CHEMISTRY OF CARBOHYDRATES

Definition

➢ Carbohydrates may be defined as polyhydroxy-aldehydes or ketones or compounds

which produce them on hydrolysis.

Functions

1. Main sources of energy (4Cal/g) in the body, e.g. Brain cells and RBCs are almost wholly
dependent on carbohydrates.
2. Storage form of energy (starch and glycogen).
3. Precursors for many organic compounds (fats, amino acids).
4. Carbohydrates (glycoproteins and glycolipids) participate in the structure of cell membrane
and cellular functions such as cell growth, adhesion and fertilization.
5. Structural components of many organisms, e.g. fibers of plants, cell wall of micro-
organisms.
6. Utilized as raw materials for several industries, e.g. papers, plastics, textiles, alcohols etc.

Classification
Based on the number of sugar units, carbohydrates are broadly classified into 3 groups.
1. Monosaccharides
2. Oligosaccharides
3. Polysaccharides

1. Monosaccharides
(Mono: one, Saccharide: sugar)
➢ Simplest groups of carbohydrates- also called as simple sugars.
➢ General formula: Cn(H2O)n.
➢ Can not be further hydrolysed.

Classification of monosaccharides with selected examples.

Monosaccharides Aldose Ketose

• Trioses (C3H6O3) • Glyceraldehydes • Dihydroxyacetone
• Tetroses (C4H8O4) • Erythrose • Erythrulose
• Pentoses (C5H10O5) • Ribose • Ribulose
• Hexoses (C6H12O6) • Glucose • Fructose
• Heptoses (C7H14O7) • Glucoheptose • Sedoheptulose

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2. Oligosaccharides
(Oligo: Few)

➢ Contain 2-10 monosaccharide molecules which are liberated on hydrolysis.

I. Disaccharides
➢ On hydrolysis produce 2 molecules of the same or different monosaccharides.
➢ General formula: Cn(H2O)n-1

Examples:

❖ Maltose Glucose + Glucose

❖ Sucrose Glucose + Fructose
❖ Lactose Glucose + Galactose

II. Trisaccharides

❖ Raffinose Fructose + Galactose + Glucose

III. Tetrasaccharides

❖ Stachyose 2 moles of Galactose + Glucose + Fructose

IV. Pentasaccharides
❖ Verbascose 3 moles of Galactose + Glucose + Fructose

3. Polysaccharides
❖ Polysaccharides are polymerized products of many monosaccharide units.
❖ General formula : (C6H10O5)n

They are of 2 Types.

I. Homopolysaccharides (Homoglycans)

➢ Polymer of same monosaccharide units.

➢ Examples: Starch, Glycogen, Inulin, Cellulose etc.

II. Heteropolysachharides (Heteroglycans)

➢ Polymer of different monosaccharide units.

➢ Examples : Heparin, Chondroitin Sulfate etc.

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MONOSACCHARIDES

ISOMERISM OF MONOSACHHARIDES

Stereoisomers
➢ Compounds having same structural formula but differing in special configuration are
known as stereoisomers. E.g.

1. Optical activities

➢ It 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 and left.

2. Epimers
➢ Two monosaccharides differ from each other in their configuration around a single specific
carbon atom.
➢ Glucose and Mannose are epimers with regard to carbon 2 (C2-epimers).
➢ Glucose and Galactose are epimers with regard to carbon 4 (C4-epimers).

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3. Anomers (Mutarotation)
➢ The α and β cyclic forms of D-glucose are known as anomers.
➢ They differ from each other in the configuration only around C1 known as anomeric carbon.
➢ In case of α anomer, the –OH group held by anomeric carbon is on the opposite side of the
group –CH2OH of sugar ring. The reverse is true for β-anomer.

Mutarotation
➢ Mutarotation is defined as the change in the specific optical rotation representing the
interconversion of α and β forms of D-glucose to an equilibrium mixture.
➢ When D-glucose is crystallized at room temperature and afresh solution is prepared, its
specific rotation of polarized light is +112o, but after 12-18 hours it changes to +52.5o. If
initial crystallization is taking place at 98oC and then solubilised, the specific rotation is
found to be +19o, which also changes to +52.5o within a few hours. This change in rotation
with time is called mutarotation.

α-D-Glucose Equillibrium mixture β-D-Glucose

+112o +52.5o +19o

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REACTIONS OR PROPERTIES OF MONOSACCHARIDES (CARBOHYDRATES)

1. Tautomerization or Enolization
➢ The process of shifting a hydrogen atom from one carbon atom to another to produce
enediols is known as Tautomerization.
➢ When glucose is kept in alkaline solution for several hours, it undergoes isomerization to
form fructose and mannose.
➢ This interconversion of sugars through a common enediol is called Lobry de Bruyn-Van
Ekenstein transformation.
➢ The enediols are highly reactive, hence sugars in alkaline solution are powerful reducing
agents.

2. Reducing properties
➢ In the laboratory, many tests are used to identify the reducing action of sugars. These
include Benedict’s test, Fehling’s test, Barfoed’s test etc.
➢ The enediol form or sugars reduce cupric ions (Cu2+) of copper sulphate to cuprous ions
(Cu+), which form a yellow precipitate of cuprous hydroxide or a red precipitate of cuprous
oxide.
Sugar

CuSO4 Enediol
Sugar acid

Cu2+ Cu+

2H2O + Cu2O 2Cu(OH)

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3. Oxidation

➢ Depending upon the oxidizing agent, the terminal aldehyde (or keto) or the terminal alcohol
or both the groups may be oxidized.
• Oxidation of aldehyde group results in the formation of gluconic acid.
CHO COOH

• Oxidation of terminal alcohol group leads to the production of glucuronic acid.

CH2OH COOH
• Oxidation of both the groups (aldehyde and alcohol) gives glucasaccharic acid.

4. Reduction
➢ When treated with reducing agents such as sodium amalgam, the aldehyde or keto group
of monosaccharide is reduced to corresponding alcohol.
H
2H
H-C=O H-C-OH
R R

Examples
❖ D-Glucose D-Sorbitol
❖ D-Galactose D-Dulcitol
❖ D-Mannose D-Mannitol

5. Dehydration
➢ When treated with concentrated sulfuric acid, monoaccharides undergo dehydration with
an elimination of 3 water molecules.
➢ Hexoses give hydroxymethyl furfural and pentoses give furfural on dehydration.
➢ These furfurals can condense with phenolic compounds to form coloured products.
Example: Molisch test
H-C=O H-C=O
H-C-OH C
HO-C-H Conc. H2SO4 H-C
H-C-OH H-C O

H-C-OH 3H2O C
CH2-OH CH2OH
D-Glucose Hydroxymethyl furfural

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6. Osazone formation

➢ When reducing sugars are boiled with phenylhydrazine in acetic acid results in the
formation of osazone.

Glucose + Phenylhydrazine

Glucohydrazone

Glucosazone

7. Formation of esters

➢ The alcoholic group of monosaccharides may be esterified by non-enzymatic or enzymatic

reactions.
➢ Esterification of carbohydrates with phosphoric acid is a common reaction in metabolism.
➢ Examples : Glucose-6-phosphate and Glucose-6-phosphate

GLYCOSIDES
➢ When the hemi-acetal group (hydroxyl group of the anomeric carbon) of a monosaccharide
is condensed with an alcohol or phenol group, it is called a glycoside. The non-
carbohydrate group is called aglycone.
➢ The bond so formed is known as glycosidic bond.

Physiologically important glycosides

➢ Cardiac glycosides : Digoxin and digitoxin contain the aglycone steroid and they stimulate
muscle contraction.
➢ Streptomycin : an antibiotic used in the treatment of tuberculosis.
➢ Ouabain : inhibits Na+- K+ ATPase and blocks the active transport of Na+.

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DERIVATIVES OF MONOSACCHARIDES

➢ There are several derivatives of monosaccharides, some of which are physiologically

important.

1. Sugar acids

Oxidation of aldehyde or primary alcohol group in monosaccharide results in sugar acids. E.g.
Gluconic acid and glucuronic acid from glucose.
 Oxidation of aldehyde group results in the formation of gluconic acid.

CHO COOH

 Oxidation of terminal alcohol group leads to the production of glucuronic acid.

CH2OH COOH

 Oxidation of both the groups (aldehyde and alcohol) gives glucosaccharic acid.

2. Sugar alcohols

➢ They are produced by reduction of aldoses or ketoses. E.g sorbitol from glucose and
mannitol from mannose.

H
2H
H-C=O H-C-OH
R R

Examples
❖ D-Glucose D-Sorbitol
❖ D-Galactose D-Dulcitol
❖ D-Mannose D-Mannitol
3. Amino sugars

➢ When one or more hydroxyl groups of the monosaccharides are replaced by amino groups,
the products formed are amino sugars. Eg D-glucosamine, D-galactosamine.

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5. Deoxysugars

➢ These are the sugars that contain one oxygen less than that present in the parent molecule.
E.g. D-2-Deoxyribose.

DISACCHARIDES

➢ When two monosaccharides are combined together by glycosidic linkage, a disaccharide

is formed.
➢ General molecular formula : C12H22O11

It is of two types.

I. Reducing : disaccharides with free aldehyde or keto group. Eg maltose, lactose.

II. Non-reducing : disaccharides with no free aldehyde or keto group. Eg sucrose.

Maltose (malt sugar)

➢ Maltose is formed by two α-D-glucose units held together by α (1 4) glycosidic bond.

➢ It is not found in free form in the body.

➢ It is produced during the course of digestion of starch by the enzyme amylase.
➢ It gives osazone formations (Sunflower shaped).

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Sucrose (Cane sugar)
➢ Sucrose mostly produced by sugar cane, sugar beets and various fruits.
➢ It is made up of α-D-Glucose and β-D-Fructose.

➢ These two monosaccharides are held together by a glycosidic bond (α1 β2), between C1
of α-glucose and C2 of β-Fructose.
➢ The reducing groups of glucose and fructose are involved in glycosidic bond, hence sucrose
is a non-reducing sugar, and it cannot form osazones.
➢ Also called as “Invert sugar”.
➢ It is the major carbohydrate produced in the photosynthesis.
➢ It is sweeter than most other common sugars (except fructose) namely glucose, lactose and
maltose. Hence it is used as a sweetening agent is food industry.
➢ Sucrose is hydrolysed by sucrase into glucose and fructose in intestine which are absorbed.

Lactose (Milk sugar)

➢ It is present in milk hence called as milk sugar.
➢ Lactose is composed of β-D-galactose and β-D-glucose held together by β(1 4) glycosidic
bond.

➢ It is a reducing sugar and forms osazone (powder puff or hedgehog shape).

➢ It is the most important sugar in the nutrition of young mammals.
➢ It is hydrolyzed by the intestinal enzyme lactase to glucose and galactose.

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POLYSACCHARIDES

➢ Polysaccharides are polymerized products of many monosaccharide units.

➢ It is of 2 types

1. Homopolysaccharides (Homoglycans)

➢ Polymer of same monosaccharide units.

➢ Examples : starch, glycogen and cellulose.
2. Heteropolysaccharides (heteroglycans)
➢ Polymer of different monosaccharide units.
➢ Examples : hyaluronic acid, chondroitin sulphate.

STARCH

Sources : Potatoes, cereals (rice, wheat) and other food grains.

• It is the reserve carbohydrate of plants, which is the most important dietary sources for
higher animals, including man.
• Starch is composed of amylose and amylopectin.
• When starch is treated with boiling water, 10-20% is solubilised; this part is called amylose
and non-solubilised (80-90%) part is called amylopectin.
• Amylose is made up of glucose units with α (1 4) glycosidic linkages to form an
unbranched long chain with a molecular weight 400,000 D or more.
• Amylopectin is also made up of glucose units with α (1 6) glycosidic linkage to form
highly branched long chain with molecular weight more than 1 million.
• Starches are hydrolysed by amylase (pancreatic or salivary) to liberate dextrins and finally
maltose and glucose units.

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INULIN

➢ Polymer of D- fructose units with repeating β(1 2) linkages.

➢ It is the reserve carbohydrate present in various bulbs and tubers such as onion, garlic etc.
➢ It is a low molecular weight (around 5,000) polysaccharide easily soluble in water.
➢ It is not utilized by the body.
➢ It is used for assessing kidney function through measurement of glomerular filtration rate.

GLYCOGEN

• It is the reserve carbohydrate in animals, hence also called as animal starch.

• It is present in high concentration in liver, followed by muscle, brain etc.
• It is also present in plans that do not possess chlorophyll e.g. yeast, fungi.
• Excess carbohydrates are deposited as glycogen.
• Glycogen is composed of glucose units joined by α(1 4) links in the straight chains and
α(1 6) linkages at branching points.
• Molecular weight = about 5 million .

Glycogen

CELLULOSE

• It is exclusively found in plants.

• It constitutes 99% of cotton, 50% of wood and is the most abundant organic material in
nature.
• It is made up of glucose units combined with β(1 4) linkages.
• It has a straight line structure, with no branching points.
• Molecular weight = 2-5million.

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HETEROPOLYSACHARIDES

➢ They are composed of two or more different monosaccharides, e.g. hyaluronic acid,
chondroitin sulphate.
MUCOPOLYSACCHARIDES OR GLYCOSAMINO GLYCANS (GAG)

• Mucopolysaccharides are heteropolysaccharides containing uronic acid and amino sugars.

• It also contain acetylated amino groups, sulfate and carbnoxy groups.
• Mucopolysaccharides in combination with proteins form mucoproteins (mucoids or
proteoglycans).
• The important mucopolysaccharides are hyaluronic acid, heparin, chondroitin sulfate,
dermatan sulfate and keratin sulfate.

HYALURONIC ACID (D-glucuronate + GlcNAc)

• Sources : Connective tissues, tendons, synovial fluid and vitreous humor.

• It serves as a lubricant in joint cavities.
• It is composed of alternate units of D-glucuronic acid and N-acetyl D-glucosamine held
together by β(1 3) glycosidic bond.

Figure: Hyaluronic acid

HEPARIN (D-glucuronate sulfate + N-sulfo-D-glucosamine)

• An anticoagulant.
Sources
❖ Blood, liver, lung, kidney, spleen, monocytes etc.
Function
❖ Activates anti-thrombin III, which in turn inactivates thrombin, factor X and factor IX.

Uses :
➢ For clinical studies when taking blood in vitro.
➢ To prevent intravascular coagulation in vivo in suspected thromboembolic conditions.
Structure
Composed of alternative units of glucuronate 2-sulfate and N-sulfo D-glucosamine-6-sulfate.

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CHONDROITIN SULPHATE (D-glucuronate + GalNAc sulfate)

• Sources : major constituent of various mammalian tissues such as bone, cartilage, tendons,
heart, valves, skin cornea etc
• It is composed of repeating disaccharide units consists of D-glucuronic acid and N-acetyl
D-galactosamine 4-sulfate.

KERATAN SULPHATE (Gal + GlcNAc sulfate)

• Sources: Cornea, tendons etc

• It is the only GAG which does not contain any uronic acid.
• The repeating units are galactose and N-acetyl glucosamine-6-sulfate in β-linkage.

DERMATAN SULPHATE (L-iduronate + GlcNAc sulfate)

• Sources: Skin, blood vessels and heart valves.

• It contains L- iduronic acid and N-acetyl galactosamine-4-sulfate in β (1 3) linkages.

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Biomedical importance
1. Chief source of energy.
2. Constituents of compound lipids and conjugated proteins.
3. Certain carbohydrate derivatives are used as drugs like cardiac glycosides, antibiotics.
4. Lactose principal sugars of milk in lactating mammary gland.
5. Degradation products utilized for synthesis of other substances such as fatty acids,
cholesterol, amino acids etc.
6. Mucopolysaccharides act as lubricants.
7. Inherited deficiency of certain enzymes in metabolic pathways of different
carbohydrates can cause diseases such as galactosemia, glycogen storage diseases,
lactose intolerance etc.
8. Derangement of glucose metabolism is seen in diabetes mellitus.

Long Essays
• Define and classify carbohydrates with suitable examples. Add a note on the functions of
carbohydrates.
• Describe the structure and functions of mucopolysaccharides.
• Discuss the structure and functions of 3 biochemically important disaccharides.
• Discuss polysaccharides.

Short Essays
• Define and classify carbohydrates with suitable examples.
• Add a note on the functions of carbohydrates.
• Isomerism of monosaccharides.
• Describe the properties of monosaccharides.
• Add a note on modified monosaccharides.
• Disaccharides
• Polysaccharides
• Describe mucopolysaccharides.

Short notes
• Epimers
• Mutarotation
• Osaone formation
• Glycosidic bond
• Sugar derivatives
• Anomers
• Enediol
• Amino sugars
• Invert sucrose
• Deoxysugars

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