Chemistry of Lipids

• Lipids are essential components of all living organisms, with highly

varied structures and diverse functions
• They are water-insoluble (or sparingly soluble) organic compounds,
with high solubility in nonpolar organic solvents such as ether,
ethanol, methanol and chloroform.
.
• Lipids are important dietary constituents due to their high energy
value, making them efficient fuel molecules and storage forms of
energy
• Fat-soluble vitamins and essential fatty acids are also contained in the
fat of natural foods.
• Biological membranes contain a variety of lipids, including
glycerophospholipids, sphingolipids and cholesterol
• Fat is deposited in adipose tissue (mainly in the form of TAG) where it
where it functions as intracellular storage molecule for metabolic
energy and serves as a thermal insulator in the subcutaneous tissues
and around certain organs.
• Waxes in cell walls, exoskeletons and skin protect the surfaces of
some organisms
Steroid hormones and eicosanoids serve as signaling molecules, thus
regulating many activities in animals/mammals

Gangliosides play important roles in growth and differentiation of

tissues. For example, they stimulate neuronal cell outgrowths,
including axons and dendrites and are involved in the formation of
synapses. They also participate in cell to cell communication.
Lipoproteins serve as the means of transporting lipids in the blood.
Lipid biochemistry aids the understanding of important biomedical
conditions, including obesity, diabetes mellitus, and atherosclerosis
• Lipids are more efficient sources of energy than carbohydrates because
they are more reduced and more hydrophobic.
• Most of the energy in organic molecules are locked up in the carbon-
hydrogen covalent bonds. When macromolecules are broken down to
produce energy, the hydrogen atoms are removed and used to fuel the
electron transport chain, which produces most of the energy of the cell in
form of ATP . Lipids have a higher ratio of hydrogen to carbon atoms than
CHOs
• Lipids are stored without water, so they can store more energy in a more
compact and smaller space. Carbohydrates, like glycogen, bind to water,
making them heavier and less energy dense.
• The body has the capacity to store far greater amount of Lipids than
Carbohydrates
• About 4kCal and 9Kcal of energy per gram are released by CHOs and
Lipids respectively
CLASSIFICATION OF LIPIDS
1.Simple lipids
Esters of fatty acids with various alcohols.
a. Fats: Esters of fatty acids with glycerol. Oils are fats in the liquid
state.
b. Waxes: Esters of fatty acids with high molecular weight monohydric
alcohols, containing 12-24 C atoms e.g beewax, used in constructing
the honeycombs of beehives.
2.Complex lipids
Esters of fatty acids containing other groups in addition
to alcohol and fatty acid.
Examples
a. Phospholipids: They possess, in addition to fatty acids and an alcohol, a
phosphoric acid residue. They also have nitrogen-containing bases and other
substituents, for example, in glycerophospholipids the alcohol is glycerol and in
sphingophospholipids the alcohol is sphingosine.
b. Glycolipids (glycosphingolipids): Lipids containing a fatty acid, sphingosine, and
carbohydrate.

3.Precursor and derived lipids

Include fatty acids, glycerol, steroids, carotenoids, terpenes, ketone bodies,
hydrocarbons, lipid-soluble vitamins, cholesterol and hormones.
Chemical Nature/ Structure of fatty acids
• Fatty acids are aliphatic carboxylic acids .They occur in the body
mainly as esters in natural fats and oils, but are also found in the
unesterified form as free fatty acids in plasma.
• Fatty acids that occur in natural fats usually contain an even number
of carbon atoms. The chain may be saturated or unsaturated.
• The fatty acid is named after the hydrocarbon with the same number
and arrangement of carbon atoms, with -oic being substituted for the
final -e Thus, saturated acids end in -anoic, for example, octanoic
acid, and unsaturated acids with double bonds end in -enoic, for
example, octadecenoic acid (oleic acid).
 Saturated Fatty Acids

Common name Chemical structure C:D[9]

Caprylic acid CH3(CH2)6COOH 8:0
Capric acid CH3(CH2)8COOH 10:0
Lauric acid CH3(CH2)10COOH 12:0
Myristic acid CH3(CH2)12COOH 14:0
Palmitic acid CH3(CH2)14COOH 16:0
Stearic acid CH3(CH2)16COOH 18:0
Arachidic acid CH3(CH2)18COOH 20:0
Behenic acid CH3(CH2)20COOH 22:0
Lignoceric acid CH3(CH2)22COOH 24:0
Cerotic acid CH3(CH2)24COOH 26:0
• Table : saturated Fatty Acids
• Carbon atoms are numbered from the carboxyl
carbon (carbon no. 1). The carbon atoms adjacent to
the carboxyl carbon (nos. 2, 3, and 4) are also known
as the α, β and γ and carbons, respectively, and the
terminal methyl carbon is known as the ω - or n-
carbon
• Various conventions use Δ for indicating the number
and position of double bonds e.g Δ 9 indicates a
double bond between carbons 9 and 10 of the fatty
acid; ω9 indicates a double bond on the ninth carbon
counting from the ω -carbon.
Linoleic acid
Structures of 18-carbon unsaturated fatty acids. The numbers
above the fatty acids indicate the n-3 (ω-3), n-6 (ω-6), n-9 (ω-
9), and n-12 positions of double bonds
• Mammals lack the enzymes to introduce double
bonds at carbon atoms beyond C-9 in the fatty acid
chain. Hence, they cannot synthesize linoleate (18:2
cis- ∆ 9, ∆ 12 ) and linolenate (18:3 cis-∆ 9, ∆ 12 ∆ 15 ),
making them the two essential fatty acids
• Unsaturated Fas in mammals are derived from either
palmitoleate, oleate, linoleate or linolenate.
Unsaturated FA contain 1 or more double bonds and may be subdivided as
• Monounsaturated ( monoenoic) acids, containing one double bond
Examples- Oleic acid, Palmitoleic acid
• Polyunsaturated (polyenoic) acids, containing two or more double bonds.
Examples
Eicosanoids: Derived from eicosa (20-carbon) polyenoic fatty acids e.g
arachidonic acid. They comprise the prostanoids, leukotrienes (LTs), and lipoxins
(LXs).
Prostanoids include prostaglandins (PGs), prostacyclins (PGIs), and thromboxanes
(TXs).
Linoleic and linolenic acids also form the starting point for the creation of longer
and more desaturated FA, known as LC-PUFA
• Essential fatty acids are needed for various cellular metabolic
proceses and for the maintenance and function of tissues and
organs.These fatty acids also are precursors to vitamins,cofactors and
eicosanoids,including prostaglandins, leukotrienes, thromoboxanes
and lipoxins.
PGE2 PGF2α
PGI2
Trans and Cis Fatty acids
A type of geometric isomerism occurs in unsaturated fatty acids, depending
on the orientation of atoms or groups around the axes of double bonds
• 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
• Double bonds in naturally occurring unsaturated long-chain fatty acids are
nearly all in the cis configuration.
• . Trans fatty acids are present in certain foods, arising as a by-product of
the saturation of fatty acids during hydrogenation, or "hardening," of
natural oils in the manufacture of margarine.
• Consumption of trans fatty acids is known to be detrimental to health and
is associated with increased risk of cardiovascular disease , stroke , cancer
and DM
• Oleic Acid