It should be noted that C and C¡ are 4.

Lipid peroxidation in vivo : n the living

different. Cells possess enzymes that can cells, lipids undergo oxidation to produce
distinguish these two carbons. Thus peroxides and free radicals which can damage
glycerokinase phosphorylates sn-3 (and not sn-1) the tissue. The free radicals are believed to cause
glycerol to give sn-glycerol 3-phosphate. inflammatory diseases, ageing, cancer,
atherosclerosis etc. It is fortunate that the cells
PROPERTIES OF TRIACYLGLYCEROLS possess antioxidants such as vitamin E, urate and
Afew important properties of triacvlglvcerols. superoxide dismutase to prevent in vivo lipid
which have biochemical relevance, are peroxidation (Chapter 34).
discussed below
Tests to check purity
1. Hydrolysis : Triacylglycerols undergo of fats and oils
stepwise enzymatic hydrolysis to finally liberate
free fatty acids and glycerol. The process of Adulteration of fats and oils is increasing day
in the
hydrolysis, catalysed by lipases is important for by day. Several tests are employed
laboratory to check the purity of fats and oils.
digestion of fat in the gastrointestinal tract and Some of them are discussed hereunder
fat mobilization from the adipose tissues.
2. Saponification : The hydrolysis of triacyl lodine number : It is defined as the grams
glycerols by alkali to produce glycerol and soaps (number) of iodine absorbed by 100 g of fat or
oil. lodine number is useful to know the relative
is known as saponification.
unsaturation of fats, and is directly proportional
Triacylglycerol + 3 NaOH to the content of unsaturated fatty acids. Thus
Glycerol +3 R-COONa (soaps) lower is the iodine number, less is the degree of
3. Rancidity: Rancidity is the term used to unsaturation. The iodine numbers of common
represent the deterioration of fats and oils oils/fats are given below.
resulting in an unpleasant taste. Fats containing
unsaturated fatty acids are more susceptible to Fat/oil lodine number
rancidity. Coconut ol 7 - 10
Rancidity occurs when fats and oils are Butter 25 28
exposed to air, moisture, light, bacteria etc. Palm oil 45 55
Hydrolytic rancidity occurs due to partial Olive oil 80 85
hydrolysis of triacylglycerols by bacterial Groundnut oil 85 100
Cottonseed oil 100-110
enzymes. Oxidative rancidity is due to oxidation
of unsaturated fatty acids. This results in the Sunflower oil 125135
Linseed oil 175 200
formation of unpleasant products such as
dicarboxylic acids, aldehydes, ketones etc. Determination of iodine number will help to
Rancid fats and oils are unsuitable for human know the degree of adulteration of a given oil.
consumption.
Saponification number : It is defined as the
Antioxidants : The substances which can mg (number) of KOH required to hydrolyse
prevent the occurrence of oxidative rancidity are (saponify) one gram of fat or oil. Saponification
known as antioxidants. Trace amounts of number is a measure of the average molecular
antioxidants such as tocopherols (vitamin E), size of the fatty acids present. The value is higher
hydroquinone, gallic acid and a-naphthol are for fats containing short chain fatty acids. The
added to the commercial preparations of fats and saponification numbers of a few fats and oils are
oils to prevent rancidity. Propyl gallate, butylated given below
hydroxyanisole (BHA) and butylated hydroxy Human fat : 195-200
toluene (BHT) are the antioxidants used in food Butter 230-240
preservation. Coconut oil : 250-260
 The fat speaks:
"With water, I say, 'Touch me not';
To the tongue, I am tasteful;
Within limits, I am dutiful;
In excess, I am dangerous!"

ipids (Greek: Iipos-fat) are of great (a) Fats and oils

(triacylglycerols) : These are
importance to the body as the chief esters of fatty acids with glycerol.
concentrated storage form of energy, besides The difference between fat and oil
their role in cellular structure and various other
only physical. Thus, oil is a
biochemical functions. As such, lipids are a liquid while fat is a solid at room
heterogeneous group of compounds and, temperature.
therefore, it is difficult to define them precisely. (b) Waxes: Esters of fatty acids (usually
Lipids may be regarded as organic substances long chain) with alcohols other than
relatively insoluble in water, soluble in organic glycerol. These alcohols may be aliphatic
solvents (alcohol, ether etc.), actually or or alicyclic. Cetyl alcohol is most
potentially related to fatty acids and utilized by commonly found in waxes. Waxes are
the living cells. used in the preparation of candles,
Unlike the polysaccharides, proteins and lubricants, cosmotics, ointments, polishes
nucleic acids, lipids are not polymers. Further, etc.

