Lipids

Lipids may be regarded as organic substances relatively insoluble in water, soluble in organic solvents (alcohol, ether)
actually or potentially related to fatty acids and utilized by the living cells.
Classification of lipids

Simple Lipids Complex lipids Derived Lipids Miscellaneous lipids

Esters of fatty acids with They contain phosphoric acid and These are the derivatives These include many compounds
alcohols. frequently a nitrogenous base. obtained on the hydrolysis of possessing the characteristics of lipids
Fats and oils Phospholipids : group 1 and group 2 lipids e.g., carotenoids, squalene,
These are esters of fatty acids with alcohols which possess the
Esters of fatty acids
containing additional groups such characteristics of
hydrocarbons such as pentacosane (in
with glycerol. bees wax), terpenes etc.
as nitrogenous
carbohydrate, lipids. For e.g., soluble
protein
phosphate, base, vitamins, steroid hormones,
Glycerophospholipids : These
phospholipids contain glycerol as the alcohol
Neutral Lipids: The lipids which are uncharged are
Waxes e.g., lecithin, cephalin.
Esters of fatty acids (usually
(Sphingophospholipids : Sphingosine is the referred to as neutral lipids. These are mono-, di-,
alcohol in this group of phospholipids and triacylglycerols, cholesterol and cholesteryl
long chain) with alcohols other than
e.g., sphingomyelin.
glycerol. These alcohols may be
Glycolipids: esters.
aliphatic
These lipids contain a fatty acid, carbohydrate and
or alicyclic. nitrogenous base. The alcohol is sphingosine, hence they 1. They are the concentrated fuel reserve of the body (triacylglycerols).
are also called as glycosphingolipids.
2.Lipids are the constituents of membrane structure and regulate the membrane
Lipoproteins : permeability (phospholipids and cholesterol).
Macromolecular complexes of lipids with proteins. 3. They serve as a source of fat-soluble vitamins (A, D, E and K).
4.Lipids are important as cellular metabolic regulators (steroid hormones and
Other complex lipids : prostaglandins).
Sulfolipids, aminolipids and lipopolysaccharides 5. Lipids protect the internal organs, serve as insulating materials and give shape
are among the other complex lipids. and smooth appearance to the body.
 Lipids
Fatty Acids Fatty acids are carboxylic acids with hydrocarbon side chain. They are the simplest form of lipids.

Saturated and unsaturated fatty acids:

Saturated fatty acids do not contain double bonds, while unsaturated fatty acids contain one or more double bonds.

Fatty acids with one double bond are monounsaturated (MUFA), and those with 2 or more double bonds are
collectively known as polyunsaturated fatty acids (PUFA).
Nomenclature of fatty acids:
The saturated fatty acids end with a suffix -anoic (e.g., octanoic acid) while the unsaturated fatty acids end with a
suffix -enoic
Numbering of carbon atoms

Length of hydrocarbon chain of fatty acids: Short chain with less than 6 carbons; medium chain with 8 to 14
carbons and long chain with 16 to 24 carbons.

Shorthand representation of fatty acids: total number of carbon atoms are written first, followed by the number of
double bonds and finally the (first carbon) position of double bonds, starting from the carboxyl end. For e.g. saturated
fatty acid, palmitic acid is written as 16 : 0, oleic acid as 18 : 1; 9, arachidonic acid as 20 : 4; 5, 8, 11, 14.
 Triacylglycerols
Triacylglycerols (formerly triglycerides) are the esters of glycerol with fatty acids. They are insoluble in water
and non-polar in character and commonly known as neutral fats.
Functions: Triacylglycerols are the most abundant group of lipids that primarily function as fuel reserves of
animals. The fat reserve of normal humans (men 20%, women 25% by weight) is sufficient to meet the body’s
caloric requirements for 2-3 months. Also present in adipose tissue.

Structure of acylglycerols:
• Monoacylglycerols, Diacylglycerols, Triacylglycerols
• Simple triacylglycerols: Same type of fatty acid residue at all 3 carbons. For e.g. tristearin
Mixed triacylglycerols : 2 or 3 types of fatty acid residues. For e.g. 1,3-palmitoyl 2-linoleoyl glycerol.

