CHEMISTRY OF LIPIDS

Learning Objectives
Define, classify and enumerate the functions of lipids

Discuss the general structure, functions, nomenclature,

numbering of fatty acids and explain essential/ nonessential
fatty acids with their importance.
Describe structure, occurrence and functions of
triacylglycerols
Describe the structure, classification with examples,
functions of phospholipids
 Describe structure, classification, functions of
glycosphingolipids and discuss various types of
sphingolipidoses.
 Describe structure and functions of cholesterol and
importance of cholesterol as the precursor steroid
hormones, bile acids and vitamin D.
 Describe structure, classification, functions of
lipoprotein
Definition, Classification & Functions Of
Lipids
Definition of lipid

Organic substances insoluble in water but soluble

in organic solvents like chloroform, ether, and
benzene; they are esters of fatty acids with alcohol
and are utilizable by the living organism.
Classification Of Lipids

1. Simple lipid

2. Complex or compound lipid

3.Derived lipids.
 Simple Lipid

Esters of fatty acids with various alcohols.

Depending on the type of alcohols:

1. Neutral fats or triacylglycerol

2. Waxes
A fat in liquid state is called an oil, e.g. vegetable oil like

groundnut oil, mustard oil, corn oil, etc.

 Complex or Compound Lipids
Esters of fatty acids, with alcohol containing
additional groups.
According to the type of additional group:

1. Phospholipids

2. Glycolipids

3. Lipoproteins
Phospholipids

Additional group is phosphoric acid.

They also have nitrogen containing bases.

Phospholipids classified as:

1.Glycerophospholipids

2. Sphingophospholipids
Glycerophospholipids
1. Phosphatidyl choline (lecithin)

2. Phosphatidyl ethanolamine (cephalin)

3. Phosphatidyl serine

4. Phosphatidyl inositol

5. Lysophospholipid

6. Plasmalogens

7. Cardiolipins
Sphingophospholipids

The alcohol present is sphingosine, e.g.

 Sphingomyelins.
 Glycolipids

Lipids containing fatty acid, alcohol sphingosine

Additional group carbohydrates

 They also have nitrogen containing bases.

They do not contain phosphate group.

Also called glycosphingolipids.

 Example of glycolipids:

1. Cerebrosides

2. Gangliosides
 Lipoproteins
Additional group is protein.

Examples:

1. Chylomicrons

2. Very low density lipoprotein (VLDL)

3. Low density lipoprotein (LDL)

4. High density lipoprotein (HDL)

Derived Lipids
Products obtained after the hydrolysis of simple and
compound lipids which possess the characteristics of

lipids, e.g.
 Fatty acids
 Steroids
 Cholesterol
 Lipid soluble vitamins and hormones
 Ketone bodies
Functions of Lipids

Storage form of energy

Structural components of membranes, e.g.

phospholipids, glycolipids and sterols.

Cholesterol, a sterol, is a precursor of many

steroid hormones, vitamin D

• Lipid acts as a thermal insulator in the
subcutaneous tissues and around certain organs.
• Nonpolar lipids act as electrical insulators in
neurons.
• Lipids are important dietary constituents because
of the fat soluble vitamins and essential fatty
acids which are present in the fat of natural foods.
 Lipids help in absorption of fat soluble vitamins

(A, D, E and K). They act as a solvent for the

transport of fat soluble vitamins

 Fatty Acids
Definition
 Fatty acids are carboxylic acids with

hydrocarbon chains (–CH2–CH2–CH2–).

 Represented by a chemical formula R-COOH

 Fatty acids are amphipathic in nature.

 Classification of Fatty Acids

Fatty acids are classified into four major classes

1. Straight chain fatty acid

2. Branched chain fatty acid

3. Substituted fatty acids

4. Cyclic fatty acid.

Functions of Fatty Acids
1. They serve as building blocks of phospholipids
and glycolipids, components of membranes.

2. Fatty acid derivatives serve as hormones, e.g.

prostaglandins.

