Chemistry of lipids and

membranes
By
Nosheen Bashir
 LIPIDS
• lipid, a category of molecules united by their inability
to mix well with water. Lipids tend to be hydrophobic,
nonpolar, and made up mostly of hydrocarbon chains,
though there are some variations on this.
• The word lipid is derived from a Greek word “lipos”
which means Fat.
 CLASSIFICATION OF LIPIDS
SIMPLE LIPIDS: They are esters of fatty acids with alcohol.
 Fats and oils
 Waxes
COMPLEX LIPIDS: They are esters of fatty acids with alcohol
containing additional groups such as phosphate, carbohydrates,
protein etc.
 Phospholipids
 Glycerophospholipids
 Sphingophospholipids
 Glycolipids
 Lipoprotein
 Other complex lipids
DERIVED LIPIDS: They are the derivatives that are obtained on
the hydrolysis of simple and complex lipids.
MISCELLANEOUS LIPIDS:
 FATTY ACIDS

• They are the carboxylic acids with hydrocarbon side

chain chains.
• They are present either in esterified form or in free or
esterified form.
 SATURATED FATTY ACIDS
• If there are only single bonds between neighboring
carbons in the hydrocarbon chain, a fatty acid is said to
be saturated.
• Saturated fatty acids tails are straight, so molecules
with fully saturated tails can pack tightly against one
another. This tight packing results in fats that are solid
at room temperature (have a relatively high melting
point). For instance, most of the fat in butter is
saturated fat.
 UNSATURATED FATTY ACIDS
• When the hydrocarbon chain has a double bond, the
fatty acid is said to be unsaturated.
• If there is just one double bond in a fatty acid,
its monounsaturated, and while if there are multiple
double bonds, it’s polyunsaturated.
• The double bonds in unsaturated fatty acids can exist
in either a cis or a trans configuration. In
the cis configuration, the two hydrogens associated
with the bond are on the same side, A cis double bond
generates a kink or bend in the fatty acid, a feature that
has important consequences for the behavior of fats.
While in a trans configuration, they are on opposite
sides.
• cis-unsaturated fatty acid tails are bent due to
the cis double bond.
• This makes it hard for fat molecules with one or
more cis-unsaturated fatty acid tails to pack tightly.
• So, fats with unsaturated tails tend to be liquid at
room temperature (have a relatively low melting
point) – they are what we commonly call oils.
• For instance, olive oil is mostly made up of
unsaturated fats
• Trans fats are rare in nature, but are readily
produced in an industrial procedure called partial
hydrogenation.
• In this process, hydrogen gas is passed through oils
(made mostly of cis-unsaturated fats), converting
some – but not all – of the double bonds to single
bonds.
• The goal of partial hydrogenation is to give the oils
some of the desirable properties of saturated fats,
such as solidity at room temperature, and increase
the shelf life of food.
• trans fats have turned out to have very negative
effects on human health. Because of a strong link
between trans fats and coronary heart disease.
 NOMENCLATURE OF FATTY
ACIDS
• Fatty acids are named on the basis of hydrocarbons
they are derived from
• Suffix for saturated fatty acids is –anoic
• Suffix for unsaturated fatty acids is –enoic
• Numbering the carbon atoms:
• Carboxyl carbon taken as 1 and so on.
• Terminal carbon containing methyl group is known
as omega.
• Starting from methyl end carbon atoms are
numbered as omega 1,2,3 and so on.
 SHORTHAND REPERESENTATION OF FATTY
ACIDS
General rule to write shorthand notations:
• Total number of carbon atoms
• Number of double bonds
• Position of double bonds, starting from the carboxyl
end.
1. Palmitic acid (16 carbon saturated) 16:0
2. Oleic acid ( 18 carbon with one double bond between
carbon 9 and 10) 18:1;9 or 18:1(∆9 )
3. Linoleic acid (18 carbon with two double bonds
between 9 and 10, 12 and 13) 18:2;9,12 or 18:2(∆9,12).
4. Arachidonic acid 20:4(∆5,8,11,14)
5. Eleostearic acid 18:3(∆9,11,13)
LENGTH OF HYDROCARBON CHAINS OF
FATTY ACIDS
• short-chain (C4 and C6)
• medium-chain (C8 and C14)
• long-chain (C16 to C24)

EVEN AND ODD CARBON FATTY ACIDS

• Lipids usually have even chain carbon fatty acids
(14C-20C)
• This is because synthesis of fatty acids occurs by
addition of two carbon units sequentially.
• Among even chain odd chain fatty acids are also
present i.e, propionic acid (3C) and valeric acid
(5C).
ESSENTIAL FATTY ACID
• A fatty acid that is essential to human health, but
cannot be manufactured in the body. Abbreviated
EFA.
• They are usually PUFA
• There are three types of EFAs: arachnoidic acid,
linoleic acid, and linolenic acid.
• When linoleic acid is obtained in the diet, it can be
converted to both arachnoidic and linolenic acid,
because linoleic is a common precursor.
 TRIACYLGLYCEROL
• Oil: A mixture of triacylglycerol that is liquid because
it contains a high proportion of unsaturated fatty acids.
• Fat: A mixture of triacylglycerol that is solid because
it contains a high proportion of saturated fatty acids.
• A fat molecule consists of two kinds of parts: a
glycerol backbone and three fatty acid tails.
• Glycerol is a small organic molecule with three
hydroxyl (OH) groups, while a fatty acid consists of a
long hydrocarbon chain attached to a carboxyl group.
• A triglyceride is called a fat if it is a solid at 25°C; it is
called oil if it is a liquid at that temperature.
• These differences in melting points reflect differences
in the degree of unsaturation and number of carbon
atoms in the constituent fatty acids.
• Triglycerides obtained from animal sources are
usually solids, while those of plant origin are
generally oils.
• Therefore, we commonly speak of animal fats and
vegetable oils.
• Fat molecules are also called triacylglycerol or
triglycerides. In the human body, triglycerides are
primarily stored in specialized fat cells, called
adipocytes, which make up a tissue known as adipose
tissue.
• If all three OH groups on the glycerol molecule are
esterified with the same fatty acid, the resulting
ester is called a simple triglyceride.
• Instead, a typical triglyceride obtained from
naturally occurring fats and oils contains two or
three different fatty acid components and is thus
termed a mixed triglyceride.
 STRUCTURE OF
ACYLGLYCEROLS
• On the basis of number of fatty acids molecules
esterified to a molecule of glycerol, acylglycerols can
be of three types:

• Monoacylglycerol – 1 molecule of fatty acid

• Diacylglycerol – 2 molecules of fatty acid

• Triacylglycerol – 3 molecules of fatty acid

 STEREOSPECIFIC NUMBERING
OF GLYCEROL

• "sn" notation, which stands

for stereospecific numbering.
• The structure of glycerol shows that C1 and C3 are
identical, which is not true in 3 dimensional structure.
• C1 and C3 are different and cells possess enzymes that
differentiate between these two carbons.
• Thus glycerol kinase phosphorylates sn-3 glycerol to
give sn-glycerol 3-phosphate.
CHEMICAL PROPERTIES OF FATS
1. Hydrolysis
2. Saponifcation
3. Rancidity
4. Lipid peroxidation
1.HYDROLYSIS
Triglycerides are easily hydrolyzed by enzymes called
lipases (catalysts) in the digestive tracts of animals to
give fatty acids and glycerol. The fatty acids so
produced play an important role in the metabolic
process in the animal body.
2.SAPONIFICATION
When triglycerides are hydrolyzed (saponified) by
alkalis, glycerol plus the salts of fatty acids are produced.
Generally the sodium or potassium salts are obtained
which are termed soaps.
3.RANCIDITY

• The term rancid is applied to any fat or oil that develops

a disagreeable odor and unpleasant taste when left
exposed to warm, moist air for any length of time.
• Rancidity is the oxidation of fats that is caused by
hydration (water), oxidation (oxygen), or microbes.
• Fats containing unsaturated fatty acids are more
susceptible to rancidity.
• Rancid fats and oils are not suitable for human
consumption.
HYDROLYTIC RANCIDITY
• Hydrolytic Rancidity is by hydrolysis of the ester
links. Hydrolytic rancidity refers to the odor that
develops when triglycerides are hydrolyzed and free
fatty acids are released.
• Hydrolysis will split fatty acid chains away from the
glycerol backbone in glycerides.
• These free fatty acids can then undergo further auto-
oxidation leads to oxidative rancidity.
• This reaction of lipid with water may require
a catalyst (enzyme) , leading to the formation of
free fatty acids and glycerol.
OXIDATIVE RANCIDITY

