Lipids

Defination
Lipids may be regarded as organic substances relatively insoluble in
water, soluble in organic solvents, potentially related to fatty acids and
utilized by the living cells.

Introduction
o The word lipid is derived from a Greek word “lipos” which means
Fat.
o Biological lipids are a chemically diverse group of organic
compounds which are insoluble in water.
o They are soluble in non-polar solvents such as- ether, chloroform,
or benzene.
o Lipids are hydrophobic in nature due to the predominance of
hydrocarbon chains. (-CH2- CH2-CH2-) in their structures.
o Unlike the proteins, nucleic acids, and polysaccharides, lipids are
not polymer.
o They are the chief storage form of energy, they provide 6-fold as
much energy as an equivalent mass of glycogen.
o Fat and oils are the principle stored forms of energy in many
organism.
o Lipids participate in oxidative phosphorylation.
o Neutral lipids upon hydrolysis yield glycerol and fatty acids
o Many lipid molecules are amphipathic.
o In aqueous environment lipid molecules associate by non-covalent
interactions to form supramolecular structures such as monolayers,
micelles, bilayers and vesicles.

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Function of lipid
o They serve as a storage form of metabolic fuel. (Fatty acid,
Triacyglycerol).
o They serve as a transport form of metabolic fuel.(free fatty acid,
triglyceride and cholesterol ester)
o They provide the structural components of membranes
(phospholipids, glycolipids, galactolipids, and sphingolipids)
o They have protective functions in bacteria, plants, insects, and
vertebrates, serving as a part of the outer coating between the body
of the organism and the environment.
o It serve as pigment (carotene), hormones (vitamin A & D), signaling
molecules (eicosanoids, phosphatidylinositol, steroid hormone)
cofactors (vitamin E, K and lipid quinones) detergent (bile salt).

Classification of lipid
Classification based on the chemical composition by BLOOR
(1943)

o SIMPLE LIPIDS or HOMOLIPIDS

1. Fats and Oils
2. Waxes
o COMPOUND /COMPLEX LIPIDS or HETEROLIPIDS
1. Phospholipids
2. Glycolipids
3. Lipoproteins
o DERIVED LIPIDS
1. Steroids
2. Terpenes

Simple Lipids/ Homolipids

o These are esters of fatty acid with alcohols.
o FATS AND OILS (triglycerides, triacylglycerols)
o are esters of fatty acids with glycerol.

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 o Difference between fat and oil is physical - oil is liquid while fat is
solid at room temperature.

WAXES
o Esters of fatty acids with alcohols other than glycerol.

Compound/ Complex/ Heterolipids

o Are esters of fatty acids with alcohols containing additional groups
like phosphate, carbohydrate, protein etc

PHOSPHOLIPIDS (PHOSPHATIDS)

o Compounds containing in addition to fatty acids and glycerol, a

phosphoric acid and nitrogen bases .

GLYCOLIPIDS (CEREBROSIDES)

o Compounds of fatty acids with carbohydrates and contain nitrogen

but no phosphoric acid

LIPOPROTEINS

Derived Lipids
o Substances derived from simple and compound lipids by
hydrolysis. These include fatty acids, alcohols, mono and
diglycerides, steroids, terpenes and carotenoids.
o Neutral Lipids
o Uncharged lipids like glycerides and cholestrol

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Simple Lipids/ Homolipids
o FATS AND OILS = TRIGLYCERIDES OR TRIACYLGLYCEROLS
o The Triglycerides are the most abundant of all lipids.
o They constitute 98% of the dietary lipids, 2% consists of
phospholipids and cholesterol and esters.
o Triglyceride molecule contain fatty acids of varying lengths, which
may be saturated or unsaturated.
o Triglycerides can be distinguished as fat and oil on the basis of
physical state at room temperature.
o Fats which are solid at room temperature, contain saturated fatty
acids.
o Oils are liquid at room temperature, contain unsaturated fatty acid.
o Major components of storage.
o They are insoluble in water, non-polar in character and are
commonly called neutral fats.
o They have lower specific gravity than water, hence they float on
water.
o Fats are stored fuel reserves
o Fats primarily occur in adipose tissue by the adipocytes of adipose
tissue, which are found in the subcutaneous layer and in abdominal
cavity.