3. Fatty acids serve as a major fuel for most cells.

 Numbering of Fatty Acid Carbon Atoms
 Carbon atoms of fatty acid are numbered starting
at the carboxyl terminus
 Carbon atoms 2 and 3 are referred to as α and β
respectively
 The methyl carbon atom at the distal end of the
chain is called ω carbon.
Figure 4.1: Numbering of fatty acid carbon.
Representation of Double Bonds of Fatty Acids

1. C-system

2. ω or n-system.
C-system
C1 being the carboxyl carbon

Position of double bond is represented by the

symbol Δ (delta), followed by a superscript
number.
Oleic acid is a C18 fatty acid with one double
bond between carbon number 9 and 10 is
represented as C: 18:1: Δ9
ω– or n-System

Carbon of terminal methyl group of fatty acid is refer to

‘ω’
Oleic acid is denoted as C: 18:1: ω-9

ω-9 represents the double bond position which is found

between 9th and 10th carbon atoms from ω carbon.
This method is widely used by nutritionists.
Figure 4.2: Representation of double bonds of unsaturated
fatty acids.
Naturally occurring unsaturated fatty acids belong
to ω-9, ω-6 and ω-3 series.

•ω-9 : Oleic acid (C:18:1:ω-9)

•ω-6 : Linoleic acid (C:18:2:ω-6)

Arachidonic acid (C:20:4:ω-6)

•ω-3 : Linolenic acid (C:18:3:ω-3)

Figure 4.2: Representation of double bonds of unsaturated
fatty acids.
Figure 4.2: Representation of double bonds of unsaturated
fatty acids.
 ESSENTIAL FATTY ACIDS
Fatty acids, that are required for optimal health and
cannot be synthesized by the body and should be supplied
in the diet are called essential fatty acids.
They are: 1. Linoleic acid (18: 2: D9,12)

2. Linolenic acid. (18: 3: D9,12,15)

3 . Arachidonic acid (C: 20: 4: D5,8,11,14)

 In deficiency of linoleic acid, arachidonic acid also
becomes essential fatty acid.
 Humans lack the enzymes to introduce double bonds
at carbon atoms beyond C9 in the fatty acid chain
Functions of Essential Fatty Acids (EFA)

1. Synthesis of Eicosanoids:

-- Prostaglandins

-- Thromboxanes

-- Leukotrienes.

2. Maintenance of Structural Integrity

3. Development of Retina and Brain

Docosahexaenoic acid (DHA: ω-3), synthesized

from linolenic acid is needed for development of
the brain and retina during the neonatal period.

4. Skin protector

EFA helps to make the skin impermeable to water

5. Antiatherogenic Effect

Essential fatty acids increase

esterification and excretion of cholesterol,
thereby lowering the serum cholesterol
level.
Essential Fatty Acid Deficiency

Deficiency of EFAs is characterized by scaly skin,

eczema (in children), loss of hair and poor wound
healing.
 Impaired lipid transport and fatty liver may occur

 Decreases efficiency of biological oxidation

Properties & Reactions Of Lipids
Physical Properties

 It depends on the length of the carbon chains, and

degree of unsaturation of fatty acids.
 Melting point of even number carbon fatty acids
increases with chain length and decreases
according to unsaturation.
 A triacylglycerol containing all saturated fatty

acids of 12-C or more is solid at body

temperature, whereas if all the three fatty acid
residues are 18:2, it is liquid to below 0°C.
 REACTIONS OF LIPIDS

 Hydrolysis by lipases

Lipid → fatty acids + glycerol.

 Saponification : Hydrolysis of a fat by alkali.

.
 Hydrogenation
Hardening of liquid fats to solid fat

Peroxidation

Auto-oxidation → Free radicals → deterioration of foods

(rancidity)

Peroxidation leads damage to tissue in vivo → Cancer

 To control and reduce peroxidation humans make use of
antioxidants
 Naturally occurring antioxidants include vitamin E and
vitamin A, which are lipid soluble and vitamin C, which

is water soluble.
 Rancidity

The unpleasant odor and taste, developed by natural fats

upon aging. Rancidity may be due to hydrolysis or
oxidation of fat.
 CHARACTERIZATION OF FAT
( TESTS FOR PURITY OF FAT)

Saponification number

Number of mgs of KOH required to saponify

one gm of fat. Saponification number of:

Butter = 220

Coconut oil = 260

Iodine Number
Number of gms of iodine required to saturate 100
gms of a given fat is known as iodine number.
High iodine number indicates high degree of
unsaturation of fatty acids

Butter fat = 27

Coconut oil = 8

Linseed oil = 200.

Acid Number
Number of mg of KOH required to neutralize free
fatty acids present in one gm of fat .
Acid number is directly proportional to rancidity.

Edibility of fat is inversely proportional to acid no.

Presence of free fatty acids in any oil indicates that

it is not pure.
 Reichert Meissl Number

Number of ml of 0.1 N alkali, required to neutralize

the volatile fatty acids distilled from 5 gm of fat,
e.g. the Reichert Meissl value for:

Butter = 26

Coconut oil = 7.
Triacylglycerols or Triacylglycerides
or Neutral Fat
Figure 4.6: Triacylglycerol.
Functions of Triacylglycerols
•Triacylglycerols are highly concentrated stores of
metabolic energy.
•Triacylglycerols have significant advantages over other
forms of metabolic fuel, polysaccharides such as glycogen.
•The carbon atoms of fatty acids are more reduced than
those of sugars and oxidation of triacylglycerides yields
twice the energy as that of carbohydrates.
 Triacylglycerol are very non-polar, hydrophobic.

 They are stored in a nearly anhydrous form, they

no need to carry the extra weight of water of
hydration.
 Proteins and carbohydrates are much more polar
and therefore, more highly hydrated and have to
carry extra weight of water.
 A gram of dry glycogen binds about two grams
of water.
 A gram of nearly anhydrous fat stores more
than six times as much energy as a gram of
hydrated glycogen.
 Glycogen stores provide energy to sustain
physiological function for about 24 hours;
whereas triacylglycerol stores allow survival
for several weeks.
 Carbohydrates do offer certain advantages as
quick sources of metabolic energy, because of
water solubility
 PHOSPHOLIPIDS

 Made up of fatty acid, glycerol or other alcohol,

phosphoric acid and nitrogenous base.

 Phospholipids are amphipathic in nature

Figure 4.7: Schematic structure of amphipathic phospholipid.
Classification Of Phospholipid

1. Glycerophospholipid Or Phosphoglyceride

2. Sphingophospholipid
Figure 4.9: Structure of glycerol and phosphatidic acid.
 Phosphatidylcholine (lecithin)
 Glycerophospholipids containing choline

Constituents of the cell membrane

 Dipalmitoyl lecithin secreted by pulmonary

type II epithelial cell, acts as a lung surfactant
and is necessary for normal lung function.
 It reduces surface tension in the alveoli,
thereby prevents alveolar collapse.
 Lecithin represents a storage form of lipotropic
factor choline and methyl group
 Constituent of lipo­proteins.
 Acute Pulmonary Respiratory Distress Syndrome (RDS)

• Insufficient surfactant dipalmitoyl phosphatidylcholine

production in infants
• The lungs of immature infants do not have enough type II
epithelial cells to synthesize sufficient amounts of
dipalmitoyl phosphatidylcholine (DPPC).

• In its absence, the lungs tend to collapse and this

condition is known as respiratory distress syndrome

 Phosphatidyl ethanolamine (Cephalin)

 Nitrogenous base is ethanolamine.

 Thromboplastin (coagulation factor III),

required for clotting process is composed

mainly cephalins.
 Phosphatidylserine

 Nitrogenous base is amino acid serine

 Found in most tissues.

 Phosphatidylinositol

 Nitrogenous base is inositol

 Act as a second messenger for the action of

hormones like oxytocine and vasopressin.

 Plasmalogens
Fatty acid chain at C1 of glycerol is linked through
an ether, rather than an ester bond and found in
myelin and in cardiac muscle.

Platelet activating factor (PAF) is a plasmalogen

and involved in platelet aggregation
 Lysophospholipids

 `Produced when one of the two acyl

groups is removed from phosphoglycerides.

 Intermediates in the metabolism of

phosphoglycerides
 Cardiolipin (Diphosphatidyl glycerol)

Two molecules of phosphatidic acid connected by

a molecule of glycerol.
 Major lipid of mitochondrial membrane and is
necessary for the electron transport process.
This is only antigenic phospholipid .
 Sphingophospholipids

 Alcohol sphingosine an amino alcohol instead of

glycerol.

 Amino group of the sphingosine is linked to a

fatty acid to yield ceramide.
Figure 4.12: Structure of sphingomyelin.
Figure 4.13: Schematic structure of ceramide.
 Sphingomyelin is one of the principal
structural lipids of membranes of nerve
tissue.
 Sphingomyelin act as electrical insulators
around nerve fibers.
 Functions Of Phospholipids
 Major lipid constituents of cellular membranes

 Regulate permeability of membranes and

activation of some membrane bound enzymes
 Sphingomyelin act as electrical insulators
around nerve fibers.
 Constituent of lipo­proteins.
 Act as a lipotropic factor. Lecithin represents a
storage form of lipotropic factor choline and
methyl group
 Good emulsifying agents and help in intestinal
absorption of lipids.
 Plasmalogens (platelet activating factor) involved
in platelet aggregation.
 Thromboplastin (coagulation factor III), is composed
mainly of cephalins
 Lecithin acts as lung surfactant, which prevents alveolar
collapse
 Phosphatidylinositol is a second messenger

 Cardiolipin is necessary for the electrons transport

process.
 GLYCOLIPIDS

 Carbohydrate containing lipids

 Glycolipids consist of alcohol sphingosine.

 One or more sugar units attached to sphingosine

• Glycolipids are widely distributed in every tissue

of body, particularly in nervous tissue.

Cerebrosides
Ceramide + Monosaccharides ( glucose or galactose )
 Galactocerebroside is found in high

concentration in nerve tissue membrane.

 Glucocerebroside is found in non-neural tissues.
 It acts as a precursor for the synthesis of more complex glycolipids, e.g. gangliosides.

.
 Sulfatides
Ceramide + Monosaccharide + Sulfate.

For exam : sulfogalactoceramide found in myelin.

 Globosides
Ceramide +Oligosaccharide
 Constituents of the RBC-membrane
 Determinants of the A,B,O blood group
 Gangliosides
(Cerebroside + Oligosaccharides + N-acetylneuraminic
acid, NANA)

• Gangliosides are complex glycolipids, derived from

glucocerebroside.

• Ganglioside contains oligosaccharides and one or more

molecules of N- acetylneuraminic acid (NANA) attached
to ceramide.
 Types of gangliosides are:

GM1, GM2,GM3, etc.

G : represents Ganglioside

M : represents mono which indicate presence of one

residue of NANA

Subscript number: assigned on the basis of

chromatographic migration of ganglioside

 Structure of sialic acid or NANA

Mannosamine + Pyruvate ————> Neuraminic acid

FUNCTIONS OF GLYCOLIPIDS
• Constituent of the nervous tissue, such as, brain and
outer leaflet of cell membrane.
• Constituent of specific receptors for polypeptide
hormones.
• Antigenic and have been identified as a source of blood
group antigens.
• Play role in regulation of cellular interactions, growth
and development
 CHOLESTEROL (ANIMAL STEROL)
 Cholesterol, a class of steroid containing 27-carbon

atoms.
 Cholesterol contains:

- 8-carbon side chain attached to the D ring at C17

- a hydroxyl group attached to C3 of the A ring

- one double bond between carbon atoms 5 and 6

- methyl side chains at position C10 and C13.

Figure 4.15: The steroid nucleus, phenanthrene (rings
A, B, and C), to which cyclopentane D-ring is attached.
Figure 4.16: The structure of cholesterol.
 Cholesterol is amphipathic
 It occurs in animal fats, but not in the plant fats.
 Most of the cholesterol in the body exists as a

cholesterol ester.
 Cholesterol is widely distributed in all the cells of the

body, but particularly in nervous tissue.

