Topics Discussed

Classification of Carbohydrates
Monosaccharides: Cyclic structure, optical activity,
isomerism, properties
Oligosaccharides:
Disaccharides - maltose, lactose, cellobiose, sucrose,
trehalose;
Trisaccharides - rhafinose;
Tetrasaccharides - stacchyose
Polysaccharides:
Homopolysaccharides - starch, dextran, glycogen,
cellulose, chitin;
 
Carbohydrates (sugars) are organic compounds
containing carbon, hydrogen and oxygen with
the general formula CnH2nOn

Polyhydroxy aldehydes or polyhydroxy ketones

Definition
The term ―carbohydrate‖ comes from the
observation that when you heat sugars, you get
carbon and water (hence, hydrate of carbon).
Sugar, and also the starches that we find in foods,
such as bread, pasta, and rice.
 Function
Carbohydrates are compounds of tremendous biological
importance:
they provide energy through oxidation = 4.2kcal/gm

they serve as a form of stored chemical energy

they form part of the structures of some cells and

tissues

They constitute an important part of free nucleotides,

DNA, RNA and coenzymes
Classification
 Monosaccharides - simple sugars with multiple
OH groups. Based on number of carbons (3, 4, 5,
6), a monosaccharide is a triose, tetrose, pentose
or hexose.
 Disaccharides - 2 monosaccharides covalently
linked.
 Oligosaccharides - a few monosaccharides
covalently linked.
 Polysaccharides - polymers consisting of chains of
monosaccharide or disaccharide units.
 Monosaccharides
Aldoses (e.g., glucose) have an Ketoses (e.g., fructose) have a
aldehyde group at one end. keto group, usually at C2.

H O
C CH2OH

H C OH C O

HO C H HO C H

H C OH H C OH

H C OH H C OH

CH2OH CH2OH

D-glucose D-fructose
 D vs L Designation
O H O H
D or L refers to the asymmetric C
farthest from the aldehyde or C C
keto group.
H – C – OH HO – C – H
HO – C – H H – C – OH
The D-conformations are
H – C – OH HO – C – H
physiologically metabolizable, H – C – OH HO – C – H
while the L-conformations are
not. CH2OH CH2OH
D-glucose L-glucose
Cyclic Structure of Monosaccharides
Pyran
 OH H
CHO H OH  6CH2OH 
C O OH .... H
H C OH H 5
H C OH H
HO C H 4 1
HO C H OH H
H C OH OH H ...... OH 
H C OH 3 2
H C OH H C O
CH2OH CH2OH H OH

Fischer's Haworth's
Open Chain - and -anomers,
(- and -anomers)
Gluco-Pyranose

Glucose

Furan
CH 2OH 6 1
CH 2OH   CH 2OH O CH 2OH ..... OH
HO OH
C O C
HO C H HO C H 5 H OH
2
H C OH H C OH
H C OH
H 4 3 OH ....... CH2OH
H C O 
CH 2OH CH 2OH
OH H

Fischer's Haworth's
Open Chain (- and -anomers) - and -anomers,
Fructo-Furanose

Fructose
 1
CHO

H C OH
2
HO C H D-glucose
3
H C OH (linear form)
4
H C OH
5
CH2OH
6

6 CH2OH 6 CH2OH
5 O 5 O
H H H OH
H H
4 H 1 4 H 1
OH OH
OH OH OH H
3 2 3 2
H OH H OH
-D-glucose -D-glucose
These representations of the cyclic sugars are called
Haworth projections.
 Isomerism in Carbohydrates
Isomers :
are substances that have the same molecular formula
but differ in distribution of the atoms into functional
groups (structural isomers) or their spatial
arrangement (stereoisomers).

Structural isomerism
It is shown by the isomers that have the same carbon
skeleton but differ in the nature of the main functional
group, e.g., aldo-/keto- isomers such as glucose and
fructose.
 Stereoisomerism
 Epimers –
are isomers that differ in distribution of H and OH groups around a
single asymmetric carbon atom, other than the anomeric and sub-
terminal carbons. e.g. Ribose is a C3-epimer of xylose, and
Glucose is a C2-epimer of mannose and C4-epimer of galactose
CHO CHO
H OH HO H
HO H HO H
H OH H OH
H OH H OH
CH2OH CH2OH
D-glucose D-mannose

epimers
Anomers
These are isomers that differ in distribution of H and OH groups
around the asymmetric anomeric carbon atom after cyclization of
the molecule, e.g., - and -glucopyranose

6 CH 2 OH 6 CH 2 OH
5 O 5 O
H H H OH
H H
4 H 1 4 H 1
OH OH
OH OH OH H
3 2 3 2
H OH H OH
-D -glucose -D -glucose

(OH below the ring)
  (OH above the ring).
D and L isomers (enantiomers):
the two D- and L-forms appear as mirror
images of each other.

CHO CHO

H C OH HO C H

CH2OH CH2OH

D-glyceraldehyde L-glyceraldehyde

CHO CHO

H C OH HO C H

CH2OH CH2OH
D-glyceraldehyde L-glyceraldehyde
 Sugar derivatives
CH 2OH CH 2OH

H O H H O H
H H
OH H OH H

OH OH OH O OH
H NH 2 H N C CH 3
H
-D-glucosamine -D-N-acetylglucosamine

1. Amino sugar - an amino group substitutes for a

hydroxyl. An example is glucosamine.
The amino group may be acetylated, as in
N-acetylglucosamine.
 Sugar derivatives
COOH CHO
CH2OH
H C OH H C OH
H C OH
HO C H HO C H
H C OH
H C OH H C OH
H C OH
H C OH H C OH
CH2OH
CH 2OH COOH
D-ribitol
D -gluconic acid D -glucuronic acid

 sugar alcohol - lacks an aldehyde or ketone; e.g., ribitol.

