General Biomolecules: Carbohydrates, Lipids

The living matter is composed of mainly six elements — carbon, hydrogen, oxygen, nitrogen,
phosphorus and sulphur. Perhaps the most important molecule for life is water. It is the fluid
of all living matter. Without water, life would not have been possible. Carbon is the most
predominant and versatile element of life. It possesses a unique property to form infinite
number of compounds. This is attributed to the ability of carbon to form stable covalent
bonds and C—C chains of unlimited length. It is estimated that about 90% of compounds
found in living system invariably contain carbon. A single cell of the bacterium, Escherichia
coli contains about 6,000 different organic compounds. The organic compounds such as
amino acids, nucleotides and monosaccharide’s serve as the monomeric units or building
blocks of complex biomolecules — proteins, nucleic acids (DNA and RNA) and
polysaccharides, respectively.

1. Carbohydrates
2. Stereochemistry
3. Lipids
4. Fatty acids
5. Functions of Lipids

Carbohydrates:

Carbohydrates are the most abundant organic molecules in nature. They are primarily
composed of the elements carbon, hydrogen and oxygen. The name carbohydrate literally
means ‘hydrates of carbon.’ Carbohydrates may be defined as polyhydroxy- aldehydes or
ketones or compounds which produce them on hydrolysis. The term ‘sugar’ is applied to
carbohydrates soluble in water and sweet to taste. The term sugar has become a synonym
with carbohydrates.

Classification of Carbohydrates:

Carbohydrates are broadly classified into 3 groups—monosaccharides, oligosaccharides and

polysaccharides. This categorization is based on the number of sugar units. Mono- and
oligosaccharides are sweet to taste, crystalline in character and soluble in water, hence they
are commonly known as sugars.
Monosaccharide’s:

Monosaccharides (Greek: mono-one) are the simplest group of carbohydrates and are often
referred to as simple sugars. They have the general formula Cn(H2O)n, and they cannot be
further hydrolysed. Based on the number of carbon atoms, the monosaccharide’s are regarded
as trioses (3C), tetroses (4C), pentoses (5C), hexoses (6C) and heptoses (7C). These terms
along with functional groups are used while naming monosaccharides. For instance, glucose
is a aldohexose while fructose is a ketohexose.

Oligosaccharides:

Oligosaccharides (Greek: oligo-few) contain 2-10 monosaccharide molecules which are

liberated on hydrolysis. Based on the number of monosaccharide units present, the
oligosaccharides are further subdivided to disaccharides, tri- saccharides and so on.Among
the disaccharides, three disaccharides are most widely known. They are sucrose, lactose and
maltose. Sucrose is the table sugar most widely produced and sold all over the world. The
increased consumption of sucrose has been attributed to many global problems like obesity.
Lactose is the mik sugar and maltose is present in germinating seeds. There are several other
disaccharides such as trehalose and cellobiose.

Polysaccharides:

Polysaccharides (Greek: poly-many) are polymers of monosaccharide units with high

molecular weight . They are usually tasteless and form colloids with water. Polysaccharides
are of two types—homopoly- saccharides , made up of a single type of mono saccharide ,and
heteropolysaccharides made up of two or more different monosaccharide units

Stereochemistry

Stereoisomerism is an important character of monosaccharides. Stereoisomers are the

compounds that have the same structural formulae but differ in their spatial configuration. A
carbon is said to be asymmetric when it is attached to four different atoms or groups. The
number of asymmetric carbon atoms (n) determines the possible isomers of a given
compound which is equal to 2n. Glucose contains 4 asymmetric carbons and thus has 16
isomers.
D- and L-isomers:

Glyceraldehyde (triose) is the simplest monosaccharide with one asymmetric carbon atom. It
exists as two stereoisomers, and has been chosen as the reference carbohydrate to represent
the structure of all other carbohydrates. The D- and L-isomers are mirror images of each
other. The special orientation of —H and —OH groups on the carbon atom (C5 for glucose)
that is adjacent to the terminal primary alcohol carbon determines whether the sugar is D- or
L-isomer. If the —OH group is on the right side, the sugar is of D-series, and if on the left
side, it belongs to L-series. The D and L configuration of Glyceraldehyde and Glucose are
shown in Fig 1.

