Lipids

Sanjay Mahato
Assistant Professor, IAAS
• The lipids are a heterogeneous group of compounds related to fatty acids
and include fats, oils, waxes and other related substances.
• These are oily or greasy organic substances, relatively insoluble in water
and considerably soluble in organic solvents like ether, chloroform and
benzene.
• They are, thus, hydrophobic in nature.
• These are variously called as lipins or lipoids.
• The latter term is, however, sometimes used to refer “fat-like” substances
which may not actually be related to the fatty acids.
• Abundantly found in nature.
• The fat and fatlike substances fall under lipid because of their similar
solubilities.
• Fatty acids are the principle components associated with most of the lipids.
 Structure of Fats & Fatty Acids
• Chemically, the fats are defined as the esters of glycerol and fatty acids or
as the triglycerides of fatty acids.
• Commonly lipids consists of Alcohol and Fatty Acids.
• So, there are two components found in lipids:
1. Alcohol, 2. Fatty Acids
1. Alcohol:
• Alcohols found in lipid molecules may be saturated. These commonly
include glycerol, cholesterol and higher alcohols such as cetyl alcohol and
myricyl alcohol.
• Among the unsaturated alcohols found in fats are included a number
of pigments like phytol and lycophyll. The former is a constituent of
chlorophyll, whereas the latter is found in tomatoes as a purple pigment.
2. Fatty Acids:
• Fatty acids are straight aliphatic chains with a methyl group at one end
and a carboxyl group at the other end.
• Fatty acids are long-chain organic acids having usually from 4 to 30
carbon atoms;
• They have a single carboxyl group and a long, nonpolar hydrocarbon
‘tail’, which gives most lipids their hydrophobic and oily or greasy nature.
• Fatty acids do not occur in free or uncombined state in cells or tissues but
are present in covalently bound form in different classes of lipids.
• Fatty acids are stored as an energy reserve (fat) through an ester linkage
to glycerol to form triglycerides.
• Fattty acids may be of following types:
1. Saturated Fatty Acids
2. Unsaturated Fatty Acids
3. Hydroxy or Oxygenated Fatty Acids
4. Cyclic Fatty Acids.
A. Saturated Fatty Acids:
• The long carbon chain contains only single bond.
• The general formula for these acids is CnH2n+1COOH.

Examples of Naturally occurring Saturated Fatty Acids:

Name Structure Sources
1. Capric acids CH3 (CH2)8COOH Coconut & Palm
Oils
2. Myristic acids CH3 (CH2)12COOH Butter & Wool fats
3. Palmitic acids CH3 (CH2)14COOH Animal & Plant fats
4. Stearic acids CH3 (CH2)16COOH Animal & plant
B. Unsaturated Fatty Acids:
• The long carbon chain contains one or more double bonds.
• Monounsaturated fatty acids (MUFA) contain one double bond and
polyunsaturated fatty acids (PUFA) contain two or more double bonds.
The double bonds of fatty acids are separated by three carbon interval.
 These may be classified, based on the degree of un-saturation:
A. Monoethenoid acids — These contain one double bond and conform to the
general formula, CnH2n–1COOH. The common example is oleic acid.
B. Diethenoid acids — Two double bonds; CnH2n−3COOH; Linoleic acid.
C. Triethenoid acids — Three double bonds; CnH2n−5COOH; Linolenic
acid.
D. Tetraethenoid acids — Four double bonds; CnH2n−7COOH; Arachidonic
acid
 carbon
Number Number of Common name Systematic name Formula
double bonds
12 0 Laurate n-Dodecanoate CH3(CH2)10COO-
14 0 Myristate n-tetradeconoate CH3(CH2)12COO-
16 0 Palmitate n-hexadeconoate CH3(CH2)14COO-
18 0 Stearate n-Octadeconoate CH3(CH2)16COO-
20 0 Arachidate n-Eicosanoate CH3(CH2)18COO-
22 0 Behenate n-Docosanoate CH3(CH2)20COO-
24 0 Lignocerate n-Tetracosanoate CH3(CH2)22COO-
16 1 Palmitoleate Cis-Δ9-Hexadecenoate CH3(CH2)5CH=CH(CH2)7COO-

