Outlines

 Carbohydrates

o Definition

o Classification
CHEMISTRY OF CARBOHYDRATES
 Monocaccharides

o Classifications

o Isomerism

o Derivatives

CLASSIFICATION
DEFINITION Carbohydrates are classified according to the hydrolytic products as follows:
 Carbohydrates (CHO) are aldehyde or ketone
derivatives of polyhydric alcohols or any substances
derived from them.
 • Based on number of sugar units present:
• Monosaccharides: Cannot be hydrolyzed further into
simpler forms.
• Disaccharides: Yield 2 molecules of same or different
monosaccharide units on hydrolysis e.g. sucrose, lactose
and maltose.
Monosaccharides
• Oligosaccharides: Yield 3-10 molecules of
monosaccharide units on hydrolysis.
• Polysaccharides: Yield more than 10 molecules of same
or different monosaccharide units on hydrolysis.
 Homo-& Heteropolysaccharides.

MONOSACCHARIDES
MONOSACCHARIDES
฀ Simplest group of carbohydrates, cannot be further
hydrolysed.
No. of C-atoms
฀ Categorization of monosaccharides is based on:
carbonyl group
• the Functional Group. (Aldehyde or keto).
Trioses
• the Number of Carbon atoms. Tetroses
Pentoses Aldoses Ketoses
Hexoses
Heptoses
 MONOSACCHARIDES BASED
ON FUNCTIONAL GROUP

Aldehyde CHO Ketone C O

• An aldose is a carbohydrate with aldehyde functionality.

• A ketose is a carbohydrate with ketone functionality.
 PENTOSES
These monosaccharides contain three carbon atoms. The smallest aldose
in human body is glyceraldehyde and the smallest ketose in human body
is dihydroxyacetone.

glyceraldehyde dihydroxyacetone

Hexoses:

These monosaccharides contain 6 carbon

atoms. The physiologically important
hexoses are glucose, galactose, fructose
and mannose.
 Fructose:
Glucose:
• It is present in fruit juices and honey.
• It is the most important sugar of carbohydrates present in
• Fructose can be changed to glucose in the liver and
fruit juices and result from the hydrolysis of starch, cane
sugar, maltose and lactose. intestine, so it can be used in the body.
• Glucose is the sugar carried by the blood and is the • Fructose serves as the major energy source of
principal sugar used by the tissues. spermatozoa. It provides the fuel for sperm while they
• It is the major source of energy ( Mainly for RBCs). are in seminal fluid.
• It is present in urine in cases of diabetes mellitus due to
• Fructose accumulation occurs in hereditary fructose
raised blood glucose.
intolerance. (hypoglycaemia, enlarged liver
(hepatomegaly), liver failure).

Galactose: Isomerism
• It is formed during hydrolysis of lactose (milk sugar). • Isomers are different compounds that have the
• Galactose can be changed to glucose and same molecular formula but different structural
or stearic formula
metabolized.
• structural isomers, in which the atoms are
• It is synthesized in the mammary gland to make the
joined in a different order, so that they have
lactose of milk. different structural formulae
• It is a constituent of glycolipids and glycoproteins.
• stereoisomerism, in which the order in which
the atoms are joined is the same, but the
• Galactose accumulation occurs in galactosemia molecules have a different spatial arrangement
( jaundice, Diarrhea, severe weight loss , Cataracts, of the atoms and hence different three
liver damage and kidney problems). dimensional shapes.
 STEREOISOMERS
Asymmetric carbon atom
Isomers are compounds having the same structural formula but
differ in spatial configuration.
• The formation of isomers is caused by the presence of
asymmetric carbon atoms i.e. carbon atoms attached to 4
different atoms.
• The number of possible isomers of a compound depends on
the number of asymmetric carbon atoms (n) and is equal to
2n. For example, glucose has 4 asymmetric carbon atoms, so – The carbon atom which is surrounded by
the number of isomers = 16 isomers. four different atoms or groups is called
asymmetric carbon atom.
• All monosaccharides have asymmetric carbon atoms except
dihydroxyacetone.

Types of isomers
C3 H6 O3
(1) D and L isomers: Same Molecular formula
A special type of isomerism in the pairs of structures that are

mirror images of each other (Enantiomers).

