CHEMISTRY OF

CARBOHYDRATES
Introduction
• Carbohydrates are the most abundant organic molecules in nature.
• Composed of carbon, hydrogen and oxygen (1:2:1).
• Hydrates of carbon.
• Some of the carbohydrates possess the empirical formula Cn(H2O)n.
• Carbohydrates also known as saccharides.
Carbohydrates may be defined as polyhydroxy aldehydes or
ketones.
Functions of carbohydrates
• Main source of energy in body (4kcal/g).
• Brain cells and RBCs have an absolute requirement of carbohydrates.
• Storage form of energy (starch and glycogen).
• Excess carbohydrate is converted to fat.
Structural basis of many organisms
Classification of carbohydrates
Monosaccharides
• They cannot be further hydrolysed into smaller units.
Structure of Monosaccharides
• It can be represented in
1. Straight chain structure,
2. Ring/ Cyclic structure
3.Boat and chain form
Straight chain structure
 Ring/ Cyclic structure
• The hydroxyl group of monosaccharides can react with its own
aldehyde or keto functional group to form hemiacetal and hemiketal.
• Thus, the aldehyde group of glucose at C1 reacts with alcohol group at
C5 to form two types of cyclic hemiacetals namely α and β.
Pyranose and furanose structures
• Haworth projection formulae are depicted by a six-membered ring
pyranose (based on pyran) or a five-membered ring furanose (based
on furan). The cyclic forms of glucose are known as α-D-
glucopyranose and α-D-glucofuranose.
Properties of
Monosaccharides
• Isomersim&
• Chemical Properties
 Stereoisomers
• Compounds having same structural formula, but differing in spatial configuration are known as
stereoisomers.
• The spatial arrangements of H and OH groups are important, since they contain asymmetric
carbon atoms.
• Asymmetric carbon means that four different groups are attached to the same carbon.
• Types of Stereoisomers
1. D and L isomerism
2. Optical isomerism St
3. Epimerism
4. Anomerism

stereoisomers
D and L Isomerism of Glucose
• D and L isomer mirror image of each other.
• The spatial orientation H & OH groups on the C-atom (C5 for glucose),
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 isomer.
• If the OH group is on the left side, the sugar is of L isomer.
• Mammalian tissue have D sugar.
 Optical Activity
• When a beam of plane-polarized light is passed through a solution of
carbohydrates, it will rotate the light either to right or to left.
• Depending on the rotation, molecules are called dextrorotatory (+) (d)
or levorotatory (-) (l).
• Racemic mixture: If D & L isomers are present in equal concentration ,
it is known as racemic mixture
Enantiomers
• Enantiomers are special type of stereoisomers, that are mirror image
of each other.
Epimers
• If two monosaccharides differ from each other in their configuration
around a single specific carbon atom, they are referred as epimers to
each other.
• Glucose and Galactose are C4 epimers.
• Glucose and Mannose are C2 epimers.
Physical Properties
• 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.
Physiologically important glycosides
• Glucovanillin (vanillin-D-glucoside) is a natural substance that imparts
vanilla flavour.
• Cardiac glycosides (steroidal glycosides) : Digoxin and digitoxin
contain the aglycone steroid and they stimulate muscle contraction.
• Streptomycin, an antibiotic used in the treatment of tuberculosis is a
glycoside.
• Ouabain inhibits Na+ – K+ ATPase and blocks the active transport of
Na+.
• Phlorhizin produces renal damage in experimental animals.
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 (hemiacetal carbon).
 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.
α-D-Glucose Equilibrium mixture β-D-Glucose
+ 112.2° +52.7° + 18.7°
• The configuration of glucose is conveniently represented either by
Fischer formulae or by Haworth projection formulae
Chemical properties of Monosaccharides
• Tautomerization or enolization,
• Oxidation,
• Reduction,
• Furfural formation,
• Osazone formation &
• Formation of esters.
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 D-fructose and D-mannose.
Reducing properties
• The sugars are classified as reducing or non reducing. The reducing
property is attributed to the free aldehyde or keto group of anomeric
carbon.
• The enediols are highly reactive, hence sugars in alkaline solution are
powerful reducing agents.
• In the laboratory reducing action of sugars Benedict’s test, Fehling’s
test, Barfoed’s test etc.
1.Detect the presence of glucose in urine (Glucosuria).
2.Diagnose diabetes mellitus.
Oxidation
• Under mild oxidation conditions (hypobromous acid, Br2/H2O), the
aldehyde group is oxidized to carboxyl group to produce aldonic acid .
• Thus, glucose is oxidized to gluconic acid, mannose to mannonic acid
and galactose to galactonic acid.
Uronic acid
• When aldehyde group is protected, and the molecule is oxidized, the
last carbon becomes COOH group to produce uronic acid.
Saccharic acids
• Under strong oxidation conditions (nitric acid + heat), the first and last
carbon atoms are simultaneously oxidized to form dicarboxylic acids,
known as saccharic acids.
Reduction
• When treated with reducing agents such as sodium amalgam,
hydrogen can reduce sugars.
• Glucose is reduced to sorbitol; mannose to mannitol; while fructose
becomes sorbitol and mannitol.
Furfural formation
• Monosaccharides when treated with concentrated sulphuric acid
undergo dehydration with the removal of 3 molecules of water.
• Hexoses give hydroxymethyl furfural and pentoses give furfural.
Osazone Formation
• All reducing sugars will form osazones with excess of phenylhydrazine
when kept at boiling temperature.
• Osazones are insoluble.
• Each sugar will have characteristic crystal form of osazones.
• The differences in glucose, fructose and mannose are dependent on
the first and second carbon atoms, and when the osazone is formed
these differences are masked.
• Hence these 3 sugars will produce the same needle shaped crystals
DERIVATIVES OF MONOSACCHARIDES
• Amino sugars
• Amino group may be substituted for hydroxyl groups of sugars to give
rise to amino sugar.
• Generally the group is added to the second C of hexoses.
• They are non-reducing and not form osazones.
• e.g. D-glucosamine, D-galactosamine.
• Certain antibiotics contain amino sugars which may be involved in the
antibiotic activity e.g. erythromycin.
Deoxysugars
• Oxygen of the hydroxyl group may be removed to form deoxy sugars.
• They are non reducing.
• Don’t form osazones.
• Deoxyribose is present in DNA.