Lipids

Lipids are a group of diverse macromolecules consisting of fatty acids and their derivatives
that are insoluble in water but soluble in organic solvents. They naturally occur in most
plants, animals, microorganisms and are used as cell membrane components, energy storage
molecules, insulators and hormones.
Properties of Lipids
 Lipids may be either liquids or non-crystalline solids at room temperature.
 Pure fats and oils are colorless, odorless, and tasteless.
 They are energy-rich organic molecules
 Insoluble in water
 Soluble in organic solvents like alcohol, chloroform, acetone, benzene, etc.
 No ionic charges
 Solid triglycerols (Fats) have high proportions of saturated fatty acids.
 Liquid triglycerols (Oils) have high proportions of unsaturated fatty acids.
 Lipids consist of fats, oils, hormones, and certain components of membranes that are grouped
together because of their hydrophobic interactions.
 The lipids are essential constituents of the diet because of their high energy value.
 These are also essential for the fat-soluble vitamins
 Fats combined with proteins (lipoproteins) are essential constituents of the cell membranes
and mitochondria of the cell.

Structure of lipids
Lipids are made of the elements Carbon, Hydrogen and Oxygen, but have a much lower
proportion of water. They are made from two molecules: Glycerol and Fatty Acids.

A glycerol molecule is made up of three carbon atoms with a hydroxyl group attached to it
and hydrogen atoms occupying the remaining positions.
Fatty acids consist of an acid group at one end of the molecule and a hydrocarbon chain,
which is usually denoted by the letter ‘R’.
Structure of Triglycerides
Triglycerides are lipids consisting of one glycerol molecule bonded with three fatty acid
molecules. The bonds between the molecules are covalent and are called Ester bonds.
They are formed during a condensation reaction. The charges are evenly distributed around
the molecule so hydrogen bonds to not form with water molecules making them insoluble in
water.
Fatty Acids
A fatty acid is a molecule characterized by the presence of a carboxyl group attached to a
long hydrocarbon chain. Their formula is R–COOH where R is a hydrocarbon chain. Fatty
acids are of two major varieties.
􀁺 Saturated fatty acids do not have any double bonds. A fatty acid is saturated when every
carbon atom in the hydrocarbon chain is bonded to as many hydrogen atoms as possible (the
carbon atoms are saturated with hydrogen). Saturated fatty acids are solids at room
temperature. Animal fats are a source of saturated fatty acids
Unsaturated fatty acids can have one or more double bonds along its hydrocarbon chain. A
fatty acid with one double bond is called monounsaturated. If it contains two or more
double bonds, we say that the fatty acid is polyunsaturated.
The melting point of a fatty acid is influenced by the number of double bonds that the
molecule contains and by the length of the hydrocarbon tail. The more double bonds it
contains, the lower the melting point. As the length of the tail increases, the melting point
increases. Plants are the source of unsaturated fatty acids.

Classification of fatty acids

􀁺 In a cis stereoisomer, two similar groups attached to the carbon double bond are found on
the same side. Naturally occurring fatty acids have cis bonds.
􀁺 In a trans stereoisomer, two similar groups attached to the carbon double bond are found
on opposite sides. Trans-fatty acids are created artificially using a process called
hydrogenation.
Lipid Classification
I type
Lipids can be divided in two major classes
1. Non-saponifiable lipids
2. Saponifiable lipids.

Non-saponifiable lipid: cannot be broken up into smaller molecules by hydrolysis, which

includes triglycerides, waxes

Saponifiable lipid: contains one or more ester groups allowing it to undergo hydrolysis in
the presence of an acid, base, or enzyme. It includes steroids, prostaglandins,
glycerophospholipids, sphingolipids and terpenes.

II type grouping
Each of these categories can be further broken down- Nonpolar lipids and polar lipids
Nonpolar lipids, such as triglycerides, are used for energy storage and fuel.
Polar lipids, which can form a barrier with an external water environment, are used in
membranes. Polar lipids include glycerophospholipids and sphingolipids.

III type
Based on their function:
 Energy-storage lipids – A fat, triacylglycerols or triglycerides.
 Membrane lipids - phospholipids, sphingoglycolipids, and cholesterol
 Emulsification lipids - bile acids, soaps and detergents
 Chemical messenger lipids - steroid hormones, eicosanoids, and prostaglandins
 Protective-coating lipids - biological waxes
 Fat-soluble vitamins-
Lipids exhibit structural diversity and some are esters, some are amides, and some are
alcohols (acyclic and cyclic) and some are polycyclic.

