Carbohydrates

chemistry
Dr. Mohammad Waseem Kausar
Assistant professor.
Imdc. biochemistry
Some properties of m/s with
reference to glucose
chiral Carbon :

ISOMERS=
2n.
 Chirality rules.

1.Monosaccharides contain one or more

asymmetric C-atoms: get D- and L-forms,
where D- and L- designate absolute
configuration
2.D-form: -OH group is attached to the right of
the asymmetric carbon
3.L-form: -OH group is attached to the left of
the asymmetric carbon
4.If there is more than one chiral C-atom:
absolute configuration of chiral C furthest
away from carbonyl group determines
whether D- or L-
Enantiomers
isomerism
the pairs of structures that
are mirror images of each
other.
The vast majority of the
sugars in humans are D-
sugars.
In the D isomeric form, the
OH group on the
asymmetric carbon (a
carbon linked to four
different atoms or groups)
farthest from the carbonyl
carbon is on the right,
in the L-isomer it is on the
left.
Enzymes known as
racemases are able to
interconvert D- and L-
Racemic solution = equal amount of d and l
 no optical activity
Resolution = the separation of optically active
isomers from a racemic mixture.
Ring formation / Ring structure

An aldose: Glucose
A ketose: Fructose
Ring Structure (Cyclization)
Linear known as “Fischer” structure”
Ring know as a “Haworth projection” 3 D
representation
Cyclization via intramolecular hemiacetal (hemiketal)
formation
C-1 becomes chiral upon cyclization - anomeric
carbon
Anomeric C contains -OH group which may be α or β
(mutarotation α ⇔ β )
m/s having 5 or more C occurs predominantly in
cyclic (ring)form owing to a reaction b/w carbonyl C
& an alcohol.
These structures have lower energies than the
straight chain forms. Aldohexosein cyclic form have
5 asymmetric C so 32 isomers.
The two cyclic compounds α and β have different
optical rotations.
Mutarotation
 Mutarotation is a term given to the change
in the observed optical rotation of a
substance with time.
 Glucose, for example, can be obtained in
either its α or β -pyranoseform. The two
forms have different physical properties such
as melting point and optical rotation.
 When either form is dissolved in water, its
initial rotation changes with time. Eventually
both solutions have the same rotation.
Mutarotation of Glucose
H O
C CH 2 OH
.. H
H C OH H O
..
or
HO C H H
C C
H C OH OH O
HO
H C OH
OH +
H
C H 2OH

CH 2OH C H 2OH
O O
OH anomeric
OR carbon
OH
OH atom
HO OH HO

OH OH

α-D-glucose β-D-glucose

[+112.2°] [+18.7°]
Mutarotation of Fructose

CH2 OH
HOCH2 O CH2 OH HOCH 2 O OH
C O
HO C H
HO OH HO CH OH
H C OH 2

OH H C OH
OH
CH2 OH

α-D-Fructose D-Fructose β-D-Fructose

OPTICAL ACTIVITY
The presence of asymmetric carbon
atoms also confers optical activity on
the compound. When a beam of
plane-polarized light is passed through
a solution of an optical isomer, it will
be rotated either to the right,
dextrorotatory (+); or to the left,
levorotatory (−). The direction of
rotation is independent of the
stereochemistry of the sugar, so it may
be designated D(−), D(+), L(−), or L(+).
For example, the naturally occurring
form of fructose is the D(−) isomer.
E P IM E R S
• Carbohydrate isomers
that differ in
configuration around
only one specific
carbon atom (with the
exception of the
carbonyl carbon)
Epimers: Isomers
differing as a result
of variations in
configuration of the
-OH and -H on carbon
atoms 2, 3, and 4 of

glucose are known as

epimers. . For example,
glucose and galactose
are C-4 epimers ,their
structures differ only in
R e d u cin g su g a rs
If the oxygen on the anomeric carbon of a
sugar is not attached to any other
structure, that sugar can act as a
reducing agent and is termed a reducing
sugar. Such sugars can react with
chromogenic agents
the anomeric carbon of the sugar
becoming oxidized.
the other hydroxyl groups on the molecule
are not involved.]

SOME PROPERTIES OF
MONOSECCHARIDES
1. formation of polyols or alcohol
when carbonyl gp is reduced to a
hydroxyl gp
Keto sugar of more then 3 c can

yeild more then one sugar

alcohal because of creation of
new asym- center at c2. e.g
fructose yeild a mixture of
sorbitol & mannitol.
Glyceradehyde & DHA = glycerol
Mannose = mannitol

 sorbitol (DM)
 Sugar alcohol though derived from
reducing m/s are not reducing
agents, exist only in straight chain
form
