O
CH2 OH HO C (CH2)14CH3
O
CH OH HO C (CH2)14CH3
O
CH2 OH HO C (CH2)14CH3 O
CH2 O C (CH2)14CH3
O
CH O C (CH2)14CH3 + 3H O
2

O
CH2 O C (CH2)14CH3
FATTY ACIDS
Definition:
 Fatty acids are aliphatic mono-carboxylic acids that
are mostly obtained from the hydrolysis of natural
fats and oils.

 Have the general formula R-(CH2)n-COOH and

mostly have straight chain.
 In this formula "n" is mostly an even number of carbon
atoms (2-34) with a few exceptions that have an odd
number.
 Fatty acids are classified according to several
bases as follows:
I. According to presence or absence of double
bonds they are classified into:
 A-Saturated Fatty Acids

 they contain no double bonds with 2-24 or

more carbons.
 They are solid at room temperature except if
they are short chained.
 They may be even or odd numbered.

 They have the following molecular formula,

CnH2n+1COOH.
Saturated fatty acids (no double )
COOH Stearic aci
(mp 70
A-Short chain Saturated F.A. (2-10 carbon).
COOH Oleic acid
a-Short chain Saturated volatile F.A.(2-6 (mp 16°

carbon).
COOH Linoleic ac
b- Short chain Saturated non volatile F.A.(7-10(mp-5
carbon).
COOH Linolenic a
B-Long chain Saturated F.A.(more then 10(mp -1
carbon)
a-Volatile short-chain fatty acids:
 They are liquid in nature and contain (1-6)
carbon atoms.
 water-soluble and volatile at room
temperature, e.g., acetic, butyric, and
caproic acids.
 Acetic F.A. (2C ) CH3-COOH.
 Butyric F.A. (4C ) CH3-(CH2)2-COOH.

 Caproic F.A. (6C ) CH3-(CH2)4-COOH.

b-Non-volatile short-chain fatty acids:
 They are solids at room temperature and
contain 7-10 carbon atoms.
 They are water-soluble and non-volatile at
room temperature include caprylic and
capric F.A.

 caprylic (8 C ) CH3-(CH2)6-COOH.
 Capric (10 C ) CH3-(CH2)8-COOH.
B-Long-chain fatty acids:
 They contain more than 10 carbon atoms.
 They occur in hydrogenated oils, animal fats, butter
and coconut and palm oils.
 They are non-volatile and water-insoluble
 Include palmitic, stearic, and lignoceric F.A.

 Palmitic(16C) CH3-(CH2)14-COOH
 Stearic (18 C ) CH3-(CH2)16-COOH
 lignoceric (24C ) CH3-(CH2)22-COOH
B-Unsaturated Fatty Acids COOH St

They contain double bond COOH O

 monounsaturated
COOH L
they contain one double bonds . COOH Steari

(CnH2n-1 COOH) COOH

(m
Li
COOH Oleic a

 polyunsaturated
(mp

they contain more the one double bond (CnH2n- (

COOH Linole

more than 1 COOH). COOH Linole

(m
1-Monounsaturated fatty acids:
1-Palmitoleic acid :
 It is found in all fats.

 It is C16:1∆9, i.e., has 16 carbons and one

double bond located at carbon number 9
and involving carbon 10.

CH3-( CH2 )5CH = CH-(CH2)7 –COOH

2-Oleic acid
 Is the most common fatty acid in natural
fats.
 It is C18:1∆9, i.e., has 18 carbons and one
double bond located at carbon number 9
and involving carbon 10.

CH3-(CH2)7- CH=CH – (CH2)7-COOH

2-Polyunsaturated fatty acids :
(Essential fatty acids):
 Definition:

 They are essential fatty acids that can not

be synthesized in the human body and
must be taken in adequate amounts in the
diet.
 They are required for normal growth and
metabolism
 Source: vegetable oils such as corn oil,
linseed oil, peanut oil, olive oil, cottonseed
oil, soybean oil and many other plant oils,
cod liver oil and animal fats.
 Deficiency: Their deficiency in the diet leads
to nutrition deficiency disease.
 Its symptoms include: poor growth and
health with susceptibility to infections,
dermatitis, decreased capacity to reproduce,
impaired transport of lipids, fatty liver, and
lowered resistance to stress.
Function of Essential Fatty Acids:
1. They are useful in the treatment of atherosclerosis by help
transporting blood cholesterol and lowering it and
transporting triglycerides.

2. The hormones are synthesized from them.

3. They enter in structure of all cellular and subcellular

membranes and the transporting plasma phospholipids.

4. They are essential for skin integrity, normal growth and

reproduction.

5. Important in preventing and treating fatty liver.

6. They can be oxidized for energy production.
1-Linoleic:
 C18:29, 12.

 It is the most important since other

essential fatty acids can be synthesized from
it in the body.