Fig.1. D and L configuration.

It may be noted that the naturally occurring monosaccharides in the mammalian tissues are
mostly of D-configuration.

Optical activity of sugars:

Optical activity is a characteristic feature of compounds with asymmetric carbon atom. When
a beam of polarized light is passed through a solution of an optical isomer, it will be rotated
either to the right or left. The term dextrorotatory (+) and levorotatory (-) are used to
compounds that respectively rotate the plane of polarized light to the right or to the left.

Derivatives of Monosaccharide’s:
There are several derivatives of monosaccharides, some of which are physiologically
important:

1. Amino sugars:

When one or more hydroxyl groups of the monosaccharides are replaced by amino groups,
the products formed are amino sugars e.g. D-glucosamine, D-galactosamine. They are present
as constituents of heteropolysaccharides.

Glucosamine

2. Deoxysugars:

These are the sugars that contain one oxygen less than that present in the parent molecule. D-
2-Deoxyribose is the most important deoxysugar since it is a structural constituent of DNA.

3. L-Ascorbic acid (vitamin C):

This is a water- soluble vitamin, the structure of which closely resembles that of a
monosaccharide.
 Ascorbic acid

Functions of Carbohydrates :

1. They are the most abundant dietary source of energy (4 Cal/g) for all organisms.

2. Carbohydrates are precursors for many organic compounds (fats, amino acids).

3. Carbohydrates (as glycoproteins and glycolipids) participate in the structure of cell

membrane and cellular functions such as cell growth, adhesion and fertilization.

4. Carbohydrates also serve as the storage form of energy (glycogen) to meet the immediate
energy demands of the body.

Abnormality in the handling of carbohydrates in the body can lead to several diseases. The
most common disease is Diabetes mellitus. It is the single most common non communicable
disease of the world.

Lipids:

Lipids (Greek: lipos-fat) are of great importance to the body as the chief concentrated storage
form of energy, besides their role in cellular structure and various other biochemical
functions. Although lipids have received some bad publicity on account of their role in
obesity and other disorders, lipids give shape to our body and cushion the vital organs. Lipids
are a heterogeneous group of compounds. 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. Unlike the polysaccharides,
proteins and nucleic acids, lipids are not polymers. They are mostly small molecules.

Classification of Lipids:

Lipids are broadly classified according to Bloor, into simple, complex, derived and
miscellaneous lipids. Each of these main groups is further subdivided.
1. Simple lipids:

Esters of fatty acids with alcohols.These are mainly of two types:

(a) Fats and oils (triacylglycerols):

These are esters of fatty acids with glycerol. The difference between fat and oil is only
physical. Thus, oil is a liquid while fat is a solid at room temperature.

(b) Waxes:

Esters of fatty acids, usually with long chain alcohols other than glycerol. Cetyl alcohol(C16 )
is most commonly found in waxes.

2. Complex (or compound) lipids:

Esters of fatty acids with alcohols containing additional groups such as phosphate,
nitrogenous base, carbohydrate, and protein . They are further divided as:

(a) Phospholipids:

Lipids containing phosphoric acid and frequently a nitrogenous base. This is in addition to
alcohol and fatty acids.

(b) Glycolipids:

These lipids contain a fatty acid, carbohydrate and nitrogenous base. The alcohol is
sphingosine, hence they are also called as glycosphingolipids. Glycerol and phosphate are
absent e.g., cerebrosides, gangliosides.

(c) Lipoproteins:

Macromolecular complexes of lipids with proteins.

(d) Other complex lipids:

Sulfolipids, amino- lipids and lipopolysaccharides are among the other complex lipids.

3. Derived lipids:
These are the derivatives obtained on the hydrolysis of group I and group 2 lipids which
possess the characteristics of lipids. These include glycerol and other alcohols, fatty acids,
mono- and diacylglycerols, lipid soluble vitamins, steroid hormones, hydrocarbons and
ketone bodies.

