BCH 202 Lecture

Lecturer: Dr Timothy Bulus

Topic: CHEMISTRY AND BIOLOGICAL FUNCTIONS OF CARBOHYDRATES

Scope of study: This topic will cover basic chemistry of monosaccharides, Classification and
functions of carbohydrates. Mention should be made of the nature of the specific bonding found
in oligo- and polysaccharides and how they relate to biological functions. Attempt will be made
to relate key diseases to carbohydrate chemistry /function.
Basic Definition of carbohydrates
Carbohydrates- are polyhydroxy carbonyl compounds (aldehydes and ketones) and their
derivatives. Their derivatives are substances that yield carbohydrates upon hydrolysis. All
carbohydrates, therefore, possess a carbonyl groups and at least two hydroxyl groups.

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 Student Exercise-1
Learn to draw the Fischer Projection Formulae of the L- and the D- forms of the
following simple sugars:
Glucose, Fructose, Mannose, Galactose, Arabinose, Ribose, Ribulose, Xylose and
Xylulose

Common carbohydrates and their occurrence in nature

Carbohydrates are widely distributed in nature, occurring mainly in plants and animals.
Carbohydrates are the most abundant biomolecule in life (Nelson and Cox, 2017).
Glyceraldehyde and Dihydroxy acetone are the simplest carbohydrates and are found as
intermediates of metabolic pathways.
Glucose is the most important carbohydrate (monosaccharide); in animals most polysaccharides
are hydrolyzed and absorbed as glucose. It is a major precursor of energy synthesis in the body
as well as the precursor for synthesis of all other carbohydrates.
Fructose is found in fruits, Sucrose in sugar cane and lactose in milk.
Cellulose is an important polysaccharide and ribose, galactose, mannose, lactose

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Functions of carbohydrates
Carbohydrates are known to have structural and metabolic roles in living organisms.
Some of the major functions of carbohydrates include:
i. Carbohydrates are the main sources of energy in the body. Brain cells and red blood cells
(RBCs) are almost exclusively dependent on carbohydrates as the energy source.
ii. Carbohydrates also serve as storage form of energy- glycogen in animals and starch in
plants.
iii. Glycoproteins and glycolipids are components of cell membrane and receptors. In these
forms, carbohydrates act as signals that determine the intracellular location or metabolic
fate of some biomolecules. In microorganisms surface saccharides can participate in
recognition and adhesion between cells.
iv. Carbohydrate polymers (also called glycans) are structural components of many
organisms. For example, cellulose is a structural component of plant cell wall. The cell
wall of microorganism is made of peptidoglycan moieties while mucopolysaccharides
exist as ground substance in higher organisms.

Classification of carbohydrates
The general molecular formula of carbohydrates is Cn(H2O)n. Glucose has the molecular formula
C6H12O6.
The major classes of carbohydrates are:
i. Monosaccharides-are also referred to as simple sugars, have only one polyhydroxy
aldehyde or ketone units. They can not be further hdrolysed into smaller units.
ii. Disaccharides- are carbohydrates formed when two monosaccharides are chemically
linked together with the elimination of a molecule of water.
iii. Trisaccharides-contain three monosaccharides
iv. Tetrasaccharides-contain four sugar groups.
v. Oligosaccharides- contain few monosaccharide units. Therefore, trisaccharides,
tetrasaccharides and pentasaccharides are oligosaccharides.
vi. Polysaccharides- This class of carbohydrates contained many monosaccharides
covalently bound to each other in a linear or branched chain structure. Example of
polysaccharides are starch and cellulose.s

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Chemistry of simple sugars (Monosaccharides)
Simple sugars exhibit different forms of isomerism
i. Aldose -Ketose isomerism:
Simple sugars are either aldehydes or ketones with two or more hydroxyl groups.
Monosaccharide having aldehyde group are called aldose sugars (aldoses) while those carrying
ketone group are called ketoses. Monosaccharides are also named according to their respective
carbon chain length: those containing three carbons (e.g. D-glyceraldehyde and
Dihydroxyacetone) are called trioses while those with four, five or six carbons are referred to
as tetroses, pentoses and hexoses respectively. There are aldoses and ketoses of each of this
chain lengths. Thus, glucose and ribose are aldohexose and aldopentose sugars, while fructose
and ribulose are ketohexose and ketopentose sugars respectively. Enzymes that catalyze the
conversion of an aldose sugar to its ketose isomer are known as Isomerases.

ii. Optical Isomers and D and L isomerism

Stereoisomerism in Monosaccharides
The presence of asymmetric (chiral) carbon atoms in these molecules make them to exhibit
optical activity and to occur in different isomeric forms. In solution, glucose is dextrorotatory,
and so glucose solutions are sometimes known as dextrose. Stereoisomerism is a phenomenon
in which compounds have same chemical formula but differ in the spatial arrangement of their
substituents (in the case of carbohydrates, the H and OH groups). The number of stereoisomers
that can occur in a chiral compound is normally given by 2n ,where n is the number of chiral
carbon(s) in the compound.
For example, Glyceraldehyde has 2 stereoisomers. Aldohexoses with four chiral centers have 24
= 16 stereoisomers.
Enantiomers are stereoisomers that are nonsuperimposable mirror images of each other. D-
glyceraldehyde and L-glyceraldehyde are good examples of enantiomers.
In stereochemistry, stereoisomers pairs of stereoisomers that are not mirror images of each other
are called diastereomers.