 sugar acid - the aldehyde at C1, or OH at C6, is oxidized
to a carboxylic acid; e.g., gluconic acid, glucuronic acid.
 O H

H3C C NH O COO
R HC OH
H H R=
HC OH
H OH
CH2OH
OH H
N-acetylneuraminate (sialic acid)

N-acetylneuraminate (N-acetylneuraminic acid, also

called sialic acid) is often found as a terminal residue
of oligosaccharide chains of glycoproteins.
Sialic acid imparts negative charge to glycoproteins,
because its carboxyl group tends to dissociate a
proton at physiological pH, as shown here.
Glycosidic Bonds

The anomeric hydroxyl and a hydroxyl of

another sugar or some other compound can join
together, splitting out water to form a glycosidic
bond:

R-OH + HO-R'  R-O-R' + H2O

Disaccharides
Two monosaccharides can be linked together
through a glycosidic linkage to form a
disaccharide
 Reducing disaccharides
Maltose: is a disaccharide with an (1 4) glycosidic link
between C1 - C4 OH of 2 glucoses. It is the  anomer (C1 O points
down). 6 CH 2 O H 6 CH 2 O H

5 O 5 O
H H H H
H H
1 4 1
4 OH H OH H

OH O OH
3 2 3 2

H OH m a lto se H OH

Lactose:  anomer (O on C1 points up). The (1 4) glycosidic

linkage is represented as a zig-zag, but one glucose is actually
flipped over relative to the other
Non reducing sugars

Sucrose (table sugar): -It is formed of -glucose

linked to -fructose by --1,2-glycosidic linkage
24
25  Homo- and Heteropolysaccharides
Homopolysaccharides
Structural homopolysaccharide
= cellulose ( β 1-4 glucose)
= chitin (β 1-4 N-Acetayl glucosamine)
= pectin (β 1-4 galactoseamine)
Storage homopolysaccharide
= inulin (β 1-2-fructose) onions
= glycogen (α 1-4, α 1-6) Glucose
= starch
amylose (α 1-4) glucose
amylopectin (α 1-4, α 1-6) Glucose
 Hetero  Different
Polysachharides composed of different type of monosaccaharide
units are known as ‘Hetero-polysaccaharides’.
They have repeating units of two or three monosaccaharide and
generally contain an amino-sugar and a uronic acid.
They are also known as ‘Muco-Polysachharides’.

Functions
Provide shape & extracellular support for cells & tissues,
Act as lubricants
Mediate in the cell-cell interactions.
Act as biological anti-coagulants and anti-freeze agents
Immunogenic and serve as targets for detection and
development of vaccines against the bacteria and viruses
Serve as the receptors for hormones
 Heteropolysachharides

Non-Nitrogenous HP Nitrogenous HP
Plant
Gums Neutral Acidic
Pectins Capsular
Agar Haptens
Sulfated Sulfate free
Blood GroupKeratan Sulfate
Hyaluronic
Substances Chondroitin
acid
Adhesion Sulfate
Chondroitin
Molecules Heparin
 Polysaccharides:
1.Starch
Storage form of carbohydrate in plant
= amylose and amylopectin = glucose polymers

Glucose storage in polymeric form minimizes osmotic effects.

Amylose is a glucose polymer with (14) linkages.

The end of the polysaccharide with an anomeric C1 not involved in a

glycosidic bond is called the reducing end.
CH 2 OH 6 CH OH CH 2 OH CH 2 OH CH 2 OH
2
O 5 O H O H O H H O H
H H H H H
H H H H H
OH H 1 4 OH H 1 OH H OH H OH H
O O O O OH
OH 2
3
H OH H OH H OH H OH H OH
a m y lo s e
 CH 2 OH CH 2 OH
H O H H O H amylopectin
H H
OH H OH H 1
O
OH
O
H OH H OH

CH 2OH CH 2 OH 6 CH 2 CH 2 OH CH 2OH
H O H H O H H 5 O H H O H H O H
H H H H H
OH H OH H OH H 1 4 OH H OH H
4 O O
O O OH
OH 2
3
H OH H OH H OH H OH H OH

Amylopectin is a glucose polymer with mainly (14)

linkages, but it also has branches formed by (16)
linkages
2. Glycogen
Glucose storage polymer in animals
Glycogen has more (16) branches than that of Starch

The highly branched structure permits rapid glucose release

from glycogen stores, e.g., in muscle during exercise.

CH 2 OH CH 2 OH
H O O
glycogen
H H H
H H
OH H OH H 1
O
OH
O
H OH H OH

CH 2 OH CH 2 OH 6 CH 2 CH 2 OH CH 2 OH
H O H H O H H 5 O H H O H H O H
H H H H H
OH H OH H OH H 1 4 OH H OH H
4 O O
O O OH
OH
3 2
H OH H OH H OH H OH H OH
 3. Cellulose,
A major constituent of plant cell walls, consists of
long linear chains of glucose with (14) linkages.

CH2OH 6CH OH CH2OH CH2OH CH2OH

2
O 5 O O H O H O OH
H H H
H H H H H
OH H 1 O 4 OH H 1 O OH H O OH H O OH H
OH H H H
H 2 H
3
H OH H OH H OH H OH H OH
cellulose
 CH 2 O H
D -glucuron ate 6
 H 5 O
6 COO H
4 1 O
O H
H 5
H OH H
4 H 1 3 2
OH
H H NH COCH 3
3 2 O
H OH N -acetyl- D -gluco sam ine
hyaluronate

4. Glycosaminoglycans
-Are linear polymers of repeating disaccharides.

-The constituent monosaccharides tend to be

modified, with acidic groups, amino groups, sulfated
hydroxyl and amino groups, etc.