Lipid

chemistry
Lecture No 2
ESSENTIAL FATTY ACIDS
Polyunsaturated fatty acids such as Linoleic and
Linolenic acids are essential for normal life functions.
They are therefore characterized as essential fatty
acids.
Arachidonic acid is considered as semi essential fatty

acid since it can be synthesized from Linoleic acid .

Essential polyunsaturated fatty acids can be

classified as belonging to one of two "families", the

omega-6 family or the omega-3 family.
 Omega 3 fatty acids
 These are long chain PUFA with the first double bond
beginning at the third bond position from the methyl
end.
 dietary w-3 PUFAs suppress cardiac arrhthmias,
reduce serum TAGs, decrease the tendency for
thrombosis, lower blood pressure and reduce the risk
of cardiovascular mortality.
 They have anti-inflammatory effects.
Omega 3 fatty acids (CONTINUED)
 The omega 3 PUFAs principally alpha linolenic
acid 18:3(9,12,15)are found in plant oils such as
flax seed and canola and some nuts.
 The AMDR for alpha linolenic acid is 0.6% to
1.2%.
 The omega three long chain PUFAs are included in
infants formulas to promote brain development.
Omega 3 fatty acid (continued)
 Linoleic acid and aipha linolenic acids are
essential fatty acids (EFAs) required for membrane
fluidity and synthesis of eicosanoids.
 EFA deficiency is characterized by scaly
dermatitis as a result of depletion of skin
ceramides.
Omega 6 fatty acid
 These are long chain PUFAs with the first double
bond beginning at the sixth bond position when
starting from methyl end of fatty acid molecule.
 Consumption of fats containing omega 6 PUFAs
principally linoleic acid obtained from vegetable
oils, lower plasma cholesterol when substituted
for saturated fats.
Omega 6 fatty acid (continued)

 Plasma LDL-C is lowered but HDL-C which

protects against CHD is also lowered.
 The powerful benefits of lowering LDLs are only
partially off set because of decreased HDL.
 Nuts, avacados, olives, soybeans and various oils
including sunflower, cotton seed,and corn oil are
common sources of these fatty acids.
Omega 6 fatty acid (continued)
 The AMDR for lionleic acid is 5% to 10%.
 The lower recommendation for PUFAs relative to
MUFAs is because of concern that free radical
mediated oxidation (per oxidation)of PUFAs may
lead to delirious products.
 Depending upon the orientation of the radicals around the
axis of the double bond-
 Cis- If the radicals are on the same side of the double
bond
 Trans- If the radicals are on the opposite side
 Oleic acid and Elaidic acid have the same formula but Oleic
acid is cis while Elaidic acid is Trans Fatty acid
The hydrocarbon chains in saturated
fatty acids are, fairly straight and can
pack closely together, making these
fats solid at room temperature.

Oils, mostly from plant sources, have

some double bonds between some of
the carbons in the hydrocarbon tail,
causing bends or ―kinks‖ in the shape
of the molecules.
Increase in the number of cis double
bonds in a fatty acid leads to a variety
of possible spatial configurations of
the molecule—eg, Arachidonic acid,
with four cis double bonds, has "kinks"
or a U shape.
 Because of the kinks in the hydrocarbon tails, unsaturated
fats can‘t pack as closely together, making them liquid at
room temperature.
 The membrane lipids, which must be fluid at all
environmental temperatures, are more unsaturated than
storage lipids.
 Lipids in tissues that are subject to cooling, eg, in
hibernators or in the extremities of animals, are more
unsaturated.
 At higher temperatures, some bonds rotate, causing
chain
shortening, which explains why biomembranes become
thinner with increases in temperature.
 The carbon chains of saturated fatty acids form a zigzag
pattern when extended, as at low temperatures.
12
 Trans fatty acids are present in certain foods,
arising as a by-product of the saturation of fatty acids during
hydrogenation, or "hardening," of natural oils in the
manufacture of margarine.
 An additional small contribution comes from the ingestion of
ruminant fat that contains trans fatty acids arising from the
action of microorganisms in the rumen.
 Naturally-occurring unsaturated vegetable oils have almost all
cis bonds, but using oil for frying causes some of the cis
bonds to convert to trans bonds.
BRANCHED CHAIN FATTY
ACIDS
Phytanic

