UNIT -II
Fatty Acids
• Fatty acids are comprised of hydrocarbon
chains terminating with carboxylic acid
groups.
• Fatty acids and their associated derivatives
are the primary components of lipids.
• The length and degree of saturation of the
hydrocarbon chain is highly variable
between each fatty acid, and dictates the
associated physical properties (e.g., melting
point and fluidity).
• Moreover, fatty acids are responsible for the
hydrophobic properties (insoluble in water)
exhibited by lipids.
• These are monocarboxylic, straight,
unbranched hydrocarbon chains
containing even number of carbon atoms
(betweeen 4- 36)
• Fatty acids are also known as acyl group
when it is a part of ester.
• Fatty acids are amphipathic in nature.
• The fatty acids may be free or esterified
with glycerol to form triglycerides.
• Palmitic acid and stearic acid – most
common
Structure of Fatty Acids
FATTY ACIDS - NOMENCLATURE Trivial, IUPAC, Carboxyl reference, Omega reference
• Thenaming of a fatty acid (systematic name) is based on
the hydrocarbon from which it is derived.

• The saturated fatty acids end with a suffix -anoic (e.g.,

octanoic acid) while the unsaturated fatty acids end with a
suffix -enoic (e.g., octadecanoic acid).

• Numbered from the carboxyl carbon (carbon No. 1)

•the carbon atom situated next to the carboxyl group is
termed the “α” carbon, followed by the “β” carbon, etc.
• ∆ for indicating the number and position of the double
bond
• Terminal methyl carbon is known as the ω or n-carbon.
ω9 indicates a double bond on the ninth carbon counting
from the ω- carbon
Depending on the length of carbon chains, fatty acids are
categorized into 3 groups—short chain with less than 6
carbons; medium chain with 8 to 14 carbons and long chain
There are other conventions of
with 16 to 24 carbons.
representing the double bonds. Δ9
indicates that the double bond is
between 9 and 10 of the fatty acid.

Shorthand representation of fatty acids ω9 represents the double bond position

Instead of writing the full structures, biochemists employ (9 and 10) from the ω end.
shorthand notations (by numbers) to represent fatty
acids. The general rule is that the total number of carbon Naturally occurring unsaturated
atoms are written first, followed by the number of fatty acids belong to ω9, ω6 and ω3
double bonds and series.
finally the (first carbon) position of double bonds,
starting from the carboxyl end.
Thus, saturated fatty acid,
palmitic acid as 16 : 0,
oleic acid as 18: 1; 9,
arachidonic acid as 20 : 4; 5, 8, 11, 14.
CLASSIFICATION OF FA

Fatty acids differ from each other in

a) length of hydrocarbon tail,
b) degree of unsaturation,
c) position of double bonds in the
chain.
Short-chain fatty acids like acetic ,
propionic and butyric acids are
intermediates in metabolism.
The fatty acids that cannot be synthesized by the body and,
therefore, should be supplied in the diet are known as
essential fatty acids (EFA).

Chemically, they are polyunsaturated fatty acids, namely

linoleic acid (18 : 2; 9, 12) omega-6 and
linolenic acid (18 : 3; 9, 12, 15). omega-3.
These FA contain double bonds beyond the ninth carbon and there is no human enzyme
systems that can introduce a double bond ninth carbon atom of FA chain.

Omega-3 and omega-6 fatty acids are precursors to important compounds called eicosanoids.
Eicosanoids are powerful hormones that control many other hormones and important body functions, such as the
central nervous system and the immune system.

Eicosanoids derived from omega-6 fatty acids are known to increase blood pressure, immune response, and
inflammation.

In contrast, eicosanoids derived from omega-3 fatty acids are known to have heart-healthy effects. Given the
contrasting effects of the omega-3 and omega-6 fatty acids, a proper dietary balance between the two must be
achieved to ensure optimal health benefits.
WHY ESSENTIAL FATTY ACIDS CAN NOT BE SYNTHESIZED IN BODY
These two fatty acids cannot be synthesized by humans
because humans lack the desaturase enzymes required for their
production. Humans have C 9,6,5,4 desaturases but lack the
ability to introduce double bonds from C 10 to ω end of the
chain.
They form the starting point for the creation of more
desaturated fatty acids, most of which also have a longer
carbon chain:
ω-6 fatty acids:

ω-3 fatty acids:

Essential fatty acids play an important role in the life

and death of cardiac cells, immune system function,
and blood pressure regulation.
Docosahexaenoic acid (DHA) is an omega-3 essential Some excellent sources of omega-3 * ω-9 fatty acids are not
fatty acid shown to play important roles in synaptic essential in humans because
and omega-6 essential fatty acids they can be synthesized from
transmission in the brain during fetal development are fish, flaxseed oil, hemp, walnuts, carbohydrates or other fatty
and leafy vegetables acids.
The molecular formula of a saturated fatty acid is CnH2n+1COOH e.g. palmitic acid is C15H31COOH.