4. Miscellaneous lipids:

These include a large number of compounds possessing the characteristics of lipids e.g.,
carotenoids, squalene, hydrocarbons such as pentacosane (in bees wax), terpenes etc.The
lipids which are uncharged are referred to as neutral lipids. These are mono-, di-, and
triacylglycerols, cholesterol and cholesteryl esters.

Fatty Acids:

Fatty acids are carboxylic acids with hydrocarbon side chain. They are the simplest form of
lipids.

Fatty acid with 12 Carbons (Lauric acid)

Even and odd carbon fatty acids:

Most of the fatty acids that occur in natural lipids are of even carbons (usually 14C-20C).
This is due to the fact that biosynthesis of fatty acids mainly occurs with the sequential
addition of 2 carbon units. Palmitic acid (16C) and stearic acid (18C) are the most common.
Among the odd chain fatty acids, propionic acid (3C) and valeric acid (5C) are well known.

Saturated and unsaturated fatty acids:

Saturated fatty acids do not contain double bonds, while unsaturated fatty acids contain one
or more double bonds. Both saturated and unsaturated fatty acids almost equally occur in the
natural lipids. Fatty acids with one double bond are known as monounsaturated and those
with 2 or more double bonds are collectively known as polyunsaturated fatty acids (PUFA).

Shorthand representation of fatty acids:

Instead of writing the full structures, biochemists employ shorthand notations (by numbers)
to represent fatty acids. The general rule is that the total number of carbon atoms is written
first, followed by the number of double bonds and finally the (first carbon) position of double
bonds, starting from the carboxyl end. Thus, 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.

Unsaturated fatty acids- ω 3 and ω 6

Fatty acids are numbered generally from the carboxyl functional group. They can be
numbered from the methyl end of the fatty acids. From the methyl end if the first double bond
is between 3rd and 4th carbon, that fatty acid is called ω 3. If the first double bond is between
6th and 7th carbon, it is called ω 6

Essential fatty acids:

The fatty acids that cannot be synthesized by the body and, therefore, should be supplied in
the diet are known as essential fatty acids (EFA). Chemically, they are polyunsaturated fatty
acids, namely linoleic acid (18 : 2; 9, 12) and linolenic acid (18 : 3; 9, 12, 15). Arachidonic
acid (20 : 4; 5, 8, 11, 14) becomes essential, if its precursor linoleic acid is not provided in the
diet in sufficient amounts.

Triacylglycerols:

Triacylglycerol’s (formerly triglycerides) are the esters of glycerol with fatty acids. The fats
and oils that are widely distributed in both plants and animals are chemically
triacylglycerol’s. They are insoluble in water and non-polar in character and commonly
known as neutral fats.

Fats as stored fuel:

Triacylglycerol’s 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 caloric requirements for 2-3 months.

Phospholipids:

These are complex or compound lipids containing phosphoric acid, in addition to fatty acids,
nitrogenous base and alcohol.

There are two classes of phospholipids:

1. Glycerophospholipids (or phosphoglycerides) that contain glycerol as the alcohol, e.g.

lecithins(PC), cephalins (PE), phosphatidylinositol, phosphatidylserine, plasmalogens.
 PLASMALOGEN

Platelet activating Factor(PAF) is an important plasmalogen. In its structure the sn2

position is esterified by acetate instead of a fatty acid.

2. Sphingophospholipids that contain sphingosine as the alcohol, e.g. sphingomyelin,

ceramide.

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, very
low density lipoproteins (VLDL), low density lipoproteins (LDL), high density lipoproteins
(HDL) and free fatty acid-albumin complexes.

High Density Lipoprotein (HDL)

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.

There are several steroids in the biological system. These include cholesterol, bile acids,
vitamin D, sex hormones and adrenocortical hormones. If the steroid contains one or more
hydroxyl groups it is commonly known as sterol (means solid alcohol).

Functions of Lipids:

Lipids perform several important functions:

1. They are the concentrated fuel reserve of the body (triacylglycerols).

2. Lipids are the constituents of membrane structure and regulate the membrane permeability
(phospholipids and cholesterol).

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 prostaglandins
and second messengers such as ceramide and Diacyl glycerol).