CHO CHO

•This type of isomerism named according to the orientation of H C OH HO C H

the -H and -OH groups around the carbon atom adjacent to the CH2OH
CH2OH
terminal primary alcohol carbon (C5 in glucose) .

D-glyceraldehyde L- glyceraldehyde
•When the -OH group is on the right, the sugar is a member of
the D-series, when it is on the left, It is a member of the L-series.
Most of naturally occuring are D sugars.
 O H O H Enantiomers
non-superimposable mirror images
C C (also called optical isomers)

H – C – OH HO – C – H
W W
HO – C – H H – C – OH
H – C – OH HO – C – H C C
X Y Y X
H – C – OH HO – C – H Z Z
CH2OH CH2OH
D-glucose L-glucose

(2) Alpha and beta isomers (Anomers)

These are isomers differing in the configuration of -OH
and -H on C1 in the cyclic structure
Pyranose and Furanose ring structure:
The cyclic structure of glucose is favored and
accounts for most of its chemical properties.
 The stable ring structures of monosaccharides are
similar to the ring structures of either pyran or furan.
99% of glucose in solution is in the pyranose form.
 1
CHO 6 CH2OH 6 CH2OH

H C OH 5 O 5 O
2 H H H OH
H H
HO C H D-glucose 4
OH H 1 4 OH H 1
3
H C OH (linear form) OH OH OH H
4 3 2 3 2

H C OH H OH H OH
5
-D-glucose -D-glucose
CH2OH
6

6 CH2OH 6 CH2OH
Cyclization of glucose produces a new asymmetric
5 O 5 O
H H H OH
H H
center at C1. The 2 stereoisomers are called
4 H 1 4 H 1
OH OH
OH OH OH H anomers,  & . the OH at the anomeric C1:
3 2 3 2
H OH H OH ฀  (OH below the ring).
-D-glucose -D-glucose ฀  (OH above the ring).

1
CH2OH

2C O

HO C H
1 CH2OH
3 HOH2C 6 O
H C OH HO
4 5 H 2

H C OH H 4 3 OH
5
OH H
6
CH2OH

D-fructose (linear) -D-fructofuranose

(3) Epimers: CARBON-2 EPIMERS
• These are isomers differing in the configuration of
H C O H C O
the -OH and -H on carbon atoms 2 or 3 or 4 of
H C OH HO C H
glucose.
HO C H HO C H
• The most important epimers of glucose are
H C OH H C OH
mannose and galactose.
H C OH H C OH
• Mannose is formed by epimerization at carbon 2
CH2OH CH2OH
whereas, galactose by epimerization at carbon 4.
D-GLUCOSE D-MANNOSE

CARBON-4 EPIMERS (4) Aldoses and Ketoses:

• Depending on the presence of aldehyde or keto group in
H C O H C O
the sugar.
H C OH H C OH • Fructose contains ketone group in position 2, whereas
HO C H HO C H there is an aldehyde group in position 1 of glucose.

H C OH HO C H
H C OH H C OH
CH2OH CH2OH
D-GLUCOSE D-GALACTOSE
(5) Geometrical isomers
The carbonyl group - monosaccharides
there are two forms of geometrical isomers :
• The cis-Isomer :
In which the two identical atoms or groups are present in the
same side of the two carbon atoms in the molecule.
• The Trans-Isomer :
In which the two identical atoms or group are in two opposite
sides of the two carbon atoms in the molecule.

Sugar derivatives
 All monosaccharides contain a free carbonyl
group (aldo or keto). Ester formation
 So all monosaccharides are reducing sugars. Sugar acids
Sugar alcohols
 All monosaccharides reduce Benedict and
amino sugar
fehling reagents. amino sugar acids
Deoxy sugars
(Sugar derivatives)

Esterification:
Alcoholic groups of sugars react with acids to
form esters.

The most important biological esters are esters

with phosphoric acid

• Sugar acids 1.Aldonic

1. Produced by oxidation of
carbonyl carbon to carboxylic
group.
2. Or by oxidation of last hydroxy
carbon to carboxylic group.
3. Or by oxidation of both.
2-Uronic Importance of Glucuronic acid
 It is a highly polar molecule which is incorporated into
proteoglycans.( Hyaluronic acid, Heparin).