18 1 Oleate Cis-Δ9-Octadecenoate CH3(CH2)7CH=CH(CH2)7COO-

18 2 Linoleate Cis,Cis-Δ9, Δ12- CH3(CH2)4(CH=CHCH2)2(CH2)6COO

Octadecadienoate -

18 3 Linolenate all-Cis-Δ9, Δ12, Δ15- CH3CH2(CH=CHCH2)3(CH2)6COO-

Octadecatrienoate
20 4 Arachidonate all-Cis- Δ5,Δ8, Δ11, Δ14- CH3(CH2)4(CH=CHCH2)4(CH2)2COO
Eicosatetraenoate -
Examples of Naturally occurring Unsaturated Fatty Acids:
Fatty Acids Structure Sources
1.Palmitoleic Acid CH3 (CH2)5CH=CH(CH2)7COOH Animal &
Plant

2. Oleic Acid CH3 (CH2)7CH=CH(CH2)7COOH Animal &

Plant

3. Linoleic Acid CH3(CH2)4CH=CHCH2 CH=CH (CH2)7COOH Linseed &

Cotton oils
seeds

4. Linolenic Acid CH3CH2CH=CHCH2CH=CHCH2CH=CH(CH2)7COOH

Linseed
oil

5. Arachidonic Acid CH3(CH2)4CH=CHCH2CH=CHCH2CH=CHCH2CH=CH

(CH2)3COOH Animal fat
C. Hydroxy or Oxygenated Fatty Acids:
• One of these found in castor oil is ricinoleic acid (87%). It is a C 18 acid
with a double bond at C9 and an OH group on C12.

• Similarly, 9, 10-epoxystearic acid is example of oxygenated fatty acid

D. Cyclic fatty acids:
• These are of rare occurrence. Chaulmoogra oil, obtained from the plant
Hydnocarpus kurzil and used in the treatment of leprosy, contains 2 such
acids hydnocarpic and chaulmoogric. Chaulmoogric acid has a
cyclopentenyl ring in its 18-carbon structure.
Functions of fatty acids:

• They are the constituents of phospholipids and glycolipids (component of

biological membranes).
• Fatty acids are fuel molecules. They are stored as triacylglycerols, which
are uncharged esters of glycerol.
• They provide physical protection for the organ of the body.
• Fatty acid derivatives such as prostaglandins, leukotrienes and
thromboxanes serve as local hormones and as a intracellular messenger in
cell signaling mechanism.
ESSENTIAL FATTY ACIDS
• Those polyunsaturated fatty acids (PUFA) that cannot be synthesized that
must be supplied through the diet are called essential fatty acids.
• Essential fatty acids for many species including man are
– Linoleic (ω6) acid
– linolenic(ω3) acid
– Arachidonic acid is also an essential fatty acid and it can be formed from
linoleic acid in most mammals.
Deficiency causes
– Scaly dermatitis
– Decreased availability of precursors for eicosanoid synthesis. (Eicosa
is the Greek word for the number 20)
– Affects fluidity of membrane structure.
– The ordinary dietary oils are rich in linoleic acid (ω6). The ω-3 type of
polyunsaturated fatty acids is produced by vegetation that grows in
cold water. Fish that feeds on these organisms contain large amounts of
ω-3 fatty acids. Hence, fish oils are richer in ω-3 type of fatty acids.
 Classification of Lipids Lipids

Simple Lipids B. Compound Lipids C. Derived Lipids

(HomoLipids) (HeteroLipids) (HydrolysisLipids)
1. Fats & Oils
(Triacylglycerols 1. Steroids
2. Glycolipids e.g.: Ergesterol &
1. Phospholipids Cholesterol
2. Waxes a. Gangliosides
2. Terpenes
b. Sulfolipids
c.Sulfatids 3.Carotenoids