IV type General classification- Lipids are generally classified into three main classes
1. Simple Lipids
2. Compound Lipids
3. Derived Lipids
4. Miscellaneous Lipids

Simple lipids:
They are esters of fatty acids with alcohols. According to the types of alcohols, there are two
main sub-groups:
1. Neutral fats or triacylglycerol (TAG): They are esters of three fatty acids with glycerol.
2. Waxes: They are esters of one fatty acid with long chain monohydroxyalcohol higher than
glycerol. Ex. bee’s wax, Cholesteryl esters.

Neutral fats or triacylglycerol (TAG) (Triglyceride):

I
Neutral fats are classified into –
a) Oils: They are liquid at room temperature due to their high content of USFA.
b) Solid fats: They are solid at room temperature due to their high content of long chains
SFA.

Physical Properties of Neutral Fats:

- Pure, freshly prepared TAGs are colorless, odorless and tasteless. The yellow color of fats
and oils is due to the presence of certain pigments e.g. carotenoids.
- They are insoluble in water but soluble in fat solvents.

Chemical Properties of Neutral Fats:

A- Addition of hydrogen (reduction or hardening):
It is the addition of hydrogen through the double bonds to convert USFA into SFA. So the
liquid oils will be converted into solid fats.
B- Hydrolysis of TAG:
1. Acid hydrolysis: gives glycerol and free fatty acid
2. Enzymatic hydrolysis: gives glycerol and free fatty acid
3. Alkaline hydrolysis (saponification): Forms salt of specific base

Rancidity:
Rancidity is due to exposure of fats or oils to high temperature, oxygen, moisture or
humidity, light and metals (act as catalysts). There is development of bad odor and taste of
fats and oils.
Types of Rancidity:
a) Hydrolytic rancidity: due to the hydrolysis of TAG by lipase enzyme
b) Oxidative rancidity: Oxidation of USFA produces peroxides, lower chain fatty acids,
fatty aldehydes and ketones.
Protection against rancidity: By Addition of antioxidants e.g. vitamin E, phenols and
quinones

II- Compound lipids:

They contain fatty acids, alcohols and other groups. According to the type of the attached
group they are classified into:
1- Phospholipids: Containing phosphate radicals.
2- Glycolipids: Containing carbohydrate radicals.
3. Lipoprotein: Containing protein radicals
1- Phospholipids
They are classified according to the alcohol present into two main sub-groups:
A- Glycerophospholipids: Containing glycerol.
B- Sphingomyelin: Containing sphingosine (sphingol).

A- Glycerophospholipids(Glycerophosphatides):
They are phospholipids containing glycerol. They include phosphatidic acid and its
derivatives as follows:
I.Glycerophospholipids with nitrogen base:
1. Phosphatidic acid (Diacylglycerolphosphate):
On hydrolysis: It gives one glycerol, one saturated fatty acid (usually at position 1), one
unsaturated fatty acid (usually at position 2), and phosphoric acid.

2. Lecithin (Phosphatidylcholine):
It is formed of phosphatidic acid and choline. It is usually present in the cell membranes
especially in the liver, lung and brain. It is also present in blood plasma. It serves as
neurotransmitter Acetylcholine.helps in esterification of clolesterol.

3. Cephalin (Phosphatidylethanolamine):
It is formed of phosphatidic acid and ethanolamine. It is present in the cell membranes and
blood plasma. It forms thromboplastin ,required for blood clotting.

4. Phosphatidylserine:
It is formed of phosphatidic acid and serine amino acid. It is present in cell membranes. Play
a key role in cell signalling mainly during apoptosis.
5. Phosphatidylglycerol:
It is formed of phosphatidic acid and glycerol.

6. Plasmalogens:
Plasmalogens are a type of ether phospholipid characterized by the presence of an
enol form of fatty alcohol in ether linkage at the position-1, a fatty acid at the position-2 and
an R group at the position-3. The R-group is in the form of serine, ethanolamine or choline.
Plasmalogens are found in numerous human tissues e.g. nervous and cardiovascular system.