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o Chemically, triglycerides are ESTERS OF GLYCEROL WITH 3
FATTY ACID MOLECULES.
o SIMPLE / SYMMETRICAL TRIGLYCERIDES – contain SAME
TYPE OF FATTY ACID molecules at all the three carbons.
o MIXED TRIGLYCERIDES – are more common. They contain more
than one type of fatty acid residue. Eg. Oleodipalmitin,
Oleopalmitostearin
o Triglycerides of plants have higher content of unsaturated fatty
acids compared to that of animals.
o When groups attached to the carbon 1 and 3 are different, a centre
of asymmetry is created at C2. The naturally occurying fats are of L-
type.

o Depending on the no. of fatty acid esterified to the glycerol,

there may be mono, di or triglyceride

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 WAXES

o Waxes are esters of long chain saturated and unsaturated fatty

acids with long chain monohydroxy alcohols.
o Waxes also occur as protective coating on fruits and leaves. The
leaves of many plants like Rhododendron, Calotropis are shiny
because of deposition of protective waxy coating.
o Animal Wax - Beeswax is obtained from the honeycomb
o The sperm whale wax (spermaceti) and beeswax are composed
mainly of palmitic acid esterified with either hexacosanol,
CH3(CH2)24CH2OH or triacontanol (myricyl alcohol or
melissyl alcohol), CH3(CH2)28CH2OH
o Lanolin (from lamb’s wool), beeswax (from honeycomb),
carnauba wax (from Brazilizn palm tree) and spermaceti oil
(from sperm whales) are widely used in the manufacture of
lotions, ointments and polishes.

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 Properties

 Hydrolysis
o Triacylglycerols undergo enzymatic hydrolysis to liberate free
fatty acids and glycerol.
o The hydrolysis is calatysed by lipases.
o It is important for digestion of fat in the gastrointestinal tract
and fat mobilization from adipose tissues. .
 Saponification
o Hydrolysis of triacylglycerol by alkalis such as NaOH or KOH
to produce glycerol and soaps is called saponification.
o Triglycerol + 3 NaOH Glycerol +3 R COONa (Soap)
 Saponification number
o The number of milligram of KOH required to saponify
(hydrolyse) one gram of fat is known as saponification number.
o The saponification number measures the average molecular size
of fatty acids present.
o The value is higher for fats containing short chain fatty acids.
o Eg Saponification no. of Butter : 195 -200 Coconut oil : 250 – 260
 Iodine number
o The number of grams of iodine that can be added to 100 g
sample of fat or oil is called Iodine number.
o It is used to determine the degree of unsaturation
o It is directly proportional to the content of unsaturated fatty
acids.
o Thus, lower the iodine number, less is the degree of
unsaturation.
o Determination of iodine number helps to know the degree of
adulteration of a given oil.

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 Rancidity
o Rancidity is the term used to represent the deterioration of fats
and oils resulting in an unpleasant taste.
o Fats containing unsaturated fatty acids are more susceptible to
rancidity.
o Rancidity occurs when fats and oils are exposed to air, moisture,
light, bacteria etc.
o Hydrolytic rancidity occurs due to partial hydrolysis of
triglycerols by bacterial enzymes.
o 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.
o Rancid fats and oils are unsuitable for human consumption.
 Antioxidants
o The substance which can prevent the occurrence of oxidative
rancidity are known as antioxidants.
o Trace amounts of antioxidants such as tocopherols (vit E),
hydroquinone, gallic acid and α-naphthol are added to the
commercial preparation of fats and oils to prevent rancidity.
o Propyl gallate, butylated hydroxyanisole (BHA) and butylated
hydroxytoluene (BHT) are the antioxidants used in food
preservation.
 Acid Number
o It is defined as the number of mg of KOH required to neutralize
free fatty acids present in one gram fat or oil.
o Normally refined oils are free from any free fatty acids.
o Oils on decomposition (due to chemical or bacterial
contamination) yield free fatty acids.
o Thus, oils with increases acid number are unsafe for human
consumption.
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Compound/ Complex/ Heterolipids

 Phospholipids
o Are most abundant membrane lipids.
o They serve as structural components of membranes.
o They differ from triglycerides in possessing one hydrophilic
polar ‘head’ group and 2 hydrophobic nonpolar ‘tails’. Because
of which they are known as Polar Lipids. Thus Phospholipids
are amphipathic.
o They contain phosphorous in the form of phosphoric acid
groups.
o In phospholipids two of the OH groups in glycerol are linked to
fatty acids while the third OH group is linked to phosphoric
acid. The group attached to the phosphoric acid changes.
o They contain phosphoric acid, nitrogenous base in addition to
alcohol and fatty acids.
o There are two classes of Phospholipids

Glycerophospholipids / Phosphoglycerides –

o contain Glycerol as alcohol

Sphingophospholipids / Sphingomyelins –

o contain sphingosine as alcohol

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 Phosphatidic acid

o Simplest phospholipid.
o It has got 2 molecules of fatty acid esterified to glycerol. The
phosphoric acid is esterified at terminal end.
o The other glycerophospholipids containing different
nitrogenous bases or other groups may be regarded as
derivatives of phosphatidic acid.
o Phosphoglyceride are classified according to which alcohol
becomes esterified to the phosphate group, like serine,
ethanolamine, choline, glycerol, and inositol.