. Phosphoglycerides b. Phosphoinositides c. Phosphosphingosides

1. Lecithins
i. Phosphatidyl ethanolamine
2. Cephalins
ii. Phosphatidyl Serine
3. Plasmalogens
 Classification of Lipids
 Based on their chemical composition, Lipids can be classified as;
A. Simple lipids
B. Compound lipids
C. Derived lipids

A. Simple lipids or Homolipids:

• These are esters of fatty acid with various alcohols.
1. Fats and oils (triglycerides, triacylglycerols):
• These are esters of fatty acids with a trihydroxy alcohol, glycerol.
• A fat is solid at ordinary room temperature whereas an oil is liquid.

2. Waxes:
• These are esters of fatty acids with high molecular weight monohydroxy
alcohols.
B. Compound lipids or Heterolipids:
• These are esters of fatty acids with alcohol and possess additional group(s)
also:
1. Phospholipids (phosphatids):
• These are compounds containing, in addition to fatty acids and glycerol, a
phosphoric acid, nitrogen bases and other substituent.
2. Glycolipids (cerebrosides):
• These are the compounds of fatty acids with carbohydrates and contain
nitrogen but no phosphoric acid.
• The glycolipids also include certain structurally-related compounds
comprising the groups, gangliosides, sulfolipids and sulfatids.

C. Derived lipids.
• These are the substances derived from simple and compound lipids
hydrolysis.
• These include fatty acids, alcohols, mono- and diglycerides, steroids,
terpenes and carotenoids.
A. Simple Lipids:
1. FATS AND OILS
( = Triglycerides or Triacylglycerols)
• The triglycerides are the most abundant of all lipids.
• They are the major components of storage or depot fats in plant and
animal cells but are not normally found in membranes.
• They are nonpolar, hydrophobic molecules since they contain no
electrically charged or highly polar functional groups.
• In animals, the fat cells or adipocytes contain very large quantities of
triglycerides in the form of fat droplets.
• Most animal fats such as those from meat, milk and eggs are relatively
rich in saturated fatty acids and exists in solid state.
• The plant fats, on the other hand, contain a large proportion of
unsaturated fatty acids (esp., polyunsaturated) and exists in liquid
state.
• Chemically, triglycerides are esters of glycerol with 3 fatty acid molecules.
Their generic formula is shown in Fig:

2. Waxes:
• These are esters of long-chain saturated and unsaturated fatty acids
with long-chain monohydroxy alcohols.
• The fatty acids range in between C14 and C36 and the alcohols range from
C16 to C30. Most of the waxes are mixtures of esters.
• Waxes are the chief storage form of metabolic fuel.
• Waxes serve as protective coat on fruits and leaves, which protects
against parasites and prevents excessive evaporation of water. The leaves
of many plants such as Rhododendron, Calotropis etc., are shiny because
of the deposition of protective waxy coating.
• Waxes are insoluble in water and provide a water barrier for animals such
as sheep.
• Birds such as waterfowl, secret waxes from their preen glands to make
their feathers water repellant.
• Biological waxes are used in the pharmaceutical industry in the
manufacturing of lotions, ointments and polishes. The waxes used are
lanolin (wool wax), bees wax, carnauba wax (palm tree wax) and
spermaceti oil (from whales).
• In vertebrates, waxes are secreted by cutaneous glands as a protective
coating.
• Thus, sperm whale wax (spermaceti) and beeswax are composed mainly
of palmitic acid esterified with either hexacosanol, or triacontanol.
• Moreover, sperm whale wax is also rich in cetyl palmitate and the
beeswax in myricyl palmitate.
B. COMPOUND LIPIDS:
1.PHOSPHOLIPIDS (= Phosphatids):
• Phospholipids are the most abundant membrane lipids.
• They serve primarily as structural components of membranes and are
never stored in large quantities.
• As their name implies, phospholipids contain phosphorus in the form of
phosphoric acid groups.
• They differ from triglycerides in possessing usually one hydrophilic polar
“head” group and usually two hydrophobic nonpolar “tails”.
• For this reason, they are often called polar lipids. Thus, phospholipids are
amphipathic, whereas the storage lipids (triglycerides and waxes) are not.
 Phospholipids are classified as;
1. Phosphoglycerides
2. Phosphoinositides
3. Phosphosphingosides
A. Phosphoglycerides:
• These are the major phospholipids found in membranes and contain two
fatty acid molecules or “tails” esterified to the first and second hydroxyl
groups of glycerol.
• The third hydroxyl group of glycerol forms an ester linkage with
phosphoric acid.
• In addition, phosphoglycerides contain a second alcohol, which is also
esterified to the phosporic acid.