I. Glycerophospholipids without nitrogen base:

1. Phosphatidylinositol (Lipositol):
It is formed of phosphatidic acid and inositol. It is present in cell membranes. acts as
secondary messenger in the process of intracellular signal transduction.
2.Cardiolipins (Diphosphatidylglycerol): They are formed of two molecules of
phosphatidic acid connected by a molecule of glycerol. So, they contain 4 FAs, 3 glycerol
and 2 phosphates

B- Sphingomyelin:
This type is present in cell membranes specially of the lungs and brain mainly in the myelin
sheath. It contains sphingosine (sphingol) which is an 18 carbon amino alcohol. Fatty acids
are linked to sphingosine by an amide bond to form ceramide, which is connected to
phoshocholine to form sphingomyelin.
Importance and Functions of Phospholipids:
1) Phospholipids are amphipathic molecules that contain non-polar groups of fatty acid side
chains and polar groups of glycerol, phosphate, serine, ethanolamine, choline and inositol.
They form micelles in water.
2) They are good emulsifying factors, important for digestion and absorption of dietary fats.
3) They are essential for blood clotting, as they provide the platelet activating factor (PAF),
which is a plasmalogen that contains choline, palmityl alcohol at position 1 and acetic acid at
position 2.
4) Intracellular signal transduction: Many chemical transmitters (e.g. acetylcholine,
histamine and serotonin), hormones (e.g. vasopressin and α-1 receptors for epinephrine and
norepinephrine) and growth factors act through activation of phospholipase C.
5) They are important constituents of lipid bilayer in cell membranes.

2- Glycolipids
They are formed of ceramide (sphingosine alcohol and fatty acid) and a carbohydrate radical.
They include the following types:

A- Cerebrosides:
They contain ceramide (Sphingosine +fatty acid) and sugar- either galactose
(galactocerebrosides) or glucose (glucocerebrosides). They are widely distributed in brain
tissues and brain centers.
B- Sulpholipids (Sulphatides):
They are present in the liver, muscles and testis. They have the same structure as cerebrosides
but there is a sulphate group attached to the hydroxyl group of C3 of galactose. Present in
myelin.

C. Globoside: They contain either ceramide (Sphingosine +fatty acid) and oligosaccharide is
present. Constituent of RBC member and determinants of ABO blood grouping.

C- Gangliosides:
They are formed of ceramide connected to a complex carbohydrate radical containing
mixture of glucose, galactose, amino sugars and NANA (N-Acetyl Neuraminic Acid). The
fatty acid usually contains 18 carbon atoms e.g. oleic acid or stearic acid.

Importance of glycolipids:
They are found mainly in brain tissues, myelin sheath and cell membrane of RBCs. They are
components of cell membrane receptors for hormones and external stimuli, also they provide
recognition properties.

LIPOPROTEINS
Protein combine with lipids to form several classes of lipoprotein particles
(Apolipoproteins). They are spherical complexes with hydrophobic lipids in the core and
hydrophilic amino acid side chains at the surface. Different combinations of lipids and
proteins produce particles of different densities, ranging from chylomicrons to high-density
lipoproteins. Each class of lipoprotein has a specific function, determined by its point of
synthesis, lipid composition, and apolipoprotein content. There are 4 different lipoproteins
found in the blood that are clinically important. They vary in their densities, size and
triglyceride/cholesterol ester ratios.
Functions of lipoprotein:
1. Transport fat molecules, such as triacylglycerols (also known as triglycerides),
phospholipids, and cholesterol within the extracellular water of the body to all the cells and
tissues of the body.
2. Act as structural margin, recognise cell membrane surface receptors and activate enzyme
of lipid metabolism.

III- Derived Lipids

They are produced by hydrolysis of either simple or conjugated lipids or they are associated
with lipids in nature. They include the following:
1. Fatty acids. 2. Alcohols.
3. Steroids. 4. Ketone bodies 5. Prostagladins

STEROIDS
They are compounds containing steroid nucleus. This nucleus is composed of four fused rings
with 17 carbon atoms.
Ex. five major classes of steroid hormones: testosterone (androgen), estradiol (estrogen),
progesterone (progestin), cortisol/corticosterone (glucocorticoid), and aldosterone
(mineralocorticoids)
Miscellaneous Lipids - Carotenoids
They are fat soluble pigments yellow to red in color. They are widely distributed in plants
and responsible for many colors of fruits and vegetables e.g. orange, apricot, apple, tomato
and carrots. They are also found in human and animal fats, milk, butter and egg yolk. They
are precursors of vitamin A that have an important role in vision and normal development.
They are powerful antioxidants that can help in the prevention of certain human diseases,
such as atherosclerosis or cancer. They enhance immune response against infections.

Squalene
Squalene is a colorless poly-unsaturated hydrocarbon liquid that's found naturally in many
animals and plants, including human sebum
Uses
Squalene can reduce cholesterol and triglyceride levels.
It helps increase hydration, and anti-inflammatory properties of skin.