Unit -III

Carbohydrates
 Introduction

• Carbohydrates are aldehyde or ketone

compounds with multiple hydroxyl groups.

• Empirical formula (CH2O)n , where n=3 or

more
 Carbohydrates constitute a versatile class of molecules

• Energy from the sun captured by green plants, algae, and some bacteria during

photosynthesis is stored in the form of carbohydrates. In turn, carbohydrates are the

metabolic precursors of virtually all other biomolecules.

• Breakdown of carbohydrates provides the energy that sustains animal life.

• Carbohydrates are covalently linked with a variety of other molecules. Carbohydrates linked

to lipid molecules, or glycolipids, are common components of biological membranes.

• Proteins that have covalently linked carbohydrates are called glycoproteins. These two classes

of biomolecules, together called glycoconjugates, are important components of cell walls and

extracellular structures in plants, animals, and bacteria.

• Enable recognition between cell types or recognition of cellular structures by other

molecules. Recognition events are important in normal cell growth, fertilization,

transformation of cells, and other processes.

 Roles
1. Carbohydrates serve as energy stores, fuels, and metabolic
intermediates.
2. Ribose and deoxyribose sugars form part of the structural framework of
RNA and DNA.
3. Polysaccharides are structural elements in the cell walls of bacteria and
plants

All of these functions are made possible by the characteristic chemical

features of carbohydrates:
(1) the existence of at least one and often two or more asymmetric centers,
(2) the ability to exist either in linear or ring structures,
(3) the capacity to form polymeric structures via glycosidic bonds, and
(4) the potential to form multiple hydrogen bonds with water or other
molecules in their environment
 Carbohydrate nomenclature
Carbohydrates are generally classified into three groups:
• monosaccharides
• oligosaccharides,
• and polysaccharides.
The monosaccharides are also called simple sugars and have the formula (CH2O)n.
Monosaccharides cannot be broken down into smaller sugars under mild conditions.
Oligosaccharides derive their name from the Greek word oligo, meaning “few,” and
consist of from two to ten simple sugar molecules. Disaccharides are common in
nature, and trisaccharides also occur frequently. Four- to six-sugar-unit
oligosaccharides are usually bound covalently to other molecules, including
glycoproteins.
Polysaccharides are polymers of the simple sugars and their derivatives. They may be
either linear or branched polymers and may contain hundreds or even thousands of
monosaccharide units. Their molecular weights range up to 1 million or more
 Monosaccharides
Monosaccharides consist typically of three to seven carbon atoms and are described
either as aldoses or ketoses, depending on whether the molecule contains an
aldehyde function or a ketone group.

The simplest aldose is glyceraldehyde, and the simplest ketose is dihydroxyacetone.

These two simple sugars are termed trioses because they each contain three
carbon atoms.

Hexoses are the most abundant sugars in nature. Nevertheless, sugars from all these
classes are important in metabolism

ENANTIOMERS (mirror images)

 Monosaccharides: Aldoses and
ketoses
• Colorless, crystalline solids
• Soluble in water but insoluble in nonpolar
solvents
• Most have a sweet taste.
• 2 classes:
– Aldose: If the carbonyl group is at an end of the
carbon chain
– Ketose: carbonyl group is at any other position
• There are more possible configurations of the
aldose form than ketose due to the presence of
more chiral carbons found in aldoses.
 TRIOSES
PENTOSE SUGAR OF NUCLEIC ACID

HEXOSES
The structures and names of a family of aldoses and ketoses with three, four, five, and
six carbons
For molecules that possess two or more
chiral centers, more than two stereoisomers
can exist. Pairs of isomers that have opposite
configurations at one or more of the chiral
centers but that are not mirror images of
each other are called diastereomers.
Two sugars that differ in configuration at only
one chiral center are described as epimers.
For example, D-mannose and D-talose are
epimers and D-glucose and D-mannose are
epimers, whereas D-glucose and D-talose are
not epimers but merely diastere omers
• Monosaccharides with four, five, six, and seven carbon atoms are called tetroses,
pentoses, hexoses, and heptoses.

• Stereochemistry: Aldoses with at least three carbons and ketoses with at least four
carbons contain chiral centers. For monosaccharides with two or more asymmetric
carbons, the prefix D or L refers to the configuration of the highest numbered
asymmetric carbon (the asymmetric carbon farthest from the carbonyl carbon). A
monosaccharide is designated D if the hydroxyl group on the highest numbered
asymmetric carbon is drawn to the right in a Fischer projection, as in D-glyceraldehyde.

• D-forms of monosaccharides predominate in nature (These preferences, established in

apparently random choices early in evolution, persist uniformly in nature because of
the stereospecificity of the enzymes that synthesize and metabolize these small
molecules)

• L-Monosaccharides do exist in nature, serving a few relatively specialized roles. L-

Galactose is a constituent of certain polysaccharides, and L-arabinose is a constituent of
bacterial cell walls
 Common monosaccharides exist as
cyclic structures
• In aqueous solution, monosaccharides with 5 or
more C-atom assume a ring structure, which is more
stable.
• An aldehyde can react with an alcohol to form
a hemiacetal.
• Similarly a ketone can react with an alcohol to form
a hemiketal.
 The Cyclic Structure of
Monosaccharides: Haworth Structures
The cyclic structure of monosaccharides is commonly represented
using Haworth projections, named after the English chemist Sir
Walter N. Haworth

Haworth Structures for glucose

• In Glucose, the C-1 aldehyde in the open-chain
form of glucose reacts with the C-5 hydroxyl
group to form an intramolecular hemiacetal

• The resulting cyclic hemiacetal, a six-membered

ring, is called pyranose.
The designation α means that the hydroxyl group attached to C-1 is below the plane
of the ring; β means that it is above the plane of the ring. The C-1 carbon atom is
called the anomeric carbon atom, and the a and b forms are called anomers
In fructose, the C-2 keto group in the open-chain form can react with the C-6
hydroxyl group to form a six-membered cyclic hemiketal or a 5-membered ring.
 Monosaccharides Are Reducing Agents

Reducing sugars: Monosaccharides can be oxidized by mild

oxidizing agents such as ferric (Fe3+) or cupric (Cu2+) ion.

Basis of Fehling’s reaction/Benedict’s reaction

By measuring the amount of oxidizing agent reduced by a

solution of a sugar, it is also possible to estimate the
concentration of that sugar

Diagnosis of diabetes (old method)

 Oxidation of the anomeric carbon of glucose and other sugars is the basis
for Fehling’s reaction.

 All monosaccharides and all common disaccharides (except

sucrose) are reducing sugars.
 Mutarotation
The α and β anomers of D-glucose interconvert
in aqueous solution by a process called
mutarotation.
An equilibrium mixture of glucose contains
approximately one-third alpha anomer, two-
thirds beta anomer, and <1% of the open
chain form
Disaccharides Contain a Glycosidic Bond
 Disaccharides consist of two monosaccharides joined
covalently by an O-glycosidic bond.
 Examples: maltose, lactose, and sucrose
 Because sugars contain many hydroxyl groups,
glycosidic bonds can join one monosaccharide to
another.
 Glycosidic bonds are formed when a hydroxyl group of
one sugar reacts with the anomeric carbon of the
other.
Formation of a disaccharide
 Almost all disaccharides are reducing
sugars
1. The oxidation of a sugar’s anomeric carbon by cupric or ferric ion
(Fehling’s/Benedict’s reaction) occurs only with the linear form,
which exists in equilibrium with the cyclic form(s).

2. Exceptions: In disaccharides like sucrose and trehalose, the

anomeric carbon is involved in a glycosidic bond; hence, sugar
residue cannot take the linear form and therefore becomes a
nonreducing sugar.

 Reducing sugars: Sugars with a free aldehyde or ketone group

 All monosaccharides and some disaccharides are reducing sugars.

Why is Sucrose a non-reducing sugar?

TREHALOSE

The glycosidic bond involves both anomeric

carbons; therefore there is no free aldehyde group
 SUCROSE
LACTOSE

Glucose Fructose
Galactose Glucose
α, β (1->2) glycosidic bond β (1->4) glycosidic bond
Hydrolysis of lactose:
Lactase in human beings
β-galactosidase in bacteria

MALTOSE

Hydrolysis of maltose:
Glucose Maltase
Glucose
Maltose is obtained from
the hydrolysis of starch
α(1->4) glycosidic bond
Oligosaccharides
• short chains of monosaccharide units, or
residues, joined by characteristic linkages
called glycosidic bonds.
• sucrose (cane sugar): D-glucose and D-
fructose
Polysaccharides are sugar polymers containing more than
20 or so monosaccharide units, and some have
hundreds or thousands of units.

Cellulose: linear chains; glycogen: branched