• Based on second alcohol group, Phosphoglycerides are of following

types:
1. Lecithins
2. Cephalins
3. Plasmalogens
1. Lecithins (Phosphatidyl Cholines)

Fatty acid

Phosphoric acid

Fatty acid
Glycerol
Choline

• In addition to glycerol and 2 moles of fatty acids, the lecithins also

contain phosphoric acid and a nitrogen base choline at either the end or
middle carbon atom of glycerol unit.
• The lecithins are required for the normal transport and utilization of as
other lipids esp., in the liver of animals.
2. Cephalins:
 There are two types of cephalins:
a. Phosphatidyl ethanolamine b. Phosphatidyl serine

Phosphatidyl ethanolamine

Phosphatidyl Serine
3. Plasmalogens (=Phosphoglyceracetals):
• These resemble lecithins and cephalins but have one of the fatty acids
replaced by an unsaturated ether.
• Since the nitrogen base can be choline, ethanolamine or serine, three
types of plasmalogens are accordingly distinguished :
phosphatidal choline, phosphatidal ethanolamine and
phosphatidal serine.
B. Phosphoinositides (=Phosphatidyl inositols):
• These are phospholipids where a cyclic hexahydroxy alcohol called
inositol replaces base.
• On hydrolysis, the phosphoinositides yield 1 mole of glycerol, two moles
of fatty acid, 1 mole of inositol and 1, 2, or 3 moles of phosphoric acid.
• Accordingly, mono-, di- or triphosphoinositides are found.
• Phosphoinositides are also classified as glycolipids, in as much as they
contain carbohydrate residue.
C. Phosphosphingosides (=Sphingomyelins):
• These differ from other phospholipids in their lack of glycerol and the
presence of another nitrogenous base sphingosine or a closely related
dihydrosphingosine, besides choline, in place of glycerol.
• On hydrolysis, the phosphosphingosides yield equimolar amounts of
fatty acid, phosphoric acid, choline and sphingosine or
dihydrosphingosine but no glycerol.
2. GLYCOLIPIDS (= Cerebrosides or Glycosphingosides):
• The cerebrosides are important constituent of brain. These may also
occur in tissues other than brain.
• Like phospholipids, glycolipids are composed of a hydrophobic region,
containing 2 long hydrocarbon tails, and a polar region, which now
contains one or more sugar residues and no phosphate.
• These are of following types:
a. Gangliosides
b. Sulfolipids
c. Sulfatides
a. Gangliosides:
• A ganglioside is a molecule composed of a glycosphingolipid (ceramide
and oligosaccharide) with one or more sialic acids (e.g. n-
acetylneuraminic acid, NANA) linked on the sugar chain.
• These are found in significant concentrations in ganglion cells of nervous
tissue (hence so named) and also in most parenchymatous tissues like
spleen and erythrocytes.
• Gangliosides are thought to act as receptors for toxic agents like the
pathogens, Vibrio cholerae, Influenza virus and Tetanus toxin.
• Natural and semisynthetic gangliosides are considered possible
therapeutics for neurodegenerative disorders.