CH3-(CH2)4-CH = CH-CH2-CH=CH-(CH2)7-COOH
2-Linolenic acid:
 C18:39, 12, 15,

 in corn, linseed, peanut, olive, cottonseed

and soybean oils.

CH3-CH2-CH=CH-CH2-CH=CH-CH2-CH=CH-
(CH2)7-COOH
3-Arachidonic acid:
 C20:45, 8, 11, 14.

 It is an important component of
phospholipids in animal and in peanut oil
from which prostaglandins are synthesized.

CH3-(CH2)4-CH=CH-CH2-CH=CH-CH2-CH=CH-
CH2-CH=CH-(CH2)3-COOH
1-Simple Lipids
A-Neutral Fats and oils (Triglycerides)
Definition:
 They are called neutral because they are
uncharged due to absence of ionizable
groups in it.
 The neutral fats are the most abundant
lipids in nature. They constitute about 98%
of the lipids of adipose tissue, 30% of
plasma or liver lipids, less than 10% of
erythrocyte lipids.
 They are esters of glycerol with various fatty acids.
Since the 3 hydroxyl groups of glycerol are
esterified, the neutral fats are also called
“Triglycerides”.
 Esterification of glycerol with one molecule of fatty
acid gives monoglyceride, and that with 2
molecules gives diglyceride.

O O
HO C R1 CH2 OH H2C O C R1
O
O
HO C R2 + HO C H R2 C O C H
O
O
CH2 OH 3 H 2O H2C O C R3
HO C R3
Glycerol Triglycerides
Fatty acids (Triacylglycerol)
TYPES OF TRIGLYCERIDES
1-Simple triglycerides: If the three fatty acids
connected to glycerol are of the same type the
triglyceride is called simple triglyceride, e.g.,
tripalmitin.
2-Mixed triglycerides: if they are of different types, it
is called mixed triglycerides, e.g., stearo-diolein and
palmito-oleo-stearin.
 Natural fats are mixtures of mixed triglycerides
with a small amount of simple triglycerides.
 O
CH2 O C (CH2)14 CH3
O
CH3 (CH2)14 C O C H
O
CH2 O C (CH2)14 CH3
Tripalmitin
(simple triacylglycerol)
O
CH2 O C (CH2)16 CH3
O
CH3 (CH2)7 CH CH (CH2)7 C O C H
O
CH2 O C (CH2)7 CH CH (CH2)7 CH3
1-Stearo-2,3-diolein
(mixed triacylglycerol)
O
CH2 O C (CH2)14 CH3
O
CH3 (CH2)7 CH CH (CH2)7 C O C H
O
CH2 O C (CH2)16 CH3
1-palmito-2-oleo-3-stearin
(mixed triacylglycerol)
 The commonest fatty acids in animal
fats are palmitic, stearic and oleic
acids.
 The main difference between fats and
oils is for oils being liquid at room
temperature, whereas, fats are solids.
 This is mainly due to presence of larger
percentage of unsaturated fatty acids in
oils than fats that has mostly saturated
fatty acids.
Physical properties of fat and oils:
1. Freshly prepared fats and oils are colorless,
odorless and tasteless. Any color, or taste is due
to association with other foreign substances, e.g.,
the yellow color of body fat or milk fat is due to
carotene pigments(cow milk).
2. Fats have specific gravity less than 1 and,
therefore, they float on water.
3. Fats are insoluble in water, but soluble in organic
solvents as ether and benzene.
4. Melting points of fats are usually low, but
higher than the solidification point,
Chemical Properties of fats and oils:
1-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 pancreas).
 - 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
2-Saponification. Alkaline hydrolysis produces
glycerol and salts of fatty acids (soaps).
 Soaps cause emulsification of oily material this
help easy washing of the fatty materials

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)
3-Halogenation
 Neutral fats containing unsaturated fatty acids have the
ability of adding halogens (e.g., hydrogen or hydrogenation
and iodine or iodination) at the double bonds.
 It is a very important property to determine the degree of
unsaturation of the fat or oil that determines its biological
value

CH3 (CH2)4 CH CH CH2 CH CH (CH2)7 COOH

Linoleic acid
2 I2

CH3 (CH2)4 CH CH CH2 CH CH (CH2)7 COOH

I I I I
Stearate-tetra-iodinate
4-Hydrogenation or hardening of oils:
 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 base of hardening of oils (margarine
manufacturing), e.g., change of oleic acid of fats
(liquid) into stearic acid (solid).
 It is advisable not to saturate all double bonds;
otherwise margarine produced will be very hard, of
very low biological value and difficult to digest.
 Oils Hydrogen, high pressure, nickel Hard fat
(liquid) (margarine, solid)
(with unsaturated (with saturated
fatty acids, e.g., oleic) fatty acids, e.g., stearic)

Advantages for hydrogenated oil or fat are as follows:

1. It is more pleasant as cooking fat.
2. It is digestible and utilizable as normal animal fats and
oils.
3. It is less liable to cause gastric or intestinal irritation.
4. It is easily stored and transported and less liable to
rancidity.
Disadvantages of hydrogenated
 fats include lack of fat-soluble vitamins (A, D, E and K) and
essential fatty acids
5-Oxidation(Rancidty)
 This toxic reaction of triglycerides leads to
unpleasant odour or taste of oils and fats
developing after oxidation by oxygen of air,
bacteria, or moisture.