Higher melting point Butyric acid (4), Caproic

Solid at room temperature
acid (6) Caprylic acid (8)
Capric acid (10), Laurie acid
(12), Myristic acid (14),
Palmitic acid, (16) Stearic
acid (18), Arachidic acid
(20)

Low melting point General formula Cn H2n–1 COOH

Liquid at room temperature
Isomerism in unsaturated fatty acids
Unsaturated fatty acids exhibit geometric isomerism
depending on the orientation of the groups around the
double bond axis.

In the cis isomeric form, there is a molecular binding at

the double bond.
Thus, oleic acid exists in an L-shape while elaidic acid is a
straight chain.
Increase in the number of double bonds will cause more
bends (kinks) and arachidonic acid with 4 double bonds
will have a U-shape.
It is believed that cis isomers of fatty acids with their
characteristic bonds will compactly pack the membrane
structure.
• Non polar, Hydrophobic and major form of stored lipid.
Adipocytes of adipose tissue—predominantly found in the subcutaneous layer
and in the abdominal cavity—are specialized for storage of triacylglycerols.
• The fat is stored in the form of globules dispersed in the entire cytoplasm.
• No charge , also referred as neutral fats. (COOH-glycerol
covalent bonded
• Two types: simple and mixed
 Eg: tripalmitin, tristearin

Eg. oleodipalmitin and oleopalmitostearin

Physical Properties of FA
SOLUBILITY IN WATER
Solubility in water decreases with increase in chain
length and degree of unsaturation of the fatty acids.
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. Except acetic acid , all other fatty acids are
lighter than water.
MELTING (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 acids12:0 to 24:0 have a waxy consistency at R.T.
while unsaturated fatty acids of the same chain length
are oily liquids . Fats containing fatty acids 18:2 are
liquid below 0 oC.
*The length and degree of unsaturation of the hydrocarbon chain
determines many of the properties of the fatty acids
ISOMERISM
The presence of double bonds in the fatty acid chain
results in the existence of isomers. Cis isomers are
common in nature but unstable, while trans isomers are
less common but more stable. Most fatty acids in our body
are of the cis type. Trans fatty acids are common in the
triglycerides of dairy and meat products, and in partially
hydrogenated oils. Saturated fatty
acids like stearic acid, and unsaturated fatty acids with
trans bonds, have linear shapes but the presence of a cis
double bond bends the shape of the molecule
AMPHIPATHIC NATURE
The carboxylic ends of fatty acid molecules are hydrophilic
and react with the cellular environment, while the ‘R’
chains are hydrophobic and interact with each other. This
amphipathic nature is important in the formation and
function of micelles and membranes.
* 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.
Esterification
 Fats are characterized (purity check) or otherwise assessed by determining
CHARACTERIZATION OF FATS certain chemical constants for individual fats-

SAPONIFICATION NUMBER REICHERT – MEISSL (RM) NUMBER

It is defined as the mg (number) of KOH required to hydrolyse
(saponify) one gram of fat or oil. A high saponification number
indicates that the fat is made up of low molecular weight
fatty acids (short chain FA) and vice versa.
Human fat 195–200
Butter 230–240
Coconut oil 250–260
IODINE NUMBER
The number ( gms) of Iodine required to saturate 100
gms of a fat. Since Iodine is taken up by the double bonds, a
high iodine number indicates a high degree of unsaturation
of the fatty acids of the fat.
Coconut oil 7 — 10
Sunflower oil 125 — 135
ACID NUMBER
Number of mgs of KOH required to neutralize the free
fatty acids in a gm of fat is known as acid number . The
acid number indicates the degree of rancidity of the
given fat.
The number of mls of 0.1N alkali (KOH)required to neutralize
the soluble volatile fatty acids(saponification, acidification and
steam distillation of the fat) distilled from 5 g fat.
RM number is useful in testing the purity of butter since it
contains a good concentration of volatile fatty acids (butyric
acid, caproic acid and caprylic acid). This is in contrast to other
fats and oils which have a negligible amount of volatile fatty
acids. Butter has a RM number in the range 25-30, while it is
less than 1 for most other edible oils. Thus any adulteration of
butter can be easily tested by this sensitive RM number.
*Polenske number -It is the number of milliliters of 0.1N KOH
required to neutralize the insoluble fatty acids(those which are
not volatile with steam distillation) obtained from 5 gm. of fat.
*Acetyl number-It is the number of milligrams of KOH
required to neutralize the acetic acid obtained by
saponification of 1 gm of fat after it has been acetylated.
measure of the number of OH groups in the fat
 Waxes:
Waxes are part of the lipid family.

Waxes are esters of long-chain saturated and unsaturated fatty acids (having 14- 36
carbon atoms) with long-chain of monohydroxy alcohol(having 16-30 carbon atoms).

Waxes are low- melting, stable solids which appear in nature in both plants and
animals. A wax coat protects surface of many plant leaves from water loss and attack by
microorganisms.

Most of the waxes are mixtures of esters.

Thus, sperm whale wax (spermaceti) and beeswax are composed mainly of palmitic acid
esterified with either hexacosanol, CH3(CH2)24.CH2OH or triacontanol, CH3(CH2)28.CH2OH.
 Waxes are unusually inert due to their saturated nature of the hydrocarbon chain.
However, they can be split slowly with hot alcoholic KOH.

They are insoluble in water and highly resistant to atmospheric oxidation. Hence, these are
used in polishing furnitures and automobiles and also in wax-coated paper used to wrap
perishable food products such as biscuits, cakes, etc. Lanolin (from lamb's wool), beeswax
(from honeycomb), carnauba wax (from a Brazilian palm tree) and spermaceti oil (from
sperm whales) are widely used in the manufacture of lotions, ointments and polishes.

In vertebrates, waxes are secreted by cutaneous glands as a protective coating to keep

the skin pliable, lubricated and water-proof. Hair, wool and fur are also coated with wax.

Birds, particularly waterfowl, secrete waxes in their preen glands to make their feathers
water-repellent. The leaves of many plants such as Rhododendron, Calotropis etc., are
shiny because of the deposition of protective waxy coating.

Waxes also serve as the chief storage form of fuel in planktons. Since marine organisms
(whale, herring, salmon) consume planktons in large quantities, waxes act as major food
and storage lipids in them.
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.
i.
Glycerides and cholesterol esters, because of their uncharged nature,
are also called neutral lipids.

However, Conn and Stumpf (1976) have traditionally classified lipids

into following 6 classes :
1. Acyl glycerols
2. Waxes
3. Phospholipids
4. Sphingolipids
5. Glycolipids
6. Terpenoid lipids including carotenoids and steroids
 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, in addition to
fatty acids, nitrogenous base and
alcohol.

• 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.

• 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 phosphate is further linked to one of
a variety of small polar head groups (alcohols).

There are two classes of phospholipids

1. Glycerophospholipids (or phosphoglycerides) that contain glycerol as the alcohol.
2. Sphingophospholipids (or sphingomyelins) that contain sphingosine as the alcohol.
 Phosphotidylethanolamine

Phosphotidylcholine
Ether lipid
Sphingosine is an amino alcohol present in
sphingomyelins (sphingophospholipids). They
do not contain glycerol at all.

Sphingomyleins are located throughout the

body in nerve cell membranes. They make up
about 25 % of the lipids in the myelin sheath
that surrounds and insulates cells of the
central nervous system
Functions of phospholipids
1. In association with proteins, phospholipids form the structural components of
membranes and regulate membrane permeability.

2. Phospholipids (lecithin, cephalin and cardiolipin) in the mitochondria maintain

the conformation of electron transport chain components, and thus cellular
respiration.

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

4. Phospholipids are essential for the synthesis of different lipoproteins, and thus
participate in the transport of lipids.

5. Accumulation of fat in liver (fatty liver) can be prevented by phospholipids,

hence they are regarded as lipotropic factors.
6. Arachidonic acid, an unsaturated fatty acid liberated from phospholipids, serves as a
precursor for the synthesis of eicosanoids (prostaglandins, prostacyclins, thromboxanes
etc.).

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

8. Phospholipids act as surfactants (agents lowering surface tension). For instance,

dipalmitoyl phosphatidylcholine is an important lung surfactant.
Respiratory distress syndrome in infants is associated with insufficient production of this
surfactant.

9. Cephalins, an important group of phospholipids participate in blood clotting.

10. Phosphatidylinositol is the source of second messengers—inositol triphosphate and

diacylglyceol, that are involved in the action of some hormones.

GLYCOLIPIDS
• Glycolipids are glycoconjugates of lipids.
• The term glycolipid designates any compound
containing one or more monosaccharide residues
bound by a glycosidic linkage .
• It is a structural lipid . Glycolipids are biomolecular
structures in the phospholipid bilayer of the cell
membrane whose carbohydrate component
extends to the outside of the cell.
The basic structure of a glycolipid consists of a mono-
or oligosaccharide group attached to a sphingolipid
or a glycerol group (can be acetylated or alkylated)
with one or two fatty acids.
These make up the classes of glycosphingolipids and
glycoglycerolipids, respectively.
Glycolipids interact and bind to the lipid-bilayer
through the hydrophobic nature of the lipid tail which
anchors it to the surface of the plasma membrane.