Structure of GM1 ganglioside

b. Sulfolipids:
• It is widely distributed in plants.
• Sulfolipids are a class of lipids which possess a sulfur-containing
functional group.
• An abundant sulfolipid is sulfoquinovosyl diacylglycerol, which is
composed of a glycoside of sulfoquinovose and diacylglycerol.
• In plants, sulfoquinovosyl diacylglycerides (SQDG) are important
members of the sulfur cycle.
c. Sulfatides:
• A sulfate ester analogue of phrenosin, abundant in white matter of brain,
is another sulfur-containing glycolipid.
• Sulfatide, also known as 3-O-sulfogalactosylceramide, SM4, or sulfated
galactocerebroside, is a class of sulfolipids, specifically a class of
sulfoglycolipids, which are glycolipids that contain a sulfate group.
• Sulfatide is synthesized primarily starting in the endoplasmic reticulum
and ending in the Golgi apparatus where ceramide is converted to
galactocerebroside and later sulfated to make sulfatide.
• Of all of the galactolipids that are found in the myelin sheath, one fifth of
them are sulfatide.
• Sulfatide is a multifunctional molecule important in several biological
functions of the immune system, hemostasis/thrombosis, nervous
system, cancer, microbial infections, and insulin secretion.
C. DERIVED LIPIDS:
 Derived lipids are of following types:
a. Steroids b. Terpenes C. Carotenoids

a. Steroids:
• These are widely found in animals and plants.
• The most important steroid is sterol ( steroid alcohol).

• In animals most commonly found steroid is cholesterol whereas in

plants Ergosterol, stigmasterol are found.
• Cholesterol is an important components of some cell membranes and of
plasma lipoproteins. It is also precursor of many other biologically
important steroids, such as bile acids and various steroid hormones.
• Ergosterol is present in ergot , yeast, and the mould Neurospora. It acts
as precursor of several types of vitamins.
 Fig : Structure of Steroid nucleus

Structure of Ergosterol Structure of Cholesterol

Cholesterol
•Cholesterol has steroid nucleus (cyclopentanoperhydrophenanthrene).
•The molecule contains 27 carbon atoms. There is one double bond between
carbon atom 5 and 6 and a hydroxyl group at position 3.
•A branch consisting of 8-carbon unit is attached to the D –ring at position 17.
Two methyl groups are attached at positions 10 and 13, constituting carbon
atom 19 and 18 respectively.
•It occurs in animal fats but not in plant fats.
•Cholesterol is amphipathic with a polar head group (hydroxyl group at C3) and
a non-polar hydrocarbon body.
•Much of the plasma cholesterol is in an esterified form, with a fatty acid
attached at C3, which makes the structure more hydrophobic.

