Lipids

Lipids are heterogeneous group of

compounds, which are related more
by their physical than by their
chemical properties.
Lipids are biological molecules that
are insoluble in aqueous solutions but
soluble in organic/ non-polar solvents
such as hydrocarbons, chloroform,
benzene, ethers and alcohols.

 Lipids constitute a broad group of

naturally occurring molecules that
include fats, waxes, glycerides,
phospholipids, sphingolipids, sterols
and related compounds

CLASSES OF LIPIDS
Simple lipids are defined as esters of
fatty acids with various alcohols. On
hydrolysis they yield at most two types
of primary product per mole. Examples
are fats, oils and waxes.
Fats: Esters of fatty acids with glycerol.
Oils: are fats in the liquid state.
Waxes: Esters of fatty acids with higher
molecular weight monohydric alcohols.

 Complex lipids: Esters of fatty acids

containing
groups in addition to an alcohol and a
fatty acid. They yield three or more
primary hydrolysis products per molecule.
Examples
are
phospholipids,
sphingolipids, glycolipids,
lipoproteins,
sulfolipids and aminolipids..
Phospholipids: Lipids containing, in
addition
to fatty acids and an alcohol, a phosphoric
acid residue.

 They frequently have nitrogen containing

bases and other substituents, eg, in
glycerophospholipids the alcohol is
glycerol
and in sphingophospholipids the
alcohol is
sphingosine.
Glycolipids (glycosphingolipids):
Lipids
containing a fatty acid, sphingosine, and
carbohydrate.

Fatty acid as building blocks

of complex lipids

Classes of lipids contd

Precursor and derived lipids: These

include fatty acids, glycerol, steroids,
other alcohols, fatty aldehydes, ketone
bodies, hydrocarbons,
lipid-soluble vitamins, and hormones.

Because they are uncharged, acylglycerols

(glycerides), cholesterol, and cholesteryl
esters are termed neutral lipids.

 In general, lipids are insoluble in water since

they contain a predominance of nonpolar
(hydrocarbon) groups.
However, in some lipids, part of the molecule
is hydrophobic or water-insoluble; and part
is hydrophilic or water-soluble. Such
molecules are described as amphipathic.
They become oriented at oil:water interfaces
with the polar group in the water phase and
the nonpolar group in the oil phase. They
interact with other molecules and with
aqueous solvents via hydrogen bonding and
electrostatic interactions

Common lipids:
Fats: These are three fatty acids
linked to an ester of glycerol. They can
be saturated or unsaturated.

Waxes: are similar to fats but are

composed of much longer fatty acids.
Molecular attractions between fatty
acid chains accounts for their higher
melting point.

Phospholipids: are similar to fats but

one of the fatty acid groups is replaced
by a phosphate group. The structure of
this lipid gives it the amphipathic
properties. The ester of glycerol is
hydrophilic but the fatty acid chains are
hydrophobic.
Steroids: Steroids have a four carbon
ring structure and a high hydrogen to
carbon ratio. Examples of steroids
include cholesterol and hormones like
testosterone and oestrogen.

Fatty acids

The fatty acid structure is one of the

most
fundamental
categories
of
biological lipids, and is commonly used
as a building block of more structurally
complex lipids.
Fatty acids occur mainly as esters in
natural fats and oils but do occur in the
unesterified form as free fatty acids,
a transport form found in the plasma.

 Fatty acids are long-chain organic acids

having 2 to 24 carbon atoms with a single
carboxyl group and a long non-polar
hydrocarbon tail which gives most lipids
their water insoluble and oily or greasy
nature.
Fatty acids are straight chain hydrocarbons
possessing a carboxyl (COOH) group at one
end. The carbon next to the carboxylate is
known as , the next carbon , and so forth.
Since biological fatty acids can be of
different lengths, the last position is labelled
as a "", the last letter in the Greek
alphabet.

 Fatty acids that occur in natural fats

are usually straight-chain derivatives
containing an even number of carbon
atoms.
The chain may be saturated
(containing no double
bonds) or unsaturated (containing
one or more double bonds).

General Structure of Fatty

Acid

Carboxylic acid head group shown in red

Hydrocarbon tail shown in black

Types of fatty acids

Fatty acids can be saturated and
unsaturated, depending on double bonds.
fatty acids have different lengths, often
categorized as short, medium, or long.
Short-chain fatty acids (SCFA) are fatty
acids with aliphatic tails of fewer than six
carbons.
Medium-chain fatty acids (MCFA) are
fatty acids with aliphatic tails of 612
carbons.

Types of fatty acids

Long-chain fatty acids (LCFA) are
fatty acids with aliphatic tails longer
than 12 carbons.
Very-Long-chain fatty acids
(VLCFA) are fatty acids with aliphatic
tails longer than 22 carbons.

Saturated fatty acids

Saturated fatty acids are long-chain
carboxylic acids that have no double bonds.
Each carbon atom within the chain has 2
hydrogen atoms (except for the omega
carbon at the end that has 3 hydrogens).
Saturated fatty acids of less than 8 carbon
atoms
are
liquid
at
physiological
temperature, whereas those containing
more than ten are solid. An unsaturated fat
can be made into saturated fat through
Hydrogenation reaction.

Palmitic Acid 16:0

EXAMPLES OF SATURATED FATTY

ACIDS
Common
12:
Formular
name
0
CH3(CH2)10COO
Lauric acid
12:0
H
CH3(CH2)12COO
Myristic acid
14:0
H
CH3(CH2)14COO
Palmitic acid
16:0
H
CH3(CH2)16COO
Stearic acid
18:0

Unsaturated fatty acids

Unsaturated fatty acids resemble saturated
fatty acids, except that the chain has one
or more double-bonds between carbon
atoms.
The site of unsaturation is indicated by the
symbol
The two carbon atoms in the chain that are
bound next to either side of the double
bond can occur in a cis or trans
configuration.

Types of unsaturation
(1) Monounsaturated acids,
containing one double bond.
(2) Polyunsaturated acids,
containing two or more double
bonds.

Some important fatty acids

Saturated and unsaturated

f/acid
The melting point of fatty acids
increases as the number of carbon
atoms increases.
The
introduction
of
sites
of
unsaturation results in lower melting
points when comparing a saturated
and an unsaturated fatty acid of the
same number of carbons.

Unsaturated fatty acid

the physiological properties of
unsaturated fatty acids largely depend
on the position of the first unsaturation
relative to the end position and not the
carboxylate, the position is signified by
( minus n). For example, the term -3
signifies that the first double bond exists
as the third carbon-carbon bond from the
terminal CH3 end () of the carbon chain

Unsaturated fatty acid

contd
The number of carbons and the
number of double bonds is also
listed. -3 18:4 (stearidonic acid) or
18:4 -3 or 18:4 n3 indicates an
18-carbon chain with 4 double bonds,
and with the first double bond in the
third position from the CH3 end

Examples of Unsaturated fatty

acids
Common
name

Formula

Numer
ical
symbo
l

Palmitoleic
acid

CH3(CH2)5CH=CH(CH2)7COOH

16:1

Oleic acid

CH3(CH2)7CH=CH(CH2)7COOH

18:1

Linoleic
acid

CH3(CH2)4CH=CHCH2CH=CH( 18:2
9,12
CH2)7COOH

Linolenic
acid

CH3CH2CH=CHCH2CH=CHCH2 18:3
9.12.15
CH=CH(CH2)7COOH

Arachidoni

CH3(CH2)4CH=CHCH2CH=CHC 20:4

Unsaturated fatty acids

Most Naturally Occurring Unsaturated
Fatty Acids Have cis Double Bonds
The carbon chains of saturated fatty acids
form a zigzag pattern when extended at
low temperatures. At higher temperatures,
some bonds rotate, causing chain
shortening, which explains why
biomembranes become thinner with
increases in temperature.

Unsaturated fatty acids of physiologic

and
nutritional
significance.

Monoenoic acids (one double bond)

16:1;9 7 Palmitoleic In nearly all fats.
18:1;9 9 Oleic Possibly the most
common fatty acid in natural fats.
18:1;9 9 Elaidic Hydrogenated and
ruminant fats.
Dienoic acids (two double bonds)
18:2;9,12 6 Linoleic Corn, peanut,
cottonseed, soybean and many plant
oils.

 Trienoic acids (three double bonds)

18:3;6,9,12 6 -Linoleic Some plants,
eg, oil of evening primrose, borage oil;
minor fatty acid in animals.
18:3;9,12,15 3 -Linolenic Frequently
found with linoleic acid but particularly
in linseed oil.
Tetraenoic acids (four double
bonds)
20:4;5,8,11,14 6 Arachidonic Found
in animal fats and in peanut oil.

Fatty acid and nutrition

Essential fatty acids: linoleic and linolenic fatty
acids;
Good fats: high in polyunsaturated fats.
Typical foods include vegetable oils, like olive,
canola, sunflower, etc.
Bad fats: high in saturated fats. stearic
(beef); palm and coconut oils (found in candy)
Really bad fats: trans fatty acids; result from
partial hydrogenation of vegetable oils.
Margarine has trans fatty acids- difficult to
metabolize; lead to increased cholesterol levels
in the blood

Geometric isomerism
A type of geometric isomerism
occurs in unsaturated fatty acids,
depending on the orientation of atoms
or groups around the axes of double
bonds, which do not allow rotation. If
the acyl chains are on the same side of
the bond, it is cis-, as in oleic acid; if on
opposite sides, it is trans-, as in elaidic
acid, the trans isomer of oleic acid

Configuration
A cis configuration means that
adjacent hydrogen atoms are on the
same side of the double bond. The
more double bonds the chain has in
the cis configuration, the less flexibility
it is. For example, oleic acid, with one
double bond, has a "kink" in it,
whereas linoleic acid, with two double
bonds, has a more pronounced bend.
Alpha-linolenic acid, with three double
bonds, favours a hooked shape.

Configuration contd
cis bonds limit the ability of fatty acids
to be closely packed, and therefore
could affect the melting temperature
of the membrane or of the fat.
A trans configuration, by contrast,
means that the next two hydrogen
atoms are bound to opposite sides of
the double bond. Their shape is similar
to straight saturated fatty acids.

Configuration contd
Most fatty acids in the trans
configuration are not found in nature
and are the result of human
processing (e.g. hydrogenation).
Trans fatty acids are produced by
fermentation in the rumen of dairy
animals
and are obtained from dairy products
and meat.

Trans and Cis configuration

Orientation of cis and trans

configuration

ESSENTIAL FATTY ACIDS

Fatty acids that are required by the body
but cannot be made in sufficient quantity
from other substrates, therefore must be
obtained from food are called essential fatty
acids. Mammals lack the ability to introduce
double bonds in fatty acids beyond carbon 9
and 10, hence -6 linoleic acid (18:2,9,12),
abbreviated LA, and the -3 linolenic acid
(18:3,9,12,15), abbreviated ALA, are
essential for man in the diet.

Essential fatty acids

In humans, arachidonic acid
(20:4,5,8,11,14) can be synthesized
from LA by desaturation and chain
elongation (though some carnivores
like cats cannot do this, and require
arachadonate in the diet).

 Animal tissues have limited capacity for

desaturating fatty acids, and that
process
requires
certain
dietary
polyunsaturated fatty acids derived
from plants.
Other C20, C22, and C24 polyenoic fatty
acids may be derived from oleic,
linoleic, and linolenic acids by chain
elongation. Palmitoleic and oleic acids
are not essential in the diet because the
tissues can introduce a double bond at
the 9 position of a saturated fatty acid.

Omega -3 and 6 fatty acids

The essential fatty acids start with the short
chain polyunsaturated fatty acids (SCPUFA):
-3 fatty acids: -Linolenic acid or ALA
(18:3)
-6 fatty acids: Linoleic acid or LA (18:2)
These two fatty acids cannot be synthesised
by humans, as humans lack the desaturase
enzymes required for their production.

 Linoleic and linolenic acids are

the only fatty acids known to be
essential for the complete nutrition
of many species of animals, including
humans, and are known as the
nutritionally essential fatty
acids.

Linolenic acid

TRIACYLGLYCEROLS

They are the main storage forms of

fatty acids
These are esters of glycerol and fatty acids.
Fatty acids can be linked to glycerol to form
monoacylglycerols, diacylglycerides and
triacylglycerides.
The most well-known being the fatty acid
esters of glycerol (triacylglycerols), also
known
as
triglycerides.
In
these
compounds, the three hydroxyl groups of
glycerol are each esterified, usually by
different fatty acids.

Triacylglycerols
They
are
nonpolar,
hydrophobic
molecules, since they contain no
electrically charged or highly polar
functional groups. The polar hydroxyls of
glycerol and the polar carboxylates of the
fatty acids are bound in ester linkages.
The hydrolysis of the ester bonds of
triacylglycerols and the release of
glycerol and fatty acids from adipose
tissue is called fat mobilization.

Basic composition of
Triglyceride

PHOSPHOGLYCERIDE
One class of phospholipids are the
phosphoglycerides, which are made
from diacylglycerides linked to a
phosphate group. Phosphoglycerides
usually have the following arrangement:
Hydroxyl No 1 of glycerol is usually
esterified to a saturated fatty acid
Hydroxyl No 2 of glycerol is usually
esterified to an unsaturated fatty acid
Hydroxyl No 3 of glycerol is esterified to
a phosphate group

Basic composition of
phospholipids

Sphingolipids
Sphingolipids, have the same shape as
phosphoglycerides but have different
chemistry, using sphingosine in place of
glycerol.
Sphingosine
has
a
long
hydrocarbon tail similar to fatty acids
attached to a structure that is similar to
the amino acid serine. A fatty acid can
attach to the amine group, and a "head"
group can attach to a hydroxyl.
Sphingolipids are named according to this
head group:

 If there is no head group it is called a

ceramide
If the head group is phosphate and
choline, it is called sphingomyelin
If the head group is a sugar, it is called
a glycosphingolipid (or a glycolipid)
Sphingolipids are a complex family of
compounds that share a common
structural feature, a sphingoid base
backbone that is synthesized from the
amino acid serine and a long-chain
fatty acyl CoA,

General structure of
Sphingolipid

Lipoprotein
A lipoprotein is a biochemical
assembly that contains both proteins
and lipids water-bound to the
proteins. Many enzymes,
transporters, structural proteins,
antigens, adhesins and toxins are
lipoproteins. Examples include the
high density (HDL) and low density
(LDL) lipoproteins

Classification of lipoprotein
Chylomicrons carry triglycerides (fat) from
the intestines to the liver, skeletal muscle,
and to adipose tissue.
Very low density lipoproteins (VLDL) carry
(newly synthesised) triacylglycerol from
the liver to adipose tissue.
Intermediate density lipoproteins (IDL) are
intermediate between VLDL and LDL. They
are not usually detectable in the blood.

Lipoproteins contd
Low density lipoproteins (LDL) carry
cholesterol from the liver to cells of
the body. LDLs are sometimes referred
to as the "bad cholesterol" lipoprotein.
High density lipoproteins (HDL) collect
cholesterol from the body's tissues,
and bring it back to the liver. HDLs are
sometimes referred to as the "good
cholesterol" lipoprotein.

FUNCTIONS OF LIPIDS
PHOSPHOLIPIDS ARE THE MAIN LIPID
CONSTITUENTS OF MEMBRANES

Phosphoacylglycerols containing
choline are the most abundant
phospholipids of the cell membrane
and represent a large proportion of
the bodys store of choline. Choline is
important in nervous transmission,
as acetylcholine

 As internal signals or second

messengers
Phosphatidylinositol 4,5-bisphosphate
is an important constituent of cell
membrane phospholipids; upon stimulation
by a suitable hormone agonist, it is
cleaved into diacylglycerol and inositol
trisphosphate, both of which act as
internal signals or second messengers.
Plasmalogens Occur in Brain & Muscle
These compounds constitute as much as
10% of the phospholipids of brain and
muscle.

Functions
Sphingomyelins Are Found in the
Nervous System: Sphingomyelins
are found in large quantities in brain
and nerve tissue. On hydrolysis, the
sphingomyelins yield a fatty acid,
phosphoric acid, choline, and a
complex
amino alcohol, sphingosine . No
glycerol is present.

Functions
GLYCOLIPIDS (GLYCOSPHINGOLIPIDS)
ARE IMPORTANT IN NERVE TISSUES
AND IN THE CELL MEMBRANE
Glycolipids are widely distributed in every
tissue of the body, particularly in nervous
tissue such as brain. They occur
particularly in the outer leaflet of the
plasma membrane, where they contribute
to cell surface carbohydrates.

 STEROIDS PLAY MANY

PHYSIOLOGICALLY IMPORTANT
ROLES
Cholesterol is probably the best known
steroid, biochemically it is the precursor
of a large number of equally important
steroids that include the bile acids,
adrenocortical hormones, sex hormones,
D vitamins and some alkaloids.
Ergosterol Is a Precursor of Vitamin
D

 LIPIDS ARE TRANSPORTED IN THE

PLASMA AS LIPOPROTEINS
Lipoproteins enable fats to be carried
in the blood stream, the transmembrane
proteins
of
the
mitochondrion and the chloroplast
and bacterial lipoproteins.
Carrier of fat soluble vitamins:
The absorption of fat-soluble vitamins
(A, D, E, K) is a function of digestion
and absorption of fats.

 Triacylglycerols Provide Stored

Energy and Insulation
There are two significant advantages to
using triacylglycerols as stored fuels,
rather than polysaccharides such as
glycogen and starch. First, because the
carbon atoms of fatty acids are more
reduced than those of sugars,
oxidation of triacylglycerols yields more
than twice as much energy, gram for
gram, as the oxidation of carbohydrates.

Functions
Waxes act as water proofing and
lubrication to keep the skin pliable,
lubricated and make feathers water
repellent.
Steroid hormones, derived from sterols,
serve
as powerful biological signals, such as
the sex
hormones.

Rancidification
This is the process which causes a
substance
to
become
rancid
(unpleasant smell or taste). It is the
hydrolysis and or autoxidation of fats
into short chain aldehydes and ketones.
Three pathways of rancidification
Hydrolytic rancidity: this is when
triglycerides are hydrolyzed and free
fatty acids are released

Rancidification contd.
Oxidative rancidity: it is associated with
degradation by oxygen in the air via a free
radical process, the double bonds of an
unsaturated fatty acid can undergo
cleavage releasing volatile aldehydes and
ketones.
Microbial rancidity: this is a process in
which micro organisms such as bacteria or
moulds, use their enzymes such as lipases
to break down fat.

LIPID PEROXIDATION IS A SOURCE

OF FREE RADICALS

Peroxidation (auto-oxidation) of lipids

exposed to oxygen is responsible not
only
for
deterioration
of
foods
(rancidity) but also for damage to
tissues in vivo, where it may be a cause
of cancer, inflammatory diseases and
aging. The deleterious effects are
considered to be caused by free
radicals (ROO, RO, OH) produced
during peroxide formation from fatty
acids

To control and reduce lipid

peroxidation
Both humans in their activities and nature
invoke the use of antioxidants. Propyl
gallate, butylated hydroxyanisole (BHA),
and butylated hydroxytoluene (BHT) are
antioxidants used as food additives.
Naturally occurring
antioxidants include
Polyphenols, Beta-carotene vitamin E
(tocopherol), which is lipid-soluble and
vitamin C, which is water-soluble. Fat
resistant to oxidation can be measured
through oxidative stability using the
Rancimat method

MEASUREMENTS OF FATS
Iodine
number:
This
is
the
percentage by weight of iodine
absorbed by the fat in the natural
state. It is an index to the degree of
unsaturation of the fats. The higher
the iodine number, the higher the
level
Fatof unsaturation.
Iodine
Fat
Iodine
No
No
Below
isoilthe7-12iodine
number
of some
Coconut
Cottonseed
100-117
oil
fat.
Palm kernel
oil

16-19

Corn oil

109-133

Palm oil

44-51

Sunflower oil

125-144

Olive oil

80-88

Soyabean oil

120-136

Saponification
Saponification is the hydrolysis of fats and
oils under basic conditions to glycerol and
the salt of the corresponding fatty acid.
Saponification number: This is the number
of milligrams of potassium hydroxide
required to convert one gram of fat
completely into glycerol and potassium soap.
The longer the carbon chain, the less acid is
liberated hence low saponification value.

MEASUREMENT CONTD
Titre test: This is the temperature at
which the mixture of fatty acids
derived from fat solidifies after it has
been melted. The temperature gives
an index to the consistency of the
original fat.