LIPIDS

Muhammad Wajid
Assistant Professor of Pharmaceutical Chemistry
Lipids Definition:

◻ Lipids may be regarded as organic substances

relatively insoluble in water, soluble in organic
solvents (Alcohol, ether etc.), actually or potentially
related to fatty acids and utilized by the living cells

◻ Derived from the Greek word: Lipos- Fat

◻ Lipids are heterogeneous group of compounds

Conti….

◻ Lipids serve as fuel molecules, signal molecules, and

components of membranes, hormones and intracellular
messengers

◻ They are esters of long chain fatty acids and alcohols

◻ LIPID describes a chemically varied group of fatty

substances and are highly concentrated energy stores
Example:
Bloor’s criteria:
◻ According to Bloor, lipids are compounds having the
following characteristics
o They are insoluble in water

o Solubility in one or more organic solvents such as ether,

chloroform, benzene, acetone, etc. so called fat solvents

o Some relationship to the fatty acids as esters either actual

or potential

o Possibility of utilization by living organism

Functions of Lipids:

◻ Lipids are the constituents of cell membrane and

regulate membrane permeability
◻ They protect internal organs, serve as insulating
materials and give shape and smoothness to the body
◻ They serve as a source of fat soluble vitamins A, D, E
and K
◻ Phospholipids in mitochondria are responsible for
transport of electron transport chain components
◻ Essential fatty acids are useful for transport of
cholesterol, formation of lipoproteins etc.
Lipoprotein Shape:
Conti…

◻ Accumulation of fat in liver is prevented by

phospholipids
◻ Phospholipids help in removal of cholesterol from the
body by participating in reverse cholesterol transport
◻ Cholesterol is a constituent of membrane structure and
it synthesizes bile acids, hormones and vitamin D
◻ Cholesterol is the principal sterol of higher animals,
abundant in nerve tissues and gallstones
Classification Of Lipids:

◻ Based on there Biological functions Lipids can be

classified into:
◻ Storage Lipids—The principle stored form of
energy
◻ Structural Lipids– The major structural elements of
Biological Membranes
◻ Lipids are signals, cofactors e.g Vitamin E as an
antioxidant and vitamin K as blood clotting factor
and pigments e.g cathaxanthin (bright red),
zeaxanthin (bright yellow)
Classification Of Lipids:
◻ LIPIDS are broadly classified into simple lipids, complex
lipids, derived lipids and miscellaneous lipids based on
their chemical composition
◻ Simple Lipids: These lipids are the esters of fatty acids
with alcohols. They are of two types: Waxes, and
Triacylglycerol
◻ Compound/Complex Lipids: These lipids are esters of
fatty acids with alcohols with additional groups such
as phosphate, nitrogenous base, etc. They are again
divided into 3 types: Phospholipids,
Glycerophosphlipids, Sphingophospholipids
Conti…
◻ Derived Lipids: These lipids are obtained on
hydrolysis of simple and complex lipids

◻ These lipids contain glycerol and other alcohols

◻ This class of lipids include steroid hormone,

cholesterol, fatty acids, fatty alcohols, mono and
diacylglycerides
Classification Scheme:
Fatty Acids:

◻ Many lipids have hydrophobic properties due to fatty

acid components
◻ Fatty acid are hydrocarbons chain that end with a
carboxylic acid group

◻ They can vary in :

o 1. Length
o 2. Degree of unsaturation
o 3. Properties such as melting point and fluidity etc.
Conti…

◻ Fatty acids are composed only of carbon, hydrogen

and oxygen in the proportion of 76%, 12.6% and
11.3% respectively

◻ Fatty Acids are carboxylic acids with hydrocarbon

chains ranging from 4-36
Classification of fatty acids:
Saturated Fatty acid:
◻ Saturated Fatty acids:
◻ Fatty acids without double bonds are known as saturated.
They are further classified as
◻ Short-chain fatty acids: are fatty acids with aliphatic tails of
fewer than six carbons (e.g. butyric acid).
◻ Medium-chain fatty acids: are fatty acids with aliphatic tails
of 6–12 carbons, which can form medium-chain triglycerides.
◻ Long-chain fatty acids: are fatty acids with aliphatic tails 13
to 21 carbons
◻ Very long chain fatty acids: are fatty acids
with aliphatic tails longer than 22 carbons
Unsaturated fatty acids:

◻ Contain one or more double bonds in the

hydrocarbon chain

◻ Monounsaturated fatty acids: have one

carbon–carbon double bond, which can occur in
different position

◻ The most common monoenes have a chain length of

16–22 and a double bond with the cis-configuration
Conti…

◻ Polyunsaturated fatty acids:

◻ The first double bond may be found between the
third and the fourth carbon atom from the ώ carbon;
these are called omega-3 fatty acids
◻ If the first double bond is between the sixth and
seventh carbon atom, then they are called ώ-6 fatty
acids
◻ Polyunsaturated fatty acids have 2-6 double bonds
Even and odd carbon fatty acid:

◻ Natural fatty acids are even carbon (usually

14C-20C)

◻ This is due to the fact that biosynthesis of fatty acids

mainly occurs with the addition of 2 carbon units

◻ Palmitic and stearic acids are most common example

◻ Odd chain fatty acids are propionic acid (3C) and

valeric acid (5C).
Nomenclature:

❑ The name of fatty acid is derived from the

hydrocarbon component the -e in the hydrocarbon is
simple replaced by -oic

❑ For example Hexadecane 🡪 Hexadecanoic (acid)

(Palmitic acid)

❑ What happened if the hydrocarbon chain is

unsaturated with one or more double bond
Conti…
Conti…

◻ We typically label carbon starting at the carboxyl

carbon and extending to other end
◻ The double bond is represented with a Δ While the
position is marked with a numerical superscript with
the first atom of the double bond indicated by
superscript number
◻ Δ4 indicates a double bond between carbon atoms 4
and 5.
Conti….
Fatty acids can also be numbered from the methyl
carbon atom, which is called the omega (ω) carbon
Length or Unsaturation:
◻ Although the most common fatty acid in biological
system are the 16 carbon and 18 carbon fatty acids
they generally range from 14 to 24 carbons in length
◻ In Animal they never branch
◻ As the length increases the melting point increases more
London dispersion forces between adjacent fatty acid
◻ Unsaturated fatty acid have lower melting point due to
weaker intermolecular interactions
◻ Weaker intermolecular bonds also make them fluids
Physical Properties of F.A:
◻ Solubility
◻ Longer chain
more hydrophobic, less soluble
◻ Double bond increases solubility
◻ Melting point
o Depends on chain length and saturation
o Double bonds lower melting point
o Saturated F.As are solids at room temperature
Isomerism:

◻ A double bond in Fatty acid chain permits two types

of geometrical isomers, Cis and trans
◻ Cis isomers have a curved configuration
◻ Trans isomers have a linear configuration
◻ Due to curve configuration Cis unsaturated fatty acids
have a lower melting point as compared to there
trans counterpart
◻ Most of the natural unsaturated fatty acids have Cis
double bonds
◻ Cis isomer are less stable than trans isomer
Structure:
Essential fatty acids:

◻ The term essential fatty acid refers to a fatty acid

which the body cannot manufacture, and must obtain
from dietary sources

◻ Two essential fatty acids, linolenic and alpha-linoleic

acid cannot be synthesized in the body and must be
obtained from food
Biochemical basis for essentiality:

◻ Linoleic acid and Linolenic acids are essential since

humans lack the enzyme that can introduce double
bond beyond carbon 9 to 10
Function of EFA:

◻ Essential fatty acids are required for

o Membrane structure and function

o Transport of cholesterol

o Formation of lipoprotein

o Prevention of Fatty liver

o Synthesis of eicosanoids
Non essential Fatty acids:

◻ A substance that is synthesized by the body in

sufficient quantity for normal health and growth

◻ For example Palmitic acid and stearic acid

Simple lipids
◻ Simple or neutral lipids are divided into two
categories

o Waxes

o Triacylglycerol
Waxes:

◻ Waxes are esters of long chain (C14-C36)

saturated and unsaturated fatty acids with long
chain (C16-C30) monohydric alcohol alcohols
Functions of Wax:

◻ Chief storage fuels for some of the microorganisms

◻ Protect skin and hair

◻ Prevents excess water evaporation in plants

◻ Protects against parasites

Triacylglycerol:

◻ A triglyceride is an ester derived from glycerol and

three fatty acids
Conti…

❑ Saturated triacylglycerol contain saturated fatty acids

❑ Mono-unsaturated triacylglycerol have only one C=C
double bond
❑ Polyunsaturated triacylglycerol have many C=C
double bonds
❑ Increasing the number of double bonds in fatty acid
chain decreases the melting point of the
triacylglycerol
Simple triglycerides:

◻ Triglycerides in which the three fatty acid are of the

same kind are known as simple triglycerides
◻ Tristearin, triolein, tripalmitin, etc., are examples of
simple triglycerides
◻ "Mixed" Triglycerides
◻ A mixed triglyceride is one in which the three fatty
acid radicles are not all of the same kind.
◻ For example, distearo-olein (having two radicles of
stearic and one of oleic acid)
Fats and Oils:

◻ Oils:
◻ A mixture of triglycerols that is liquid because it
contains a high proportions of unsaturated fatty acids

◻ Fats:
◻ A mixture of triglycerols that is solid because it
contains a high proportions of saturated fatty acids
Compound/Complex Lipids:

◻ The compound/complex lipids can be divided into

two main categories
o Phospholipids
o Glycolipids
◻ Phospholipids can be further divided into two
subtypes
o Phosphoglycerides
o Sphingolipids
Phospholipids:

◻ Most phospholipids contain :

o A platform molecule
o One or more fatty acid
o A phosphate group
o An alcohol component
❑ Fatty acid give the phospholipid hydrophobic
properties while the phosphate and alcohol group
gave it hydrophilic properties this makes
phospholipids “amphipathic”
Phosphoglycerides:

◻ Phospholipids that contain the glycerol as the platform

of attachment are called Phosphoglycerides
◻ In Phosphoglycerides C-1 and C-2 of the glycerol
backbone are esterified to two fatty acids while the
C-3 of the glycerol is esterified to the phosphate
group
◻ The simplest Phosphoglycerides is called
phosphatidate
◻ It contains an unmodified phosphate group and is
found in the cell membrane in small quantities
Conti…
Conti….
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◻ The most often than not, Phosphoglycerides have a

fourth group attached to the phosphate group
Conti…
Sphingolipids:

◻ Another platform on which phospholipids can be

built is sphingosine
◻ Sphingosine is more complex alcohol that contain an
amino group and a long, Unsaturated hydrocarbon
component
◻ The nitrogen of sphingosine is bound to a fatty acid
via an amide bond while primary alcohol is bound
to the phosphate group via an ester bond
Conti…
Glycolipids:

◻ Glycolipids are carbohydrates containing lipids

molecules that resembles Sphingolipids (a type of
phospholipids) because it contain sphingosine
Conti…

◻ Sphingosine acts as the backbone of attachment for a

fatty acid and carbohydrates component

◻ The sphingosine-fatty acid is the hydrophobic region

that stretches across the non polar membrane while
the carbohydrates moiety interacts with the aqueous
extracellular environment
Conti….
Derived lipids:

◻ These lipids are obtained on hydrolysis of simple and

complex lipids

◻ This class of lipids include steroid, fatty acids, fatty

alcohols, monoacylglycerides and diacylglycerides
Steroids:

◻ Steroids are the class of molecule that includes

o Sex hormones

o Vitamins

o Cholesterol
Conti…

◻ Steroids always have four membered ring structure

◻ A, B and C are six membered rings, while the D is
five membered ring
◻ C10 and C13 have always -CH3group
Sex hormones:

◻ These can be divided into three categories

o Estrogen (Female Sex hormone)

o Androgens (Male Hormone)

o Progestin (Pregnancy Hormone)

Estrogens:
◻ Secreted by the ovary of the females to initiate puberty

◻ Consist of two hormone estrone and estradiol

◻ They differ from each other at just C17

◻ Estradiol is responsible for secondary sex characters in

females

◻ Estrone is just metabolites of estradiol

Conti…
Androgens:

◻ Male hormone are called androgens

◻ Consist of androsterone and testosterone

◻ Testosterone is responsible for secondary sex

characters in males

◻ Androsterone is a metabolites of testosterone

Conti…
Progestins:

◻ Progesterone is the most important pregnancy

hormone
◻ It prepares the uterus lining for implantation of
fertilized egg
◻ It is a 21carbon steroid hormone also known as
pregn-4-ene-3,20-dione
◻ It has double bond between C4 and C5
◻ Two ketone groups at C3 and C20
◻ Two –CH3 groups at C10 and C13
Conti…
Cholesterol:

◻ Cholesterol is a steroid, which means it is composed of

four fused rings called
cyclopentanoperhydrophenanthrene nucleus.
◻ Its molecular formula is C27H46O
◻ It has –OH group at C3
◻ It has unsaturated double bond between C5 and C6
◻ It has two –CH3 groups at C10 and C13
◻ It has an eight carbon side chain attached to C17
Conti….
Ergosterol:

◻ It occurs in plants

◻ It is also found in the membrane of yeast

◻ Ergosterol is a precursor of Vitamin D

◻ When exposed to light the ring B of ergosterol is

opens and converted to ergocalciferol, a compound
containing Vitamin D activity
Conti….