Importance of cholesterol
•It is a constituent of membrane.
•It is the precursor of bile acids, steroid hormones and vitamin D.
•It is a component of lipoproteins.
•It is a poor conductor of heat, hence acts as an insulating material.
Bile salts:
• Cholesterol is not degraded to yield energy as there is no enzyme to
degrade the ring structure of cholesterol.
• They are eliminated from the body mostly in the form of bile acids, in
which the ring structure is intact.
Reactions
• Cholesterol is the converted to 7α-hydroxycholesterol by the enzyme 7-α-
hydroxylase. This reaction needs NADPH,O2 and Vit-C.
• In the subsequent step, the double bond is reduced; the side chain is
oxidized and converted to a five carbon branch possessing a carboxyl
group at the end, followed by hydroxylation to form two compounds.
• One has hydroxyl group at positions 3 and 7 and the other at positions 3,7
& 12, namely chenodeoxycholic acid and cholic acid respectively. These
compounds are called primary bile acids ( they are produced in the liver).
• They are then conjugated to a molecule of glycine or taurine by an amide
bond. These new structures are called as bile salts and they are
• Glycocholic acid
• Glycochenodeoxycholic acid
• Taurocholic acid
• Taurochenodeoxycholic acid.
• The bile salts are then transported to the intestine via the bile.
• Bacteria in the intestine can remove glycine and taurine from the bile
salts.
• Some of the primary acids are also converted into secondary bile acids by
removing a hydroxyl group attached at carbon 7, producing deoxycholic
acid from cholic acid and lithocholic acid from chenodeoxycholic acid.
• About 94% of the bile salts are reabsorbed and returns to liver by
enterohepatic circulation and 6% is lost in the feces.
Function:
• Bile salts lower surface tension and are required for digestion and
absorption of lipids.
Prostaglandin:
•The prostaglandins (PG) are a group of physiologically active lipid
compounds called eicosanoids having diverse hormone-like effects in
animals.
•Prostaglandins have been found in almost every tissue in humans and other
animals. They are derived enzymatically from the fatty acid arachidonic acid.
Function
•The prostaglandins are a group of lipids made at sites of tissue damage or
infection that are involved in dealing with injury and illness.
•They control processes such as inflammation, blood flow, the formation of
blood clots and the induction of labour.
b. Terpenes:
• Terpenes are a large and diverse class of organic compounds, produced by
a variety of plants, particularly conifers, and by some insects. Terpenes
are hydrocarbons.
• Terpenoids (or isoprenoids) are modified terpenes as they contain
additional functional groups, usually oxygen-containing. Vitamin A is a
terpenoid.
• Terpenes are the major components of rosin and of turpentine produced
from resin.
• The extraction of terpenes and terpenoids from natural sources is often
problematic.
• Terpenes are made up of Isoprenoid unit which is also called as Isoprene.
• Isoprene does not occur freely in nature. Its biologically active counter
part which is known as isopentenyl pyrophosphate formed from
mevalonic acid is found.
• Terpenes have desirable properties for use in food, cosmetics,
pharmaceutical and biotechnology industries.
• Terpenes may be classified by the number of isoprene units in the
molecule.
General structure of a carotenoid
C. Carotenoids:
• Carotenoids (also called tetraterpenoids) are yellow, orange, and red
organic pigments that are produced by plants and algae, several bacteria,
and fungi, aphids, and spider mites.
• Carotenoids give the characteristic color to pumpkins, carrots, corn,
tomatoes, canaries, flamingos, salmon, lobster, shrimp, and daffodils.
• Carotenoids from the diet are stored in the fatty tissues of animals, and
exclusively carnivorous animals obtain the compounds from animal fat.
• There are over 1,100 known carotenoids which can be further categorized
into two classes, xanthophylls (which contain oxygen) and carotenes
(which are purely hydrocarbons and contain no oxygen).
• Carotenoids are derivatives of tetraterpenes, meaning that they are
produced from 8 isoprene molecules and contain 40 carbon atoms.
• They are isoprene derivatives with a high degree of unsaturation.
• Because of the presence of many conjugated double bonds, they are
colored red or yellow.
• Most important carotenoid is beta-carotene. Beta-carotene is cleaved in
the intestinal mucosa cells to form retinol (Vitamin-A)
 Functions of Lipids
 The lipids perform a wide variety of functions. These are briefly listed
below:
1. Food material:
• Lipids provide food, highly rich in calorific value. One gram lipid produces
9.3 kilocalories of heat.
2. Food reserve.
• Lipids provide are insoluble in aqueous solutions and hence can be stored
readily in the body as a food reserve.
3. Structural component.
• Lipids are an important constituent of the cell membrance.
4. Heat insulation
• The fats are characterized for their high insulating capacity. Great
quantities of fat are deposited in the subcutaneous layers in aquatic
mammals such as whale and in animals living in cold climates.
5. Fatty acid absorption:
• Phospholipids play an important role in the absorption and transportation
of fatty acids.
6. Hormone synthesis:
• The sex hormones, adrenocorticoids, cholic acids and also vitamin D are
all synthesized from cholesterol, a steroidal lipid.
7. Vitamin carriers:
• Lipids act as carriers of natural fat-soluble vitamins such as vitamin A, D
and E.
8. Antibiotic agent:
• Squalamine, a steroid from the blood of sharks, has been shown to be an
antibiotic and antifungal agent of intense activity.
9. Electrical & heat insulator: