CARBOHYDRATES

Carbohydrates are the most abundant biomolecules on earth. Each year,

photosynthesis converts more than 100 billion metric tones of carbon dioxide and
water into cellulose and other plant products. Carbohydrates are polyhydroxy
aldehydes or ketones or substances that yield such compounds on hydrolysis.
Many but not all carbohydrates have the empirical formula (CH2O)n. Some
carbohydrates also contain nitrogen, phosphorous or sulfur. So, the carbohydrates
are defined as polyhydroxy aldehydes or ketones or their condensation products
or derived products. The basic condensing bond is glycosidic bond.

Functions of carbohydrates:
1. Carbohydrates such as sugar and starch are dietary staple in most parts of
the world and the oxidation of glucose is the central energy yielding pathway
in most cells.
2. They are the reserve or storage forms of energy in plants (starch, inulin)
and in animals (Glycogen)
3. The insoluble carbohydrate polymers serve as structural and protective
elements in the cell walls of bacteria and plants and in connective tissue
of the animals. i.e., they give structural rigidity. Eg: cellulose in cell wall,
chitin in insects and mucopolysaccharides in bacteria.
4. They are important components of nucleidc acids, coenzymes and
flavoproteins (ribose)

Classification
Carbohydrates vary greatly in size ranging from smaller glyceraldehyde
molecule to larger starch molecule. Large carbohydrate molecules are polymers of
small molecules. The carbohydrates have been classified based on the degree of
polymerization into
Monosaccharides: These are the simple sugars which cannot be further broken
down.
Oligosaccharides: They are composed of short chains of monosaccharides.
Polysaccharides: They are composed of several monosaccharide units.
Conjugated polysaccharides: In addition to carbohydrates, these polysaccharides
contain proteins and lipids also.

Monosaccharides: They cannot be further hydrolysed under normal conditions of

hydrolysis. They are further classified based on the number of carbon atoms
present in the monosaccharide into trioses (3C), tetroses (4C), pentoses (5C),
hexoses (6C) and heptoses (7C).
Based on the functional group, they are classified as aldoses and ketoses
depending on whether they have aldehyde or ketone as functional group.
Aldoses Ketoses
Triose Glyceraldehyde Dihydroxy acetone
Tetrose Erythrose Erythrulose
Pentose Ribose, Xylose, Ribulose, Xylulose
Arabinose
Hexose Glucose, Fructose
Galactose,
Mannose
Heptose Heptulose

Pentoses and hexoses are the predominant type of monosaccharides found in

nature.
Some of the biologically important aldoses and ketoses are shown in the figure.

Aldoses

D-Glyceraldehyde D- Erythrose D-Ribose

D-Xylose D-Arabinose

D-Glucose D-Mannose D-Galactose

Ketoses
 D- Erythrulose

Isomerism

a) Stereoisomerism: Most of the monosaccharides contain the same number of

atoms and the same kinds of groups, yet they are definitely distinct substance. For
example, the formula C6H12O6 represents 16 different simple sugars, all
possessing the structure CH2OH. CHOH CHOH CHOH CHOH CHO. This is due
to different arrangement of the constituent groups of the molecule in space. This
phenomenon is called as stereoisomerism and these sugars are called as
stereoisomers. For example; Glucose, mannose & galactose are stereoisomers.
When there are several asymmetric carbon atoms in a chain molecule and the end
groups are not identical, the number of stereoisomers possible is equal to 2 n where
n is the number of asymmetric carbon atoms. Thus there are 16 stereoisomers
possible corresponding to the formula CH2OH. CHOH CHOH CHOH CHOH CHO,
which contains four asymmetric carbon atoms(2n).
Monosaccharides belong to D or L series depending on the position of OH
group on the penultimate carbon atom. If OH is towards right side of the
penultimate carbon atom it is called as D sugar and if OH is towards left side of the
penultimate carbon atom it is called as L sugar. Glyceraldehyde, the simplest sugar
is used as a reference compound for representing D & L forms of sugars. The
structures of D and L glyceraldehydes are shown in the figure.
 D & L forms of sugars which are non super imposable mirror images of each
other are called enantiomers. Eg: D& L Threose molecules as shown in figure

D-Threose L-Threose

In nature, D-sugars are more widely distributed than L-sugars.

The stereoisomers which are not mirror images of each other are called
diastereomers
Eg: 1) D-Erythrose & D- Threose 2) D- Glucose, D- Mannose & D-
Galactose as shown in figure

D-Erythrose D-Threose

D-Glucose D-Mannose D-Galactose

Among the diastereoisomers, those which differ in configuration at a single carbon

atom are called epimers. Mannose is an epimer of glucose at 2nd carbon atom
whereas galactose is an epimer of glucose at 4th carbon atom whereas galactose
& glucose bear no epimeric relationship. The structural formulae of these sugars
are shown above.

a) Structural isomerism: Some compounds have same molecular formula but

different structural formulae. For example Glucose, galactose & mannose have
same molecular formula but different structures and hence they are called
structural isomers.
C )Functional isomerism: Glucose and fructose have same molecular formula but
glucose is an aldose while fructose is a ketose. This kind of isomerism is called
Functional isomerism.
d) Optical isomerism: Carbohydrates exhibit another kind of isomerism called
optical isomerism. It is shown by the compounds having an asymmetric carbon.
They have same molecular and structural formulae but differ in their behaviour
towards plane polarized light. An optical isomer rotating the plane of polarized light
toward right is called dextrorotatory ‘d’ (+) while one rotating the plane of polarized
light toward left is called levorotatory ‘l’ (-).

Ring Structures: The aldehyde or ketone group of a monosaccharide can react

with a hydroxyl group to form a covalent bond. Formally, the reaction between an
aldehyde and the hydroxyl group of a sugar (an alcohol) creates a hemiacetal
structure whereas a ketone reacts with hydroxyl group of a sugar (alcohol) to form
a hemiketal structure.

For tetroses and larger sugars, the reaction can take place within the same
molecule so that the straight chain form of the sugar cyclizes. The following figure
shows the cyclization of D-glucose to form a six-carbon ring.

A new asymmetric center is formed during cyclization of an aldehyde at C-

1. Thus two isomers of glucose exists as α – D-Glucose in which OH group at C- 1
lies below the plane of the ring and β-D-Glucose in which the OH group at C-1 lies
above the plane of ring. The C-1 carbon is called anomeric carbon atom and the
alpha and beta forms are called anomers. In aqueous solution the alpha and beta
forms are rapidly inter convertible via the open chain structure to give an
equilibrium mixture and this is termed as mutarotation. Because of the structural
similarity to the ring compound called pyran, the six membered ring structures of
hexoses are called pyranoses.
Five membered sugars such as D-ribose and D-deoxyribose and six carbon
ketose sugars such as D-fructose, form rings called furanoses as their structures
are similar to the furan ring. Again the furanoses can exists both in
alpha and beta forms except here the nomeneclature refers to the hydroxyl group
attached to C-2 which is the anomeric carbon atom.

The pyranose ring of a six-carbon aldose sugar can exist in either a boat or
a chair configuration. The substituents attached to the ring carbons that extend
parallel to the symmetry axis are said to be axial (a) whilst those that extend
outward from this axis are said to be equatorial (b) . In the boat form, there is
considerable steric hindrance between the various groups attached to the carbon
atoms of the ring and therefore this form is less favorable energetically. Hence the
chair form predominates, as shown for β-D-glucose where all the axial positions are
occupied by hydrogen atoms.

Oligosaccharides: The monosaccharides condense with each other through

glycosidic linkage to form oligosaccharides. The oligosaccharides are further
classified depending upon the number of monosaccharide units present.

Disaccharides: The hydroxyl group on the anomeric carbon atom of one

monosaccharide can react with the hydroxyl group of a second monosaccharide
to form a disaccharide. The covalent bond formed is called a glycosidic bond.

Eg: a) Lactose: It is a disaccharide formed between the anorexic carbon C-1 of

β-D-galactose and C-4 of α- D-glucose. Since the anomeric carbon of galactose
molecule is involved in the bond and is in the beta-configuration, this is called β
(14) bond which can be abbreviated as β14.
b) Maltose: It is a disaccharide formed between the C-1 and C-4 positions of
two α- D glucose units. However, here the configuration of the anomeric carbon
atom involved is the alpha form and hence the bond is called an α (14) bond or
abbreviated as α14. For lactose and maltose, one of the anomeric carbons has
been used to form the bond, leaving the second anomeric carbon free. Thus both
lactose and maltose have a reducing end. Hence they are called as reducing
disaccharides.
 c) Sucrose: It is a disaccharide formed by glycosidic bond formation between the
anomeric C-1 of α- D - glucose and the anomeric C-2 of β-D fructose so that
sucrose lacks a free reducing group. Thus sucrose is a non reducing disaccharide.
It is formed by condensation of Glucose & Fructose

Trisaccharides: Three monosaccharide units condense with each other to form

trisaccharides.
Eg: Raffinose is formed by condensation of Galactose , Glucose & Fructose

Polysaccharides: Many monosaccharide units condense to form

polysaccharides through glysosidic linkage.

Polysaccharide classification:
They are classified depending on the function, nature of branching and repeating
unit.

1. Functional classification:
a. Structural polysaccharide: Polysaccharides belonging to this class help in
maintaining the cell structure.
Eg: Cellulose, chitin, Hemicellulose, pectin.
b. Storage polysaccharide: Polysaccharides belonging to this class help in
storing carbohydrate material in the cell.
Eg: Starch, glycogen, inulin.
2. Nature of branching:
a. Linear: Polysaccharides belonging to this class have a linear glycosidic
bonding only. Eg: Cellulose, chitin, amylose
b. Branched: Polysaccharides belonging to this class have a branched
glycosidic bonding. Eg: Starch, amylopectin, glycogen.

3. Repeating Unit:
a. Homopolysaccharide: Polysaccharides belonging to this class contain the
same basic repeating monosaccharide unit. Eg:Starch, glycogen, chitin,
inulin
b. Heteropolysaccharides: Polysaccharides belonging to this class contain
more than one basic repeating unit. Eg: Hemicellulose, pectin.

Polysaccharides are long chains of sugar units joined together. Depending

on the polysaccharide, the chains may be linear or branched. In plants, the storage
form of glucose is the polysaccharide called as starch where as in animals excess
glucose is stored as a large branched polysaccharide called glycogen. These
polysaccharides serve as nutritional reserves and when
required they are broken down and the monosaccharide products are metabolized
to yield energy. In contrast, cellulose is present in cell walls and behaves as a
structural polysaccharide.

Starch: Starch exists in plants as insoluble starch granules in the cytoplasm. Each
starch molecule contains a mixture of two polysaccharide forms, amylose and
amylopectin. Amylose is unbranched polymer of glucose residues joined in α 14
linkages. Amylopectin is the branched form in which most of the glucose residues
are joined in α 14 linkages but additional α 16 bonds occur at every 25-30
residues creating the branch points.

Glycogen: Glycogen molecule consists of glucose units which are linked in long
chains by α14 bonds. For every 10 units or so, the chain is branched by the
formation of α 16 glycosidic bond. The glycogen chain terminates in a non
reducing end with a free 4’-OH group. Since the enzyme that degrades glycogen
catalyzes the removal of glycosyl units from non reducing end of glycogen chain,
the numerous branches, each with a non reducing end, greatly increase the
accessibility of the polysachharide to degradation. The α16 branches are
removed by debranching enzyme.

Dextran is a glucose polymer where the glucose residues are mainly linked by the
α 16 bonds. A few branches also occur which is formed by α12, α13 or α
14 bonds depending on the bacterial or yeast species that is the source of
dextran.

Cellulose: Cellulose is an unbranched polysaccharide of glucose units linked by

β 14 bonds. The glucose residues in cellulose are arranged as straight fibrils. In
plant cell walls, the cellulose fibrils are embedded in a matrix of other
polysachharides. In wood, the matrix also contains lignin, a complex polymer of
phenolic residues. Mammals including humans, lack enzymes capable of digesting
the β14 linkages of cellulose and so cannot digest plant cell walls.
Conjugated polysaccharides: Besides occurring in free state, the carbohydrates
occur in nature in conjugation with other biomolecules like lipids and proteins to
form glycolipids and glycoproteins. Mucopolysaccharides are glycoproteins
characterized by the presence of amino sugars like glucosamine,
galactosamine.Eg: Hyaluronic acid & Heparin.

Industrial uses:
Monosaccharides, oligosaccharides and polysaccharides are used in number of
industries as listed below:

Monosaccharides

1. Glucose and fructose are used as energy source

2. Liquid glucose is widely used in the confectionary, bakery, and jam
preparation, canning and leather industries.
3. Glucose can be fermented to biofuel ethanol.
4. Liquid dextrose is used in fermentation industries, for the manufacture of
dextrose monohydrates, fructose and sorbitol syrups.
5. Sorbitol syrup is widely used in tooth paste, pharmaceuticals, cosmetics
and tobacco industries.
6. Fructose is used as sweetener in beverages, sport drinks and also used
as a flavoring agent.
7. Fructose is used in cosmetic and pharmaceutical industry

Oligosaccharides

1. Sucrose is used in confectionery industry and in desserts.

2. Sucrose is used in preservation of foods.
3. Sucrose is used in cosmetic and pharmaceutical industry.
4. Maltose is used in baby food industry.

Polysaccharides

1. Food industry: Starch plays a leading role in determining the texture of

many foods and texture is of vital concern to both the consumers and
the manufacturers. Starch finds numerous uses in the baking industry
for the production of cakes, cookies, in ice-cream preparations etc
2. Paper industry: In Paper industry, a large quantity of starch is consumed
as a surface-sizing agent, as a binder, as a paper coating agent etc.
Starch is used in the manufacture of various adhesives or glues for book-
binding, wall paper adhesives, gummed paper, envelop adhesives,
school glues and bottle labeling
3. Textile industry: In textile industry, starch is used in sizing to strengthen
the warp yarn, in finishing and changing the appearance of fabric after it
is bleached, dyed or printed. Starch is used as a component in finishing
agent to glaze and polish sizing thread. Clothing starch or laundry starch
is a liquid that is prepared by mixing a vegetable starch in water.
4. Pharmaceutical industry: Starch is used as an excipient, a binder in
medications to aid the formation of tablets
5. Printing industry : In the printing industry, food grade
starch is used in the manufacture of anti-set-off spray
powder used to separate printed sheets of paper to
avoid wet ink being set off.
6. Plastic industry: Starch is used to produce various
bioplastics, synthetic polymers that are biodegradable.