Functions of the Cholesterol
 Structural constituent of the cell membranes and

plasma lipoproteins
 Precursor for Steroid hormones

-- Progesterone

-- Glucocorticoids

-- Mineralocorticoids

-- Androgens (male sex hormones)

-- Estrogen (female sex hormones).

Precursor for Bile acids, emulsify dietary fats

 Precursor for Vitamin D, essential in calcium and

phosphate metabolism.
 LIPOPROTEINS
 Lipoproteins are formed by a combination of lipid

and protein that transport lipids.

 Lipoproteins consist of :

lipid core containing nonpolar triacylglycerol

cholesterol ester surrounded by a single layer of

amphipathic phospholipids and free cholesterol molecules
with some proteins

.
Figure 4.18: Structure of lipoprotein.
 The protein components are referred to as apoprotein
or apolipoprotein.
 There are four major types of apolipoproteins
designated by letters A, B,C and E with subgroups given
in Roman numerals I, II, III, etc.
Classes of Lipoproteins

1. Chylomicrons

2. Very low density lipoproteins (VLDL)

3. Low density lipoprotein (LDL)

4. High density lipoprotein (HDL).

 Lipoprotein complexes contain diffèrent proportions
of lipids and proteins
 The density of these lipoproteins is inversely

proportional to triacylglycerol content.

 As the density increases, the diameter of the
particle

decreases
Figure 4.19: Diagrammatic representation of lipoprotein with
increasing densities and their composition.
 Triacylglycerol is the predominant lipid in

chylomicrons and VLDL.

 Cholesterol is the predominant lipid in LDL

 Phospholipid is the predominant lipid in HDL.

 EICOSANOIDS

 Prostaglandins ,thromboxanes and leukotrienes,

are collectively known as eicosanoids.

 Synthesized from arachidonic acid

 Prostaglandins (PGs)

 Group of compounds derived from arachidonic acid

 Prostaglandins are abbreviated as PG.

PGs are structurally related to prostanoic acid, having :

 Cyclopentane ring
 Two aliphatic side chains R1 and R2
 A hydroxyl group at carbon 15
 A double bond between carbons13 and 14
 Various substituents on the ring.
Classification of prostaglandins
 Classified into groups designated by capital letter

A, B, C, D, E, F, G, H and I depending on the

substituents on the cyclopentane ring.

 Sub-classified by a subscript number 1, 2,or 3

corresponding to the number of double bonds in

the side chains but not in the cyclopentane ring.

 Sixteen naturally occurring prostaglandins have

been described but only seven are found commonly

through out the body. These are :

PGE1, PGE2, PGF1α, PGF2α, PGG2, PGH2, PGI2.

 Prostaglandins are not stored, instead the precursor C-20

arochidonic acids are stored in tissues.

Functions of Prostaglandins
 Prostaglandins have hormone like actions.
 Prostaglandins in many tissues act by regulating

the synthesis of cyclic AMP (c-AMP).

 As c-AMP mediates the action of many hormones,

and affect tissue functions. Some of these are :

Smooth muscle contraction and relaxation

- PGF2α stimulate uterine contraction.

- PGE2 are involved in relaxation of

bronchial smooth muscle.

 Inflammatory response causing pain, oedema,

swelling and erythema

 Platelet aggregation:

-- PGE2 promote aggregation and are thus,

involved in the blood clotting

-- whereas PGI2 inhibits platelet aggregation

 Blood pressure regulation: PGE2 decrease blood pressure.

 Body temperature: Prostaglandins elevate body

temperature producing fever and cause inflammation,
resulting in pain.
 Gastric secretion: PGE2 suppress gastric secretion.
Nonsteroidal anti-inflammatory drugs (NSAIDs) such as:

-- aspirin

-- ibuferon

-- indomethacin, etc.

block the formation of prostaglandins from arachidonic

acid by

inhibiting the enzyme cyclooxygenase (COX).

Figure 4.20: Synthesis of eicosanoids and inhibitors of
eicosanoid synthesis.
THANK YOU