 Lecithins/Phosphatidylcholine –

o It is a phosphatidic acid with choline as the base. They are found

in animals and plants. They are essential constituents of cells,
especially membranes. These are found in soybean and yeast.
o Lecithin has a glycerol, 2 molecules of fatty acids, phosphoric
acid and a nitrogenous base choline

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 Cephalins / Phosphatidylethanolamine –

o Ethanolamine is the nitrogenous base present in cephalins. They

are found in soybean oil.
 Phosphatidylinositol –

o Here a cyclic hexahydroxyalcohol called inositol replaces base.

The stereoisomer myo-inositol is attached to phosphatidic acid
to give phosphatidylinositol (PI).
o This is an important component of cell membrane. They have
been found to occur in phospholipid of brain tissue and of
soybeans.
 Phosphatidylserine –

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 o Consists of 2 fatty acids, attached in ester linkage to the first and
second carbon of glycerol and serine attached through a
phosphodiester linkage to the third carbon of the glycerol.

 Plasmalogens –

o Here fatty acid (unsaturated) is attached by an ether linkage at

C1 of glycerol. Polar group may be ethanolamine, choline,
inositol or serine. Not significant in plants. It is found in brain.
 Cardiolipin –

o So named because was first isolated from heart muscle.

o Here two molecules of phosphatidic acid are held by glycerol
through phosphate groups. It is an important component of
inner mitochondrial membrane.
 Sphingophospholipids/ Sphingomyelins
o Sphingosine is an 18 C amino alcohol present in
sphingomyelins, instead of glycerol.
o Sphingosine is attached by an amide linkage to a fatty acid to
produce ceramide.
o The alcohol group of sphingosine is bound to
phosphorylcholine in sphingomyelin structure.

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 o Sphingomyelins are found in good quantity in brain and
nervous tissue. They apparently lack in plants

 Glycolipids

 Glycolipids/ glycosphingolipids - are substances whose

molecules consist of a lipid attached with a single or complex sugar
molecule. They are important constituents of cell membrane and
nervous tissues.
 Cerebrosides – simplest form of glycolipids. They contain
ceramide (sphingosine attached to a fatty acid) and one sugars/
monosaccharide attached . It will form galactosylceramide, when
galactose is attached. It contains fatty acid cerebronic acid.
 Gangliosides –They are derivatives of cerebrosides. They contain
1 or more molecules of N-acetylneuraminic acid (NANA), sialic
acid. Gangliosides with one sialic acid residue are known as GM (M
for mono), They are found in ganglions , in brain.
 Globosides – A type of glycolipids with 2 or more sugars linked
to ceramide. The sugars usually present are glucose and galactose.
Eg.Lactosylceramide (ceramide-galactoseglucose)

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 Lipoproteins
o In plasma, the lipids are associated with proteins. They form
Lipoproteins.
o They are the transport vehicles for lipids in circulation. Blood
plasma contains a number of soluble lipoproteins, classified
according to their densities into 4 major types.
o These lipid protein complexes function as a lipid transport system
because isolated lipids are insoluble in blood.
o There are 5 basic types of lipoproteins
o Chylomicrons
o Very low density lipoproteins (VLDL)
o Low density lipoproteins (LDL)
o High density lipoproteins (HDL)
o Free fatty acid –albumin complexes

Derived lipid

o Obtained by hydrolysis of simple lipid and compound lipid.

o It contains steroid/sterol, mono and di acyl glycerol, steroid
hormones.
 Steroids
o Steroids contain a cyclic steroid nucleus or ring , called CPPP
(CycloPentanoPerhydroPhenanthrene).
o It consists of a phenanthrene nucleus (ring A, B and C) to which
cyclopentane ring (D) is attached.
o The methyl side chains are attached to C 18 and C19.
o At C17, steroid contain a side chain.

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  Sterol
o When steroid contains one or more hydroxyl group, it is called
sterol.
o Cholestrol is exclusively found in animals.
 Ergosterol

o Ergosterol is a sterol found in cell membrane of fungi and

protozoa, serving many of similar functions that cholesterol
serves in animal cells.
o It is present in ergot, yeast and the mould Neurospora.
o Ergosterol has a molecular formula C28H43OH, with one OH
group at C3 and 3 double bonds at C5, C7 and C22.
o A number of sterols have been obtained from many plants like
o Stigmasterol from soybean and wheat germ oil
o Spinasterol from spinach and cabbage
o Sitosterol from many higher plants
o

Fatty acid
o Fatty acids are the simplest form of lipids.
o These are monocarboxylic, straight, unbranched hydrocarbon
chains containing even number of carbon atoms (betweeen 4- 36)
o Fatty acids are also known as acyl group when it is a part of ester.
o Fatty acids are amphipathic in nature.
o The fatty acids may be free or esterified with glycerol to form
triglycerides.

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Types of fatty acid

 Saturated fatty acid

o Saturated fatty acids have no double bonds in the chain or contain
single chain.
o Their general formula is CH3-(CH2)n-COOH, where n specifies the
number of methylene groups between the methyl and carboxyl
carbons.
o They have higher melting points
o They are solid at room temperature.
o Examples- lauric, myristic, palmitic acid etc.

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 Unsaturated fatty acid
o These fatty acid contain one or more double bonds along the length
of the hydrocarbon chain.
o They are liquid at room temperature.
o Have low melting point.
o The commonly used system for designating the position of double
bond in unsaturated fatty acid is the delta (∆) numbering system.
o Example- linoleic acid, oleic acid, palmitoleic acid.
o In the naturally occurring unsaturated fatty acid the double bond
are in cis configuration and trans fatty acid are produced by
fermentation in the rumen of dairy animals and are obtained from
dairy products and meat.

Type of unsaturated fatty acid

Based upon the no. of double bond present

 Monounsaturated fatty acid:-

o They contain only one double bond per fatty acid.
o The double bond is between C-9 and C-10(∆9)
 Polyunsaturated fatty acid or PUFAs:-
o They contain two or more double bonds along the length of the
hydrocarbon chains.
o PUFAs are also known as essential fatty acid.
o Examples- linoleic and linolenic acid
o

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Melting point of fatty acids
o M.P of fatty acid depends on
o the chain length
o Presence or absence of double bond
o No. of double bonds, i.e degree of unsaturation.
o The longer the length, the higher the M.P. , the greater the no. of
double bonds, the lower the M.P.
o The presence of double bond makes unsaturated chain more rigid
and creates a kink in the chain.
o As a result, unsaturated chains cannot pack themselves in crystals
efficiency and densely as saturated chain, so they have a lower
melting point as compared to saturated fatty acids. The
hydrocarbon chain of saturated fatty acids eg. Stearic acid (18:0)
CH3 (CH2 )16COOH, has a zigzag configuration with the C –C
bond forming a bond angle of 109o .
o In simple form, the long chain of CH2 groups are represented by a
zigzag line, where each corner represents a C atom .

Nomenclature
o The saturated fatty acids end with a suffix –anoic , eg octanoic acid
o The unsaturated fatty acids end with a suffix – enoic, eg.
Octadecanoic acid.
o The numbering of carbon atom starts from the carboxyl carbon. It is
given no. 1. The carbon adjacent to this carboxyl carbon are 2, 3, 4
and so on OR α, β, γ and so on.
o The terminal carbon containing methyl group is known as omega
carbon. Starting from the methyl end, the carbon atoms in a fatty
acid are numbered as omega 1,2,3 and so on

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Isomerism in unsaturated fatty acids
o Unsaturated fatty acids show isomerism, depending on the
orientation of the groups around the double bond axis.
o If the atoms or groups are present on the same side of the double
bond, it is a cis configuration.
o If the groups occur on the opposite side, it is Trans configuration.
o Eg. Oleic acid is a cis isomer, elaidic acid is a Trans isomer.
o Cis isomers are less stable than Trans isomers.
o Trans isomer is more stable than cis isomer because in cis isomer,
the bulky groups are on the same side of the double bond. The steric
repulsion of the group makes the cis isomer less stable than the
Trans isomer in which bulky groups are on the opposite side of the
double bond.
o Most of the naturally occurring unsaturated fatty acids exist as cis
isomers.

 HYDROXY /OXYGENATED FATTY ACIDS

o Eg . Ricinoleic acid, found in Castor oil. It is a C18 acid, with = at
C9 and OH group on C12.

 CYCLIC FATTY ACIDS

o Eg. Lactobacillic acid, with a cyclopropyl group and a methylene
group across the double bond of vaccenic acid .
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