lipids are mostly small molecules. 2. Complex (or compound) lipids : These
Classification of lipids are esters of fatty acids with alcohols containing
additional groups such as phosphate,
Lipids are broadly classified (modified from nitrogenous base, carbohydrate, protein etc.
Bloor) into simple, complex, derived and They are further divided as follows
miscellaneous lipids, which are further subdivided
into different groups (a) Phospholipids : They contain phosphoric
acid and frequently a nitrogenous base.
1. Simple lipids: Esters of fatty acids with This is in addition to alcohol and fatty
alcohols. These are mainly of two types acids.

28
 Chapter 3: LIPIDS 29

(0 Glycerophospholipids : These phospho 5. Lipids protect the internal organs, serve as

lipids contain glycerol as the alcohol insulating materials and give shape and smooth
e.g., lecithin, cephalin. appearance to the body.
(ii) Sphingophospholipids : Sphingosine is
the alcohol in this group of phospho
lipids e.g., sphingomyelin. FATTY ACIDS
(b) Glycolipids : These lipids contain a fatty
acid, carbohydrate and nitrogenous base. Fatty acids are carboxylic acids with
The alcohol is sphingosine, hence they hydrocarbon side chain. They are the simplest
are also called as glycosphingolipids. form of lipids.
Glycerol and phosphate are absent e.g.,
cerebrosides, gangliosides. Occurrence
(c) Lipoproteins : Macromolecular complexes Fatty acids mainly occur in the esterified form
of lipids with proteins. as major constituents of various lipids. They are
also present as free (unesterified) fatty acids.
(d) Other complex lipids : Sulfolipids, amino Fatty acids of animal orgin are much simpler in
lipids and lipopolysaccharides are among
the other complex lipids. structure in contrast to those of plant origin
which often contain groups such as epoxy, keto,
3. Derived lipids : These are the derivatives hydroxy and cyclopentane rings.
obtained on the hydrolysis of group 1and group
2 lipids which possess the characteristics of Even and odd carbon fatty acids
lipids. These include glycerol and other alcohols,
Most of the fatty acids that occur in natural
fatty acids, mono- and diacylglycerols, lipid (fat)
soluble vitamins, steroid hormones, hydro lipids are of even carbons (usually 14C- 20C).
This is due to the fact that biosynthesis of fatty
carbons and ketone bodies.
acids mainly occurs with the sequential addition
4. Miscellaneous lipids : These include a of 2 carbon units. Palmitic acid (16C) and
large number of compounds possessing the stearic acid (18C) are the most common. Among
characteristics of lipids e.g., carotenoids, the odd chain fatty acids, propionic acid (3C)
squalene, hydrocarbons such as pentacosane (in and valeric acid (5C) are well known.
bees wax), terpenes etc.
Saturated and unsaturated
NEUTRAL LIPIDS : The lipids which are
uncharged are referred to as neutral lipids. These fatty acids
are mono-, di-, and triacylglycerols, cholesterol Saturated fatty acids do not contain double
and cholesteryl esters. bonds, while unsaturated fatty acids contain one
or more double bonds. Both saturated and
Functions of lipids unsaturated fatty acids almost equally occur in
Lipids perform several important functions the natural lipids. Fatty acids with one double
1. They are the concentrated fuel reserve of bond are monounsaturated, and those with 2 or
the body (triacylglycerols). more double bonds are collectively known as
polyunsaturated fatty acids (PUFA).
2. Lipids are the constituents of membrane
structure and regulate the membrane Nomenclature of fatty acids
permeability (phospholipids and cholesterol).
The naming of a fatty acid (systematic name)
3. They serve as a source of fat soluble
vitamins (A, D, E and K).
is based on the hydrocarbon from which it is
derived. The saturated fatty acids end with a
4. Lipids are important as cellular metabolic suffix -anoic (e.g., octanoic acid) while the
regulators (steroid hormones and prostaglandins). unsaturated fatty acids end with a suffix -enoic
 Chapter 8: DIGESTION AND ABSORPTION 175

Cholesteryl esterase
Hyo
O=0 +R-COOH
HO

Cholesterol Fatty acid

Cholesteryl ester

Fig. 8.10: Enzymatic cleavage of cholesteryl ester.