• Oxidative rancidity is the oxidation of double bonds

of the triglycerides.
• Oxidative rancidity is associated with the degradation
by oxygen in the air.
• The double bonds of an unsaturated fatty acid can be
cleaved by free-radical reactions involving molecular
oxygen.
• Oxidative rancidity leads to the formation of both
unpalatable and toxic compounds
• During the process, oxygen molecules interact with the
structure of the oil and damage its natural structure in a
way that can change its odor, its taste, and its safety for
consumption, i.e. fat is oxidized and decomposes into
compounds with shorter carbon chains such as
dicarboxylic acids, aldehydes, and ketones all of which
are volatile and contribute to the unpleasant odor of
rancid fats.
MICROBIAL RANCIDITY
• Certain microorganisms can produce the hydrolytic
enzyme called lipase, which directly interferes the
hydrolysis of triglycerides and produce glycerol and
fatty acid.
• These fatty acids undergo auto- oxidation to form
rancid. The microbial lipase requires suitable pH and
other conditions for its activity upon fats and oil.
ANTIOXIDANTS

• They are the substances that prevent the occurrence of

oxidative rancidity.
• Lipid oxidation is certainly one of the most important
alterations that affect both oils or fats and foods that
contain them.
• It is responsible for the development of unpleasant
taste and smell in foods, making them unsuitable for
consuming. The use of antioxidants permits a longer
useful life of these products.
• Hydroquinone, gallic acid, alpha-napthol and
tocopherols (vitamin E) are added for commercial
prepration of fats and oil.
• Antioxidants used in food preservation include
butylated hydroxyanisole (BHA), butylated
hydroxytoluene (BHT), propyl-3, 4, 5-
trihydroxybenzoate (also known as propyl
gallate).
4. LIPID PEROXIDATION
• Lipid peroxidation is the oxidative degradation
of lipids.
• It is the process in which free radicals extract
electrons from the lipids in cell membranes, forming
a fatty acid radical which then reacts with other fatty
acids producing lipid peroxide and more fatty acid
radicals resulting in cell damage.
• The free radicals may cause aging, cancer,
atherosclerosis etc.
• Cell possesses natural antioxidants such as vitamin
E, urate and superoxide dismutase to prevent in vivo
lipid peroxidation.
 TEST TO CHECK PURITY OF
FATS AND OILS

IODINE NUMBER:
• Iodine Number, also called Iodine value, is measure
of the degree of unsaturation of an oil, fat, or wax.
• It is the amount (mass) of iodine, in grams, that is
taken up by 100 grams of the oil, fat, or wax.
• Iodine number is directly proportional to the
content of unsaturated fatty acids. The higher the
iodine number, the more C=C bonds are present in
the fat.
SAPONIFICATION NUMBER:
• Saponification is the process by which the fatty acids
in the glycerides of the oil are hydrolyzed by an
alkali. Saponification value is the amount (mg) of
alkali (KOH) required to saponify (hydrolyze) 1 of
an oil or fat.
• This value is useful for a comparative study of the
fatty acid chain length in oils or fats.
• The value is higher for fats containing short chain
fatty acids.
REICHERT-MEISSL (RM)
NUMBER:
• The Reichert value is a value determined when
examining fat.
• The Reichert value is an indicator of how much
volatile fatty acid can be extracted from fat
through saponification.
• It is the number of ml of 0.1 N KOH solution required
for the neutralization of the water-soluble volatile fatty
acids distilled and filtered from 5 grams of a given fat.
• Higher content of Volatile fatty acids of butter
(Butyric acid ,Caproic acid &Caprylic acid)
responsible for its higher Reichert –Meissl number
• Reichert –Meissl number for butter (RM 25-30) &
negligible for fat /edible oils without volatile fatty
acids (RM< 1).
• Reichert –Meissl number of Fat/oils is useful in
testing purity /adulteration of butter.

• The value is named for the chemists who developed

it, Emil Reichert and Emerich Meissl.
ACID NUMBER:
• The acid value is defined as the number of
milligrams of Potassium hydroxide (KOH) required
to neutralize the free fatty acids present in one gram
of fat.
• It is a relative measure of rancidity as free fatty
acids are normally formed during decomposition of
triglycerides.
• Oils on decomposition due to chemical or bacterial
contamination yields free fatty acids. Therefore, oils
with increased acid numbers are unsafe for human
consumption.
• Refined oils should be free from free fatty acids.