Stereospecific numbering of glycerol

Cells possess enzymes that can distinguish these two carbons. Glycerokinase
phosphorylates sn-3 (and not sn-1) glycerol to give sn-glycerol 3-phosphate.
 Triacylglycerols
Properties of Triacylglycerols
1.Hydrolysis : Triacylglycerols undergo stepwise enzymatic hydrolysis to finally liberate free fatty acids and glycerol. The process of
hydrolysis, catalyzed by lipases is important for digestion of fat in the gastrointestinal tract and fat mobilization from the adipose
tissues.
2. Saponification : The hydrolysis of triacylglycerols by alkali to produce glycerol and soaps is known as saponification.
Triacylglycerol + 3 NaOH Glycerol + 3 R-COONa (soaps)
3.Rancidity : Rancidity is the term used to represent the deterioration of fats and oils resulting in an unpleasant taste. Fats
containing unsaturated fatty acids are more susceptible to rancidity.
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.
4.Lipid peroxidation in vivo : In the living cells, lipids undergo oxidation to produce peroxides and free radicals which can damage
the tissue.

Tests for Lipids

Iodine number It is defined as the grams (number) of iodine absorbed by 100 g of fat or oil.

Saponification number It is defined as the mg (number) of KOH required to hydrolyze (saponify) one gram of fat or oil.
Acid number It
Reichert-Meissl
is defined as the number of mg of KOH required to completely neutralize free fatty acids present in one gram fat or
(RM) number It is defined as the number of ml 0.1 N KOH required to completely neutralize the soluble volatile
oil.
fatty acids
distilled from 5 g fat
 Phosphoclipids
These are complex or compound lipids containing phosphoric acid, in addition to fatty acids, nitrogenous base and alcohol
There are two classes of phospholipids; Glycerophospholipids (or phosphoglycerides) that contain
glycerol as the alcohol and Sphingophospholipids (or sphingomyelins) that contain sphingosine as the
alcohol.
Glycerophospholipids: Glycerophospholipids are the major lipids that occur in biological membranes. They consist of glycerol
3-phosphate
esterified at its C1 and C2 with fatty acids. Usually, C1 contains a saturated fatty acid while C2 contains an unsaturated fatty acid.

Sphingomyelins
Sphingosine is an amino alcohol present in sphingomyelins (sphingophospholipids). They do not contain glycerol at all. Sphingosine is attached by an
amide linkage to a fatty acid to produce ceramide. The alcohol group of sphingosine is bound to phosphorylcholine in sphingomyelin structure.
Sphingomyelins are important constituents of myelin and are found in good quantity in brain and nervous tissues.

Functions of phospholipids
Phospholipids constitute an important group of compound lipids that perform a wide variety of functions
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. Phospholipid's act as surfactants (agents lowering surface tension). For instance, dipalmitoyl phosphatidylcholine is an important lung
 Other lipids
Glycolipids
Glycolipids (glycosphingolipids) are important constituents of cell membrane and nervous tissues (particularly the brain).
Cerebrosides are the simplest form of glycolipids. Cerebrosides are the simplest form of glycolipids. They contain a
ceramide (sphingosine attached to a fatty acid) and one or more sugars.
Lipoproteins
Lipoproteins are molecular complexes of lipids with proteins. They are the transport vehicles for lipids in the circulation.
There are five types of lipoproteins, namely chylomicrons, VLDL, LDL, HDL, and free fatty acid albumin complexes.
Steroids
Steroids are the compounds containing a cyclic steroid nucleus (or ring) namely cyclopentanoperhydrophenanthrene
(CPPP). It consists of a phenanthrene nucleus (rings A, B and C) to which a cyclopentane ring (D) is attached. For e.g.,
cholesterol, bile acids, vitamin D, sex hormones, adrenocortical hormones,
Amphipathic lipids
Molecules which contain both hydrophobic and hydrophilic groups are known as amphipathic (Greek : amphi-both,
pathos— passion).
When the amphipathic lipids are mixed in water (aqueous phase), the polar groups (heads) orient themselves
towards aqueous phase while the non-polar (tails) orient towards the opposite directions. This leads to the
formation of micelles
Other lipids