LIPIDS

LIPID CHEMISTRY

Definition Classification

Biological
importance
 LIPID CHEMISTRY

Definition

Organic substances relatively insoluble

in water but soluble in organic solvents
like chloroform, ether and benzene
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21
Animal fats and vegetable oils are the most widely occurring lipids. Fats and oils are both
esters, ester consist of an alcohol portion and an acid portion.

Formation of an ester:
O O
R'OH + HO-C-R" R'-O-C-R'' + H2O
 Glycerol esters (acylglycerols)
H
H
H C OH
H C O CO (CH2)n CH3

H C OH H C O CO (CH2)n CH3

H C OH H C O CO (CH2)n CH3

H H

Glycerol Triglyceride

• Triglycerides : most abundant family of lipids in

plant and animal cells.
• major components of the the human diet
 CLASSIFICATION OF LIPIDS

Simple Complex Derived

lipid lipid lipids
 SIMPLE LIPIDS

They are esters of FA with various alcohols

D/U the type of alcohols these are subclassified as

Neutral fats or oils Waxes

Alcohol is
Alcohol is
other than
GLYCEROL
glycerol
 NEUTRAL FATS OR OILS

Esters of FA with alcohol

GLYCEROL

Uncharged
 WAXES

Esters of FA with
higher molecular
EXAMPLES
weight  Lanolin
monohydric  Beeswax
 Whale sperm
alcohols
oil
 COMPLEX LIPIDS

These are esters of FA with alcohol containing additional[prosthetic]

groups.

Subclassified according to the type of prosthetic group

Phospholipids Glycolipids Lipoproteins

 PHOSPHOLIPIDS

FA + ALCOHOL + PHOSPHORIC ACID

They
frequently
have
nitrogen
containing
bases
 PHOSPHOLIPIDS

Phospholipids
may be
classified on the
basis of the
type of alcohol
present
A. Glycerophospholipids B. Spingophospholipids

ALCOHOL IS GLYCEROL ALCOHOL IS SPINGOSINE

 Phosphatidylcholine
 Phosphatidyl ethanolamine
 Phosphatidyl serine
 Phosphatidyl inositol  Spingomyelins
 Plasmalogens
 Cardiolipins
SPHINGOPHOSPHOLIPID
 Functions of phospholipids

In association with proteins phospholipids form the structural components of

membranes and regulate membrane permeability.

 Phospholipids participate in the absorption of fat from the intestine.

Essential for the synthesis of different lipoproteins, and thus participate in the
transport of lipids.

Accumulation of fat in liver (fatty liver) can be prevented by phospholipids, hence

they are regarded as lipotropic factors.

Arachidonic acid, an unsaturated fatty acid liberated from phospholipids, serves as a

precursor for the synthesis of eicosanoids (prostaglandins, prostacyclins,

thromboxanes etc.).
 Functions of phospholipids

Phospholipids participate in the reverse cholesterol transport and thus help in the
removal of cholesterol from the body.

Phospholipids act as surfactants (agent lowering surface tension).

Cephalins,an important group of phospholipids participatin blood clotting.

Phospholipids( phosphatidyl inositoal ) involved in signal transmission across

membranes.
 GLYCOLIPIDS

FA + ALCOHOL[SPINGOSINE] +CARBOHYDRATE
WITH NITROGEN BASE

 They do not contain phosphate group

Example
Cerebrosides
Gangliosides
GLYCOLIPIDS
 LIPOPROTEINS

Chylomicrons
Lipid with Very low density lipoprotein (VLDL)
prosthetic Low density lipoprotein (LDL)
group PROTEIN High density lipoprotein (HDL)
 DERIVED LIPIDS

These are the derivatives obtained on the hydrolysis of group 1 and

group 2 lipids which possess the characteristics of lipids.

Example

Vitamin A
Fatty acids Steroids Cholesterol
and D
 FUNCTIONS OF LIPIDS

Structural Precursor of
Act as Protection of
Storage form component many steroid
thermal internal
of energy of cell hormones,
insulator organs
membrane. vitamin D
 FUNCTIONS OF LIPIDS

Fats serve as
Helps in Acts as
Lipoproteins surfactants Improve
absorption electric
transporting by reducing taste and
of fat soluble insulators in
lipids surface palatability.
vitamins neurons.
tension.
 Fatty acids
 Fatty acids are naturally occurring carboxylic acids with an unbranched carbon
chain and an even number of carbon atoms.
 The pathway by which fatty acids are biosynthesized they almost always contain an
even number of carbon atoms.
 Long-chain fatty acids (12 to 26 carbon atoms) are found in meats and fish
 medium-chain fatty acids (6 to 10 carbon atoms) and short-chain fatty acids (fewer
than 6 carbon atoms) occur primarily in dairy products.
 There are saturated and unsaturated Fatty acids.

 Saturated fatty acid : Fatty acid chains that contain only carbon-carbon single
bonds are referred to as saturated (Palmitic acid)

Unsaturated fatty acid : Those molecules that contain one or more double bonds are said
to be unsaturated. There are mono- and polyunsaturated fatty acids (Oleic acid)
Prostaglandins are derivative of fatty polyunsaturated acids
 Fatty acids : The fundamental building blocks of many lipid are long chain
carboxylic acid. The long nonpolar tail of F.A. are responsible for most of the
fatty or oily characteristics of fats.

Carboxylic group, polar head of F.A is very hydrophilic under conditions of physiological pH
and it exists as the carboxylate anion ­COO¯.
 A 16-C fatty acid: CH3(CH2)14-COO-

Non polar polar

 A 16-C fatty acid with one cis double bond between C atoms 9-10 may be represented as
16:1 cis D9.
In aqueous solution the ion of F.As associated with one another and form spherical clusters
called Micelles: in which the non polar chain extend toward the interior of the structure a
way from water and the polar carboxylate groups face outward in contact with the water
(some time contain hundreds or thousands of F.As).
F.As held together by weak dispersion forces . Micelle is important in transport of insoluble lipids in the blood.

CH3—CH2—CH2—CH2—CH2—CH2—CH2—COOH
↓ ↓
Non polar hydrophobic Polar hydrophilic head
tail water insoluble (water soluble)
What are Essential Fatty Acids (EPA)?

There are TWO essential fatty acids.

Essential means you NEED to get them from the diet because the body cannot
manufacture them.

·-linolenic acid (LNA or ALA): an omega-3 fatty acid

1
ALA
COH
1 3 15 12 9 -Linolenic acid
O

· Linoleic acid (LA): an omega-6 fatty acid found abundantly in soy oil, sunflower seeds
pumpkin seeds, sesame seeds, corn oil, and in most nuts.
1
COH
12 9
O
Linoleic acid
9,12
cis-9,12-Octadecadienoic aicd, 18:2( )
Functions of EFA

Essential fatty acids are required for the membrane structure and function.

Transport of cholesterol.

Formation of lipoproteins.

 Prevention of fatty liver etc.

They are also needed for the synthesis of another important group of compounds,
namely eicosanoids.
 Rancidity
Rancidity: Rancidity is the term used to represent the deterioration of fats and oils
resulting in an unpleasant taste. Fats containing unsaturated fatty acids are more
susceptible to rancidity.
 Rancidity occurs when fats and oils are exposed to air, moisture, light, bacteria etc.

 Hydrolytic rancidity occurs due to partial hydrolysis of triacylglycerols by bacterial

enzymes.
 Oxidative rancidity is due to oxidation of unsaturated fatty acids.

This results in the formation of unpleasant products such as dicarboxylic acids,

aldehydes, ketones etc.

Rancid fats and oils are unsuitable for human consumption.

 Test to Check Purity of Fats and Oils

• Acid number:- It is the number of milligrams of potassium hydroxide required to

completely neutralize the free fatty acids present in 1 g of the oil or fat.

 In normal circumstances refined oils should be free from any free fatty acids.

 Oils, on decomposition due to chemical or bacterial contamination-yield free fatty

acids.

Therefore, oils with increased acid number are unsafe for human consumption
 Test to Check Purity of Fats and Oils

• Saponification number:- It is defined as the mg (number) of KOH required to

hydrolyze (saponify) one gram of fat or oil.

• Saponification number is a measure of the average molecular size of the fatty acids
present
• The value is higher for fats containing short chain fatty acids.

Human fat : 195-200

Butter :230-240
Coconut oil : 250-260
 Test to Check Purity of Fats and Oils

• Iodine number:- lt is defined as the grams (number) of iodine absorbed by 100 g of

fat or oil.

 Iodine number is useful to know the relative unsaturation of fats, and is directly
proportional to the content of unsaturated fatty acids.

 Thus lower is the iodine number, less is the degree of unsaturation.

• Determination of iodine number will help to know the degree of adulteration

of a given oil.
 Chemical Reactions of Fatty Acids

Esterification reacts fatty acids with alcohols to form esters and water
 Fatty Acid Hydrolysis

• Acid Hydrolysis reverses esterification. Fatty acids are produced from esters
 Saponification
• Saponification is the base-catalyzed hydrolysis of an ester
• Products of the reaction are
– An alcohol
– An ionized salt which is a soap
• Soaps have a long uncharged hydrocarbon tail
• Also have a negatively charged carboxylate group at end
• Form micelles that dissolve oil and dirt particles