CARBOHYDRATES

structure and Function

Dr. Brian Osoro
Department of Biochemistry
Kampala International University Tanzania
 OVERVIEW OF CARBOHYDRATES
 Carbohydrates are defined as polyhydroxy aldehydes
or ketones or compounds which produce them on
hydrolysis.
Carbohydrates:
 The most abundant organic molecules in nature.
 The name carbohydrate literally means “hydrates of
carbon”.
 The empiric formula is (C.H2O)n where n ≥ 3.
 Carbohydrates are compounds containing carbon,
hydrogen, and oxygen in which the ratio of C:H:O is
1:2:1.
 Functions of carbohydrates
 They are the most abundant dietary source of energy (4 Cal/g)
for all organisms.
 Carbohydrates are precursors for many organic compounds
(fats, amino acids).
 Carbohydrates (as glycoproteins and glycolipids) participate in
the structure of cell membrane and cellular functions such as
cell growth, adhesion and fertilization.
 They are structural components of many organisms. These
include the fiber (cellulose) of plants, exoskeleton of some
insects and the cell wall of microorganisms.
 Carbohydrates also serve as the storage form of energy
(glycogen) to meet the immediate energy demands of the body.
 Classification of Carbohydrates
Carbohydrates, also known as saccharides
There are three major classes:
This classification is based on the number of sugar
units.
1. Monosaccharides or (simple sugar).
2. Disaccharides: contain 2 monosaccharides.
3. Polysaccharides (complex sugars): contain more than
12 monosaccharides.
Mono- and oligosaccharides are sweet to taste,
crystalline in character and soluble in water, hence they
are commonly known as sugars.
 Classification of Monosaccharides

 Monosaccharides are single sugars that

cannot be broken down into other sugars.
Often referred to as simple sugars.
 Monosaccharides are classified according
to different characteristics:
1. Based on the placement of the sugar functional group
2. Based on the number of carbon atoms it contains
 1.Based on the number of carbon atoms
 Monosaccharides are regarded as trioses (3C), tetroses (4C),
pentoses (5C), hexoses (6C) and heptoses (7C).
 These terms along with functional groups are used while
naming monosaccharides.
 2. Based on the functional sugar group:
 Aldoses: When the functional group in
monosaccharides is an aldehyde, t they
are known as aldoses.
e.g. glyceraldehyde, glucose.
 Ketoses :When the functional group is a keto
group, they are referred to as ketoses.
e.g. dihydroxyacetone, fructose.
 Monosaccharides
CONT’D

Aldose Ketose
Triose Glyceraldehyde Dihydroxyacetone
Pentose Ribose Ribulose
Hexose Glucose Fructose

The most common monosaccharides are

hexoses: glucose, fructose, and galactose.
 MONOSACCHARIDES—STRUCTURAL ASPECTS

Stereoisomerism is an important character of

monosaccharides.
Stereoisomers are the compounds that have the same
structural formulae but differ in their spatial
configuration.
A carbon is said to be asymmetric when it is attached
to four different atoms or groups.
The number of asymmetric carbon atoms (n)
determines the possible isomers of a given compound
which is equal to 2n.
Glucose contains 4 asymmetric carbons,
and thus has 16 isomers.
Glyceraldehyde—the reference
carbohydrate
Glyceraldehyde (triose) is the simplest
monosaccharide with one asymmetric
carbon atom.
It exists as two stereoisomers and has
been chosen as the referenc carbohydrate
to represent the structure of all other
carbohydrates (aldoses).
 D- and L-isomers

 The D and L isomers are mirror images of each other.

 The spatial orientation of H and OH groups on the
carbon atom (C5 for glucose) that is 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-
series, and if on the left side, it belongs to L-series.
 It may be noted that the naturally occurring
monosaccharides in the mammalian tissues are
mostly of D-configuration.
 Optical activity of sugars
 Optical activity is a characteristic feature of compounds
with asymmetric carbon atom.
 When a beam of polarized light is passed through a
solution of an optical isomer, it will be rotated either to
the right or left.
 The term dextrorotatory (d+) and levorotatory (l–) are
used to compounds that respectively rotate the plane of
polarized light to the right or to the left.
 An optical isomer may be designated as D(+), D(–), L(+)
and L(–) based on its structural relation with
glyceraldehyde.
 Racemic mixture
Racemic mixture : If d- and l-isomers are
present in equal concentration, it is known as
racemic mixture or dl mixture.
 Racemic mixture does not exhibit any optical
activity, since the dextro- and levorotatory
activities cancel each other.
 In the medical practice, the term dextrose is
used for glucose in solution. This is because of
the dextrorotatory nature of glucose.
 Epimers

If two monosaccharides differ from each

other in their configuration around a single
specific carbon (other than anomeric) atom.
For instance, glucose and galactose are
epimers with regard to carbon 4 (C4-
epimers); they differ in the arrangement of
OH group at C4.
Glucose and mannose are epimers with
regard to carbon 2 (C2-epimers).
The interconversion of epimers (e.g.
glucose to galactose and vice versa) is
known as epimerization, catalyzed by
epimerases enzymes.
 Enantiomers:
Enantiomers: special type of
stereoisomers that are mirror images of
each other, designated as D- and L-
sugars.
Majority of the sugars in the higher animals
(including man) are of D-type .
 The term diastereomers is used to represent
the stereoisomers that are not mirror images
of one another.
 STRUCTURE OF GLUCOSE

 Formation of hemiacetals and hemiketals, respectively

produced when an aldehyde or a ketone reacts with
alcohol.
 The hydroxyl group of monosaccharides react with its
own aldehyde or keto functional group to form hemiacetal
and hemiketal.
 The aldehyde group of glucose at C1 reacts with alcohol
group at C5 to form two types of cyclic hemiacetals
namely α and β.
 The configuration of glucose is conveniently represented
either by Fischer formulae or by Haworth projection formulae.
 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).
 In case of α anomer, the OH group held by anomeric
carbon is on the opposite side of the group CH2OH of
sugar ring.
 The reverse is true for β -anomer.
The anomers differ in certain physical and chemical
properties.
 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
 Mutarotation
 Mutarotation : The α and β anomers of glucose have
different optical rotations.
 The specific optical rotation of a freshly prepared glucose (α
anomer) solution in water is +112.2° which gradually changes
and attains an equilibrium with a constant value of +52.7°.
 In the presence of alkali, the decrease in optical rotation is
rapid.
 The optical rotation of β -glucose is +18.7°.
 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.
 Reducing and Non-reducing sugars

The sugars are classified as reducing or non-

reducing.
The reducing property is attributed to the free
aldehyde or keto group. E.g. Glucose
On the other hand, non-reducing sugars
do not contain free aldehyde or
ketone groups and are not capable of
reducing other compounds. E.g.
Sucrose
 Reducing Properties of Monosaccharides

 Hexose sugars with a free or potentially free

aldehyde or ketone group have reducing properties
in alkaline solutions. These reducing sugars can
reduce cupric ions (Cu+2) into cuprous ions (Cu+1).

heat
Reducing + Benedict’s pH 10.5 Cu2O + Oxidation
Sugar Reagent Product
(Cu+2) Brick Red ppt.