 Also this is the base of the drying oils after

exposure to atmospheric oxygen.
Example is linseed oil, which is used in
paints and varnishes manufacturing
B-Waxes
 Definition: Waxes are solid simple lipids containing
a monohydric alcohol (with a higher molecular
weight than glycerol) esterified to long-chain fatty
acids. Examples of these alcohols are palmitoyl
alcohol, cholesterol, vitamin A or D.
 Properties of waxes: Waxes are insoluble in water,
but soluble in fat solvents and are negative for
acrolein test.
 Waxes are not easily hydrolyzed as the fats and are
indigestible by lipases and are very resistant to
rancidity.
 Thus they are of no nutritional value.
Type of Waxes:
 Waxes are widely distributed in nature such as the
secretion of certain insects as bees-wax, protective
coatings of the skins and furs of animals and
leaves and fruits of plants. They are classified into
true-waxes and wax-like compounds as follows:
A-True waxes: include:
 Bees-wax is secreted by the honeybees that use it
to form the combs. It is a mixture of waxes with the
chief constituent is mericyl palmitate.
 O O
C15H31 C OH + C30H61OH C15H31 C O C30H61

Palmitic Mericyl Mericyl

H2O
acid alcohol palmitate

B-Wax-like compounds:
 Cholesterol esters: Lanolin (or wool fat) is
prepared from the wool-associated skin glands
and is secreted by sebaceous glands of the skin.

 It is very complex mixture, contains both free and

esterified cholesterol, e.g., cholesterol-palmitate
and other sterols.
Differences between neutral lipids and waxes:

Waxes Neutral lipids

1.Digestibility: Indigestible (not hydrolyzed Digestible (hydrolyzed by lipase).

by lipase).

2-Type of Long-chain monohydric Glycerol (trihydric) + 3 fatty acids

alcohol: alcohol + one fatty acid.

3-Type of fatty Fatty acid mainly palmitic Long and short chain fatty acids.
acids: or stearic acid.

4-Acrolein test: Negative. Positive.

5-Rancidability: Never get rancid. Rancidible.

6-Nature at Hard solid. Soft solid or liquid.

room
temperature.
7-Saponification Nonsaponifiable. Saponifiable.

8-Nutritive No nutritive value. Nutritive.

value:
9-Example: Bee & carnuba waxes. Butter and vegetable oils.
 2-Compound Lipids
Definition:
 They are lipids that contain additional
substances, e.g., sulfur, phosphorus, amino
group, carbohydrate, or proteins beside fatty acid
and alcohol.
 Compound or conjugated lipids are classified into
the following types according to the nature of the
additional group:
1. Phospholipids
2. Glycolipids.
3. Lipoproteins
4. Sulfolipids and amino lipids.
 A-Phospholipids
Definition: Phospholipids or phosphatides are compound
lipids, which contain phosphoric acid group in their
structure.
Importance:
1. They are present in large amounts in the liver and brain as
well as blood. Every animal and plant cell contains
phospholipids.
2. The membranes bounding cells and subcellular organelles
are composed mainly of phospholipids. Thus, the transfer of
substances through these membranes is controlled by
properties of phospholipids.
3. They are important components of the lipoprotein coat
essential for secretion and transport of plasma lipoprotein
complexes. Thus, they are lipotropic agents that prevent
fatty liver.
4. Myelin sheath of nerves is rich with phospholipids.
5-Important in digestion and absorption of neutral
lipids and excretion of cholesterol in the bile.
6-Important function in blood clotting and platelet
aggregation.
7-They provide lung alveoli with surfactants that
prevent its irreversible collapse.
8-Important role in signal transduction across the cell
membrane.
9-Phospholipase A2 in snake venom hydrolyses
membrane phospholipids into hemolytic
lysolecithin or lysocephalin.
10-They are source of polyunsaturated fatty acids for
synthesis of eicosanoids.
 Classification of Phospholipids are classified
into 2 groups according to the type of the alcohol
present into two types:
A-Glycerophospholipids: They are regarded as derivatives
of phosphatidic acids that are the simplest type of
phospholipids and include:
1. Phosphatidic acids.
2. Lecithins
3. Cephalins.
4. Plasmalogens.
5. Inositides.
6. Cardiolipin.
B-Sphingophospholipids: They contain sphingosine as an
alcohol and are named Sphingomyelins.
A-Glycerophospholipids
1-Phosphatidic acids: They are metabolic intermediates in
synthesis of triglycerides and glycerophospholipids in the
body and may have function as a second messenger. They
exist in two forms according to the position of the
phosphate
O
Saturated
 CH2 O C R1
O fatty acid
Polyunsaturated 
fatty acid R2 C O C H
O
 CH2 O P OH Phosphate
OH
-Phosphatidic acid
O
 CH2 Saturated
O C R1
O fatty acid