2. Partition theory proposed by Frazer : This Role of bile salts in lipid absorption
theory states that the digestion of triacylglycerols Besides their participation in digestion, bile
is partial and not complete. The partially
salts are essential for absorption of lipids. Bile
digested triacylglycerols, in association with bile
salts, form emulsions. The lipids are taken up by salts form mixed micelles with lipids. These
micelles are smaller in size than the lipid
the intestinal mucosal cells. As per this theory, emulsion droplets (utilized for digestion,
resynthesis of lipids is not necessary for their entry described above). The micelles have a disk like
into the circulation.
shape with lipids (monoacylglycerol, fatty acids,
3. Bergstrom theory : This is a more recent cholesterol and phospholipids) at the interior and
and comprehensive theory to explain lipid bile salts at the periphery. The hydrophilic
absorption. It has almost replaced the earlier groups of the lipids are oriented to the outside
theories, and is briefly described hereunder (close to the aqueous environment) and the
The primary products obtained from the lipid the
hydrophobic groups to the inside. In this fashion,
bile salt micelles exert a solubilizing effect
digestion are 2-monoacylglycerol, free fatty acids
and free cholesterol. on the lipids.

Mouth Small Intestine

Stomach

Pancreatic lipase
Monoacylglycerols
Triacylglycerols Almost Free fatty acids
Phospholipids unchanged Phospholipase A Glycerol
Cholesteryl esters Cholesteryl esterase Cholesterol

Unchanged

Fig. 8.11 :Overview of digestion of lipids.

 IS. ais are TO nave

active brown adipose tissue. They eat and liberate ATHEROSCLEROSIS

it as heat, and therefore do not become obese. Atherosclerosis (Greek: athere -mush) is a
Pharmacological treatment of obesity : In complex disease characterized by thickening or
recent years, synthetic lipids such as Olestra and hardening of arteries due to the accumulation of
Orlistat are used to treat obesity. They taste like lipids (particularly cholesterol, free, and
natural lipids but cannot be digested, and esterified) collagen, fibrous tissue, proteoglycans,
excreted unchanged. calcium deposits etc. in the inner arterial wall.
Atherosclerosis is a progressive disorder that
METABOLIC SYNDROME narrows and ultimately blocks the arteries.
Metabolic syndrome (MS) is a cluster of Infarction is the term used to indicate the
different conditions that adversely affect the stoppage of blood flow resulting in the death of
health. The components contributing to MS affected tissue. Coronary arteries-the arteries
include abdominal obesity, insulin resistance, supplying blood to heart-are the most
dyslipidemia, elevated blood pressure, over commonly affected leading to myocardial
infarction or heart attacks.
nutrition, sedentary lifestyles etc. As per WHO
criteria, metabolic syndrome has the following Causes of atherosclerosis and CHD : The
characteristics development of atherosclerosis and the risk for

Chapter 14:METABOLISM OF LIPIDS 327

the coronary heart disease (CHD) is directly ALCOHOL METABOLISM

correlated with plasma cholesterol and LDL. On
the other hand, plasma HDL is inversely Walker has rightly said 'alcohol can be a
correlated with CHD. food, a drug or a poison depending on the dose.'
Disorders that may cause In small quantities, alcohol relieves tension and
atherosclerosis anxiety. Unfortunately, consumption of alcohol
seldom ends with small doses, hence the
Certain diseases are associated with atheros beneficial effects are over-shadowed by the
clerosis. These include diabetes mellitus, harmful effects.
hyperlipoproteinemias, nephrotic syndrome, Alcohol (ethanol or ethyl alcohol) is readily
hypothyroidism etc. Many other factors like absorbed by the stomach and intestine.
obesity, high consumption of saturated fat, Consequently, less than 2% of the alcohol
excessive smoking, lack of physical exercise, consumed is excreted through lungs, urine and
hypertension, stress etc., are the probable Sweat.
causes of atherosclerosis. Alcohol gets oxidized in the liver by alcohol
dobvdr ldobdo