C HO C HO

H C OH HO C H

C H2OH C H2OH

D-G lyceraldehyde L-G lyceraldehyde

C OOH
C OOH
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H C NH2 H2N C H

C H3 C H3

D-Alanine L-Alanine
Using D-glyceraldehyde and L-glyceraldehyde as references, it is possible to group stereoisomers
of an optically active compound as either D- or L- isomers, on the basis of the configuration
about the chiral center most distant from the carbonyl carbon; Those in which the configuration
at this reference carbon is the same as that of D-glyceraldehyde are designated D isomers, while
those with configuration similar to L- glyceraldehyde are L-isomer (as shown for D- and L-
glucose below). Glucose is known to occur in nature as D- isomer and not the L-form.

iii. Epimerism
Epimerism and Epimers of glucose
When sugars are different from one another , only in configuration with regard to a single carbon
atom, other than the reference carbon atom, they are called a pair of epimers and the phenomenon
is referred to as epimerism.
For example, Mannose is an epimer of glucose at C2 while Galactose is an epimer of Glucose at
C4. Note that Galactose and Mannose are not epimers but diastereoisomers.

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 iv. Occurrence of different cyclic/ring structures
In aqueous solution, aldotetroses (e.g. erythrose) and all monosaccharides with five or more
carbon atoms in the backbone occur predominantly as cyclic structures.
The ring arises as a result of a covalent bond formed between the carbonyl group and the oxygen
of a hydroxyl group along the chain. There are two forms of this ring structures:a six-membered
pyran ring (pyranose) or a five-membered furan ring (furanose). Th structures below are the
basic shape of the pyran and the furan ring.

More than 99 % of glucose in solution exist in the pyranose form

The reaction above is called the synthesis of hemiacetal or hemiketal. In monosaccharides, the
hemiacetal is formed between the carbonyl carbon and the oxygen atom present in the
participating hydroxyl group (in glucose, it is OH of carbon 5) as described by the diagram below.

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 v. Anomerism in ring structures of sugars
The reaction between the aldehyde group at C-1 and the hydroxyl group at C-5 forms a hemiacetal
linkage, as described above. However, this new ring structure produces an additional pair of
stereoisomers, the α and β anomers. Isomeric forms of monosaccharides that differ only in their
configuration about the hemiacetal or hemiketal carbon atom are called anomers, and the
carbonyl carbon atom is called the anomeric carbon.
The ring structures of monosaccharides can be drawn using both Fischer Projection Diagram
and the Haworth Perspective Formula (as illustrated with D-glucose below).
To draw the Haworth Perspective formula of any monosaccharides, the following point might be
useful guide:
(a). remember that pyranoses are six-membered rings while furanoses are five-membered rings .
(b). Beginning from carbon 1, number other carbon atoms in a clockwise direction.
(c). Draw the Fischer structure of the sugar (L or D form).
(d). Identify the OH group to be used and use it to form the Fischer Ring structure. In the Fischer
Projection, when the hydroxyl group at the anomeric carbon is on the same side (cis) of the carbon
chain of Fischer Projection as the oxygen atom at the highest numbered asymmetric carbon, the
configuration at the anomeric carbon is α, and if the relationship is trans (i.e. at opposite sides),
then the configuration is β.

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(e). While drawing the Haworth Perspective formula, note that the groups on the left side of the
carbon backbone of the Fischer Projection in (d) above, will appear above the plane of the
Haworth Formula, while groups to the right-hand side will appear below the plane.
(f). Due to torsion required to effect ring closure, the H substituent at C-5 (for α-D-
glucopyranose) will appear below the plane instead of above it.

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 Student Exercise-2
1. Draw the Fischer Projection Daigram and Harworth Perspective
Formulae of the following sugars:
i. α-D-glucopyranose
ii. α-D-Fructofuranose
iii. β-L-glucopyranose
iv. β-D-glucofuranose
v. β-L-glucofuranose
vi. α-L-Fructopyranose
vii. β-D-Mannopyranose
viii. β-L-Arabinofuranose
ix. β-L-Arabinopyranose
x. α -D-galactofuranose

2. Name the following structures

In aqueous solution, it is possible for one ring form to convert into another. This process is known
as mutarotation. In this process, one ring form (for example, the α anomer) first form a linear
structure briefly before forming a different anomeric form (in this case, the β anomer). In most
cases, such a mixture of glucose anomers contains threefold concentration of the β-D-glucose
over α-D;glucose.