Phosphate HO P O C H
OH O
Polyunsaturated
 CH2 O C R2
fatty acid
 -Phosphatidic acid
2-Lecithins:
 Definition: Lecithins are glycerophospholipids that
contain choline as a base beside phosphatidic
acid. They exist in 2 forms - and -lecithins.
Lecithins are a common cell constituent obtained
from brain (-type), egg yolk (-type), or liver (both
types). Lecithins are important in the metabolism
of fat by the liver.
 Structure: Glycerol is connected at C2 or C3 with a
polyunsaturated fatty acid, at C1 with a saturated
fatty acid, at C3 or C2 by phosphate to which the
choline base is connected. The common fatty acids
in lecithins are stearic, palmitic, oleic, linoleic,
linolenic, clupandonic or arachidonic acids.
Lysolecithin causes hemolysis of RBCs. This partially explains
toxic the effect of snake venom,. The venom contains
lecithinase, which hydrolyzes the polyunsaturated fatty
converting lecithin into lysolecithin. Lysolecithins are
intermediates in metabolism of phospholipids.

O
CH2 O C R1
O
R2 C O C H
O CH3
CH2 O P O CH2 CH2 N
+ CH3
OH Choline CH3
-Lecithin
O
CH2 O C R1
CH3 O
CH3
+N CH2 CH2 O P O C H
OH O
CH3 Choline
CH2 O C R2
 -Lecithin
3-Cephalins (or Kephalins):
 Definition: They are phosphatidyl-
ethanolamine or serine. Cephalins occur in
association with lecithins in tissues and are
isolated from the brain (Kephale = head).
 Structure: Cephalins resemble lecithins in
structure except that choline is replaced by
ethanolamine, serine or threonine amino
acids.
 Certain cephalins are constituents of the complex mixture
of phospholipids, cholesterol and fat that constitute the
lipid component of the lipoprotein “thromboplastin” which
accelerates the clotting of blood by activation of
prothrombin to thrombin in presence of calcium ions.
O
CH2 O C R1
O
R2 C O C H
O
CH2 O P O CH2 CH2 NH2 Ethanolamine
OH HO CH2 CH COOH Serine
-Cephalin
NH2
HO CH CH COOH Threonine
CH3 NH2
4-Plasmalogens:

 Definition: Plasmalogens are found in the cell

membrane phospholipids fraction of brain and
muscle (10% of it is plasmalogens), liver, semen
and eggs.
 Structure: Plasmalogens resemble lecithins and
cephalins in structure but differ in the presence of
,-unsaturated fatty alcohol rather than a fatty
acid at C1 of the glycerol connected by ether bond.
 At C2 there is an unsaturated long-chain fatty acid,
however, it may be a very short-chain fatty acid
 Properties: Similar to lecithins.

-Unsaturated
CH2 O CH CH R1 fatty alcohol
O
R2 C O C H
O CH3
CH2 O P O CH2 CH2 N CH3
+
OH CH3
-Plasmalogen
5-Inositides:
 Definition:
 - They are phosphatidyl inositol.
 Structure: They are similar to lecithins or cephalins but they
have the cyclic sugar alcohol, inositol as the base. They are
formed of glycerol, one saturated fatty acid, one
unsaturated fatty acid, phosphoric acid and inositol

O
CH2 O C R1
O
R2 C O C H
O OH OH
2 3
CH2 O P O H H H
1 OH 4
OH H
H OH
6 5
-Phosphatidylinositol OH H
6-Cardiolipins:
 Definition: They are diphosphatidyl-glycerol. They are found
in the inner membrane of mitochondria initially isolated
from heart muscle (cardio). It is formed of 3 molecules of
glycerol, 4 fatty acids and 2 phosphate groups.
 Function: Used in serological diagnosis of autoimmunity
diseases.

O OH
CH2 O C R1 CH2 O P O CH2
O
O
R2 C O C H H C OH H C O C R3
O
O
CH2 O P O CH2 R4 C O CH2
OH O
Cardiolipin