CHEMISTRY OF LIPID

Disease associated with Lipid metabolism

• Obesity
• Atherosclerosis and CVD
• In Diabetes mellitus, dearranged
metabolism of lipid is seen
• Fatty liver
• Lipid storage disorder
• Lipoproteinemias.
 Definition
• Lipids are heterogenous (=different)group of
organic compounds
• Insoluble in water or polar solvents
• Soluble in organic solvents or non-polar
solvents (eg. Ether, benzene, alcohol etc.)
 Lipids: Classification
3 major classes based on their composition:

Derived &
Simple Lipids Complex Lipids
Precursor Lipids
• Esters of fatty • Contain • The products or
acids with conjugate precursors of
alcohol compounds in simple lipids &
• Do not contain addition to fatty comp lipids
conjugate groups acids & alcohol • Examples:
• 2 types based on • Examples: • 1.Fatty acids
alcohol present • 1.Phospholipids • 2.Cholesterol
in them: • 2.Glycolipids • 3.Steroid
• 1. Fats/Oils • 3.Sulpholipids hormones
• 2. Waxes • 4.Aminolipids • 4.Ketone bodies
 The important ones are…
Triacylglyc
Fatty acids
erols

Phospholi
Glycolipids
pids
 SIMPLE LIPIDS

a. Fats/Oils

• Esters of fatty acids with glycerol (i.e. Acylglycerols)

• The 3 acylglycerols: MONO-, DI-, and TRIacylglycerol
• Natural fats & oils are mixtures of these three acylglygerols, triacylglycerol is the most abundant in fats and oils
• Fat: solid at room temperature; e.g. Butter
• Oils: liquid at room temperature; e.g. Vegetable oil

b. Waxes

• Esters of fatty acids with higher alcohols

• Example: Beeswax
 COMPOUND LIPIDS

a. Phospholipids

• Contain phosphoric acid residues in addition to fatty acids & alcohol

• 2 types depending the nature of alcohol present:
• 1. GLYCEROphospholipids – contain glycerol as alcohol (e.g. lecithin)
• 2. SPHINGOphospholipids – contain sphingosine as alcohol (e.g. sphingomyelin of myelin sheath of nerves)

b. Glycolipids

• Contain carbohydrate residues in addition to fatty acids & alcohol

• 2 types based on the type of carbohydrate residues:
• 1. Cerebrosides (contain glucose or galactose as carbohydrate residues)
• 2. Gangliosides (contain complex oligosaccharides as carbohydrate residues)
 A li’l bit more on… COMPOUND LIPIDS

c. Other compound lipids

• 1. Lipoproteins – contain protein as conjugate group (e.g.

VLDL, LDL, HDL)
• 2. Sulpholipids – contain sulphate groups as conjugate
group
• 3. Aminolipids – contain amino acid as conjugate group
 PHOSPHOLIPIDS
• Compound lipids containing phosphoric acid
residues + FA + alcohol + nitrogenous base
• There 2 types; depending on the nature of
alcohol

GLYCERO • Contain glycerol as alcohol

phospholipids • Eg. lecithin, cephalin, plasmalogen

SPHINGO • Contain sphingosine as alcohol

phospholipids • Sphingomyelin of myelin sheath
 Phospholipids: Functions
Constituents of cell membrane

Participate in lipid transport

Participate in eicosanoids synthesis

Required for the action of lipoprotein lipase

enzyme

Lung surfactant

Participate in blood coagulation

 Glycolipids
• Compound lipids containing carbohydrate (CHO)
residues in addition to fatty acids & alcohol
• 2 types:
1. Cerebrosides – contain glucose or galactose
as carbohydrate residues
2. Gangliosides - contain oligosaccharides &
sialic acids as carbohydrate residues
 Glycolipids: Functions
• Major constituents of cell membranes,
especially nervous tissues
• Present in outer layer of plasma membrane,
have vital role in cell-to-cell interaction,
growth & development
• Some hormone receptors are gangliosides
 Lipoproteins
Difference >< LDL and HDL

• All types of lipoproteins contain both lipids and proteins,

but the relative composition of each lipoprotein varies.
• LDL- 50% cholesterol + 25% protein.
• HDL- 20% cholesterol + 50% protein.
Since protein is more dense than fat, HDL particles are
more dense than LDL particles,

LDL- B-100 proteins HDL- A-I and A-II proteins.

The type of protein is significant because it determines the
function of the lipoprotein particle.
 FATTY ACIDS (FA)

Carboxyl
• Aliphatic carboxylic acids group

• General formula: R-COOH

Hydrocarbon
chain
• Classification
 Classification of FA
Based on HYDROCARBON CHAIN

SATURATED
(NO double bond)

Based on NUMBER of
CARBON atoms
EVEN ODD
CHAIN CHAIN
(even (odd
number of number of
C atoms) C atoms)
 Saturated Fatty Acids
• Do not contain any double bond
Fatty Acids Carbon Atoms Structure
Acetic acid 2 CH3COOH
Propionic acid 3 CH3 CH2COOH
Butyric acid 4 CH3 [CH2]2COOH
Valeric acid 5 CH3 [CH2]3COOH
Caproic acid 6 CH3 [CH2]4COOH
Caprylic acid 8 CH3 [CH2]6COOH
Capric acid 10 CH3 [CH2]8COOH
Lauric acid 12 CH3 [CH2]10COOH
Myristic acid 14 CH3 [CH2]12COOH
Palmitic acid 16 CH3 [CH2]14COOH
Stearic acid 18 CH3 [CH2]16COOH
Arachidic acid 20 CH3 [CH2]18COOH
Unsaturated Fatty Acids

MUFA PUFA
• More than 1 double
bond
• 1 double bond • Eg. Linoleic acid – 2 db
• Eg. Palmitoleic acid,
oleic acids • α-linolenic acid – 3 db
• Arachidonic acid – 4
db
 Nomenclature of FA
• Numbering of C atoms in FA:
- C atom is numbered from COOH carbon, numbered
1
(C-1), next to it is (C-2)
• Naming of C atom in FA:
- C-2 is named α-carbon, C-3 is β-carbon & so forth
- Terminal methyl carbon is termed ω-carbon or n-
carbon
- Starting from methyl end, C atoms are numbered ω-
1, ω-2 or n-1, n-2 etc)
• Short chain fatty acids - less than ‘6’ carbon
• Medium chain fatty acids - 8-14 carbons
• Long chain fatty acids - 16-24 carbons
• E.g; Linolenic acid,Linoleic acid and oleic acid
 Essential FA (EFA)
• Not synthesized in the body
• Have to be obtained from the diet
• Examples: Linoleic acid, α-linolenic acid,
arachidonic acid
• Are polyunsaturated fatty acids (PUFA)
• Exception: Arachidonic acid is semi essential
fatty acid because it can be synthesized from
linoleic acid (not vice versa)
 Functions of EFA (Pt. 1)

Precursor of eicosanoids

• EFA are precursors of eicosanoids

Help in lipid transport

• EFA are required for the synthesis of phospholipids which is required for the
formation of lipoprotein, which is involved in lipid transport

Important component of cell membranes

 Functions of EFA (Pt. 2)
Lowers serum cholesterol

Reproductive function

• PUFA are important constituents of lipids of gonads

Epidermal growth

• PUFA are important constituents of epidermal lipids

 Triacylglycerols
• Esters of FA with glycerol
CH2 O-H CH2 O-FA1 CH2 O-FA1 CH2 O-FA1

CH O-H CH O-H CH O-FA2 CH O-FA2

CH2 O-H CH2 O-H CH2 O-H CH2 O-FA3

Glycerol Monoacylglycerol Diacylglycerol Triacylglycerol

• 1, 2 or 3 hydroxyl groups of glycerol can be

esterified with FA
 Triacylglycerol (aka neutral fat)
• Carry three fatty acids esterified to glycerol
• Functions:

Storage form of energy

• In conditions like starvation or DM, the body derived energy from fatty acids
• Triglycerides are hydrolyzed by lipase to release fatty acids & glycerol

Concentrated form of energy

• 1 g fat = 9 kcal vs. 1 g carbohydrate = 4 kcal

Heat insulators

• The subcutaneous fat serves as insulator against heat loss from body

Shock absorbers
• Subcutaneous fat also insulate against mechanical trauma
• Fat pad around internal organs prevent injury to internal organs
 Cholesterol: General Info

• An animal sterol
• Chemical name: 3-hydroxy 5,6 cholestene
• Structure:
 Cholesterol: Functions (1)

1. Constituent of cell membranes

2. Synthesis of bile acids & bile salts

• 50-80% of cholesterol in liver is converted to bile acids /bile salts

• Bile salts are required for ____________________________

3. Formation of Vitamin D3

• A derivative of cholesterol (7-dehydrocholesterol) is converted to vitamin D3

 Cholesterol: Functions (2)

4. Synthesis of steroid
hormones

• 4 classes of steroid hormones are derived from

cholesterol
• 1. Glucocorticoids - eg Cortisol
• 2. Mineralocorticoids – eg Aldosterone
• 3. Male sex hormones – eg Testosterone
• 4. Female sex hormones – eg Progesterone
REFERENCES:
• 1. HARPERS ILLUSTRATED BIOCHEMISTRY Edition.
• 2. Lippincott’s IIIlusrtaed Reviews
OTHER REFERENCES:
• Text book of Biochemistry for Medical students by
DM Vasudevan