 Conjugated with bilirubin to form soluble conjugated

bilirubin. An inability to conjugate bilirubin, as in hepatic
disease , is a cause of jaundice.

 Conjugated with certain drugs in liver to increase their

solubility. Glucuronate-conjugated drugs are more
easily cleared from the blood by excretion in urine.

3-Aldaric Sugar alcohols

The sugar is reduced to the corresponding
alcohol:

1. Glyceraldehydes give glycerol

2. Dihydroxyacetone give glycerol
3. Ribose → ribitol
4. Glucose → sorbitol
5. Galactose → galactitol
6. Mannose → mannitol
7. Fructose → a mixture of equal amounts
of sorbitol & mannitol
 H

α -D fructose
β - D fructose
Importance of sugar alcohols
 They are used widely in the food industry
as sweeteners. They are commonly used
in place of table sugar (sucrose).
 Sugar alcohols are not metabolized by oral
bacteria, and so they do not contribute to
tooth decay.
 The glycerol backbone is found in all lipids
known as triglycerides(TAG), the storage
form of lipids in body.
 Glycerol is used in medical and personal
care preparations for improving
smoothness and providing lubrication
(Glycerine).
 Glycerol can be used as a laxative.
 Glycerol can cause a rapid, temporary

Ribitol is a part of the structure of vitamin B2 decrease in the internal pressure of the
(Riboflavin), eye. This can be useful for the initial
emergency treatment of severely elevated
eye pressure

•amino sugar •amino sugar acid

O H
CH2OH CH2OH
H3C C NH O COO
H O H H O H R HC OH
H H H H R=
OH H OH H HC OH
H OH
OH OH OH O OH CH2OH
OH H NANA
H NH2 H N C CH3
N-acetylneuraminate (sialic acid)
H
-D-glucosamine -D-N-acetylglucosamine N-acetylneuraminate (N-acetylneuraminic acid, also
called sialic acid) is often found as a terminal residue of
 amino sugar - an amino group substitutes for a oligosaccharide chains of glycoproteins and
hydroxyl. An example is glucosamine. glycosphingolipids.
 The amino group may be acetylated, as in Sialic acid imparts negative charge to glycoproteins,
because its carboxyl group tends to dissociate a proton
N-acetylglucosamine. at physiological pH.
Importance of sialic acid: Deoxy sugars
D 2.deoxy ribose Is derived from D.Ribose
by de-oxygenation at carbon–2. It is found
– Sialic acid is structural component in the in DNA.
terminal carbohydrate chains of
mucoproteins.

– sialic acid is increased in serum of tumour-

bearing humans , it can be considered as
tumor marker.
 L-fucous Is derived from L-galactose
by de-oxygenation at carbon–6.

Importance of L-fucose Which of the following monosaccharide

 L-fucose is usually has no assymetric carbon?
CHO CHO
located at the end HO C H HO C H
of the carbohydrate H C OH
Deoxygenation
H C OH
chains of H C OH at carbon-6 H C OH

mucoproteins. HO C H HO C H
CH2OH CH3
CH3

 L-fucose levels are L-Galactose L-Fucose

(LDDL) (6-deoxy-L-Galactose
high in urine and
blood of patients
with diabetes
mellitus, cancer and
some other
diseases.
 Glucose and galactose are epimers. This
-

 D-Glucose is based on position of (OH) means that:

to the right at
a)Carbon (.1) b)Carbon(2) a) They are mirror images of each other,

c) Carbon (3) d)Carbon(5) b) One is aldose and the other is ketose.

c) They rotate plane polarized light in opposite

directions.

d) They differ only in configuration about one

carbon atom.

 The minimum number of carbon in a

monosaccharide is
a.1
Carbohydrates are organic compounds made b. 2
c. 3
up of d. 4

a. Carbon and hydrogen All the following are monosaccharides except

a-Glucose
b. Carbon, hydrogen and oxygen
b-Fructose
c. Carbon, hydrogen, oxygen and nitrogen c-maltose

d. Carbon and oxygen d-galactose

A carbohydrate found in DNA is
a- Ribose

B-Deoxyribose

C-Ribulose

D-All of these