• Glycolipids are essential in providing stability of the

plasma membrane.
• Furthermore, they are also associated with cell to
cell interactions, e.g. cell adhesion to form a tissue.

• They also facilitate cellular recognition, which is

important in immunologic functions.
 Types of Glycolipids
1. Cerebrosides- Cerebroside (from cerebro=brain) are
glycolipids that are found primarily in the brain and
peripheral (other areas of the body) nervous tissue.
Cerebrosides are the simplest form of glycolipids. They
contain a ceramide (sphingosine attached to a fatty acid) Structure of galactosylceramide
and one or more sugars. For sulfagalactosylceramide R is a
Function: Provide protective coating to each nerve and act sulfatide .
as insulator.
Ceramide +glucose ---- Glucocerebroside
2. Gangliosides- predominantly found in ganglions and are Ceramide +galactose ---- Galactocerebroside
the most complex form of
glycosphingolipids.. The gangliosides are acidic in pH.
They are the derivatives of cerebrosides and contain one or
more molecules of N-acetylneuraminic acid (NANA), the 3. Sulfoglycosphingolipids- These cerebrosides
most imp Sialic acid. are also called sulfatides, They are simply
The most important gangliosides present in the brain are cerebrosides with a sulfate residue on the sugar
GM1, GM2, GD, and GT, (G represents ganglioside while M, portion of glycolipid.
D and T indicate mono-, di-or tri-sialic acid residues, and the Occurrence: this particular lipid is found primarily
number denotes the carbohydrate sequence attached to in the medulated nerve fibres.
the ceramide).
Classification of complex lipids
LIPOPROTEINS

A lipoprotein is a biochemical assembly that

contains both proteins and lipids , bound to the
proteins , which allow fats to move through the
water inside and outside cells.
Lipoproteins with high lipid content will have low density, larger size
and so float on centrifugation. Those with high protein content
sediment easily, have compact size and have a high density
present
Derived LIPIDS This system consists of 3 cyclohexane rings (A, B and C)
It includes the hydrolysis products of fused in nonlinear or phenanthrene manner and a
simple and compound lipids and also terminal cyclopentane ring (D). The sterane nucleus
various other compounds such as along with the conventional numbering of the carbon
steroids, terpenes, fatty acids, alcohols, atoms
fatty aldehydes, ketones etc.
STEROIDS
Steroids are a third type of lipids found in the
membranes of eukaryotes, and, very rarely, in
bacteria.
Steroids, along with lipid vitamins and
terpenes, are classified as isoprenoids because
their structures are related to the five carbon
molecule isoprene.
Steroids contain four fused rings: three six-
carbon rings designated A, B, and C and a five-
carbon D ring.
All steroids may be considered as derivatives of a fused and fully saturated
ring system called cyclopentanoperhydrophenanthrene or sterane.
 Cholesterol is undoubtedly the most publicized lipid in nature,
because of the strong correlation between high levels of
cholesterol in the blood and the incidence of diseases of the
cardiovascular system in humans.
It is not only an important component of some cell
membranes and of plasma lipoproteins but also the precursor
of many other biologically important steroids, such as bile acids
and various steroid hormones.

It is the principal sterol of higher animals and is especially

abundant in nerve tissues and in gallstones. It occurs either
free or as fatty esters in all animal cells. It was first isolated in
1784, from human gallstones which consist almost entirely of
cholesterol and hence so named (cholesterol literally means
‘solid alcohol from bile’).
Its main sources are fish liver oils and the brain and spinal cord
of cattle. White matter contains as much as 14%, gray matter
5%, spinal ord 12% and liver about 1% cholesterol.

Cholesterol is , however, not found in plant fats. Its parent

hydrocarbon is cholestane, C27H48. The structure of cholesterol
was determined by the German chemist, Adolph Windaus
(1879 − 1959), who received 1928 Nobel Prize in Chemistry.
Cholesterol has a molecular formula, C27H45OH.
(C27H46O)
 o

Test for cholesterol

Salkowski's test,, Liebermann-Burchard reaction and Zak's test.
Properties of Ketone Bodies

1. They are water soluble substances.

2. They are synthesized at a relatively low rate in well
nourished individuals.
3. Plasma level of ketone bodies < 1mg/dl. 4. Urinary
level of ketone bodies <3 mg/24 hour urine.
4. Acetone is synthesized in smaller amounts than
other ketone bodies. It is a non-metabolized end
product. It is a volatile substance that is excreted by
the lungs in the expired air.