Sebum
 acidcontains
also presentbranched
in butter chain fatty
acids.
fatty There
acids. may be even or odd chain
Even chain fatty acids are predominantly

present.
Cyclic fatty
 acids-
Chaulmoogric acid and Hydnocarpic
acid
Substituted fatty acids
Cerebronic acid- OH fatty acid
BIOLOGICAL IMPORTANCE OF
FATTY ACIDS
 Fatty acids are the building blocks of dietary fats.
The human body stores such fats in the form of
triglycerides.
 Fatty acids are also required for the
formation of membrane lipids such
as phospholipids and glycolipids.
 They are required for the esterificaton of
cholesterol to form cholesteryl esters.
 They act as fuel molecules and are oxidized to produce
energy.
Properties of fatty acids
SOLUBILITY IN WATER
-Solubility in water decreases with increase in
chain length. Short chains are soluble in water
owing to the polar nature of the COOH group ,
which ionizes at neutral pH. Higher fatty acids are
insoluble in water but soluble in organic
solvents.
Melting and boiling point

 Melting and boiling points increase with

increasing Chain length but decrease drastically
with increase in the number of double bonds.
 Fatty acids of chain length <8C are liquid at room
temperature.
 Saturated fatty acids 12:0 to 24:0 have a waxy
consistency at the room temperature while
unsaturated fatty acids of same carbon length are
oily liquids.
continued
 Fats containing fatty acids 18:2 are liquid
 Saturated chains have extended Zigzag
configuration at low temperature but shorten at
higher temperature owing to rotation of C-C
bonds.
 This explains why bio membranes get thinner with
increase in temperature.
Chemical properties
 Fatty acids are readily hydrolyzed by heating with
acids or alkyls or superheated steam. When boiled
with sodium or potassium hydroxide solution, the
hydrolysis products are sodium or potassium salts
of long chain fatty acids. The latter are called
soaps and alkaline hydrolysis is referred to as
saponification.
hydrogenation
On catalytic hydrogenation at low pressure,
hydrogen adds across the C=C of the acid
components of the triglyceride. This results in the
formation of saturated glycerides which are solids
fats at room temperature. This hydrogenation process
is called hardening.
oxidation
-When highly unsaturated oils are exposed to air,
they undergo oxidation and polymerization to form a
thin waterproof film. Such oils are called drying oils
and the reaction is referred to as drying.
Linseed oil, which is rich in linolenic acid, is
common drying oil used in oil based paints. Non
drying oils are either saturated or only moderately
unsaturated.
 Ester formation
Fatty acids in combination with alcohols form esters e.g glycerol
form mono, di, and tri glycerides. And with other alcohols form
waxes.
 Prostaglandins formation

They are derivative of 20 C unsaturated fatty acid. They have

important physiological and metabolic functions
 Detergent formation
 Reduction of carboxyl group of fatty acids produce alkyl
alcohal
 Alkyl alcohol may get sulfated to form alkyl sulphate which
acts as detergents.
 Detergents are good emulsifiers
Acrolein test

Fats when heated in the presence of a dehydrating agent

NaHSO4 produce an unsaturated aldehyde called Acrolein
from the glycerol moiety. Acrolein is easily recognized by its
pungent odour and thus forms the basis of the test for the
presence of glycerol in Fat molecule.
 Rancidity
HYDROLYTIC RANCIDITY-
On storage fats become rancid. This is caused by the
growth of lipase secreting microbes.
Lipase splits fats into glycerol and free fatty acids.
Fatty acids impart unpleasant odour and flavor to
the fat.
Fats should not be mixed with water and kept in cold
to avoid rancidity
 rancidity
 Oxidative rancidity
Oils containing highly unsaturated fatty acids are
spontaneously oxidized by atmospheric Oxygen
at ordinary temperatures.
The autoxidation takes place slowly and forms
short chain fatty acids(C4-C10) and aldehydes
which give rancid taste and odour to the fats.
This is observed more frequently in animal fats
than in vegetable fats. Vegetable fats contain
natural antioxidants which check autoxidation.