BIOMOLECULES

CARBOHYDRATES
DR NDOIGO .J. LYNN
 INTRODUCTION
• Carbohydrates are the most abundant
biomolecules.
• They are carbon-based molecules that are rich in
hydroxyl groups.
• Indeed, the empirical formula for many
carbohydrates is (CH2O)n—literally, a carbon
hydrate.
• are organic substances containing C, H and O
usually in the ratio of 1:2:1.
• They are defined as polyhydroxy aldehyde or
ketone derivatives
• but not all, carbohydrates have the empirical
formula (CH2O)n; some also contain nitrogen,
phosphorus, or sulfur.
• Carbohydrates are the main source of energy
in the body. Brain cells and RBCs are
exclusively depend on carbohydrates (glucose)
as the energy source.
 FUNCTIONS OF CARBOHYDRATES
1) Provides energy, i.e. as major source of
energy to the body.
2) As structural components of membranes.
3) As structural basis for DNA and RNA
(Ribose/Deoxyribose).
4) As structural basis for nucleosides and
nucleotides.
5) As source of carbon skeletons for some
amino acids.
6) As basis of some intracellular messenger
systems.
 Classification of Carbohydrates
• Carbohydrates are classified into three major
classes based on number of carbon chains
present.
• They are:
1. Monosaccharides
2. Oligosaccharides
3. Polysaccharides
All the three classes contain a saccharose group
and hence the name saccharides.
 MONOSACCARIDES
• These are simple sugars and cannot be
hydrolyzed further into simpler forms.
• Their general formula is Cn(H2O)n.
• They are also called as simple sugars.
• Monosaccharides containing three to
nine carbon atoms occur in nature.
• Monosaccharides are aldehydes or
ketones that have two or more hydroxyl
groups.
• The smallest monosaccharides, composed of
three carbon atoms, are dihydroxyacetone and
D- and L-glyceraldehyde.
• The most abundant monosaccharide in nature is
the six-carbon sugar D-glucose, sometimes
referred to as dextrose.
• Monosaccharides of four or more carbons tend to
have cyclic structures.
• Monosaccharides are further classified on the
basis of number of carbon atoms present as well
as on the presence of functional groups.
 Nomenclature
• Monosaccharides have common (trivial)
names and systematic names.
• Systematic name indicates both the number of
carbon atoms present and aldehyde or ketone
group. For example, glyceraldehyde is a simple
sugars containing three carbon atoms and a
aldehyde group.
• Simple sugars containing three carbon atoms
are referred as trioses.
• sugars containing aldehyde group or keto
group are called as aldoses or ketoses,
respectively.
• Thus, the systematic name for glyceraldehyde
is aldotriose.
• Similarly, a simple sugar with three carbon
atoms and a keto group is called as ketotriose.
Number of carbon atoms Examples Functional groups present

Trioses (3 carbon) Glyceraldehyde Aldehyde (Aldotriose)

Dihydroxyacetone

Tetroses (4 carbon) Erythrose Aldehyde (Aldotetrose)

Pentoses (5 carbons) Ribose Aldehyde (Aldopentose)

Xylose
Xylulose

Hexoses (6 carbons) Glucose Aldehyde (Aldohexose)

Galactose Aldehyde (Aldohexose)
Fructose Ketone (Ketohexose)
PROPERTIES OF MONOSACCHARIDES
PHYSICAL PROPERTIES

1. Most monosaccharides have a sweet

taste (fructose is sweetest; 73%
sweeter than sucrose).
2. They are solids at room
temperature.
 3. They are extremely soluble in water:
– Despite their high molecular weights, the
presence of large numbers of OH groups make
the monosaccharides much more water soluble
than most molecules of similar molecular
weight.
– Glucose can dissolve in minute amounts of
water to make a syrup (1 g / 1 ml H2O).
 CHEMICAL PROPERTIES OF
MONOSACCHARIDES
1. Optical Isomerism
• All the monosaccharides except
dihydroxyacetone contain at least one
asymmetric carbon (chiral) atom and hence
they exhibit optical isomerism.
• The two optical isomers of glyceraldehyde
containing one asymmetric carbon
atom(middle carbon atom) are
D-glyceraldehyde and L-glyceraldehyde. The
optical isomers are also called as enantiomers.
• D and L-glyceraldehyde are used as parent
compounds to designate all other sugars
(compounds) as D or L forms.
• the hydroxyl group on penultimate (next to
last) carbon atom points to right in ‘D’ glucose
and D- glyceraldehyde whereas it points to left
in L-glucose and L-glyceraldehyde
• D and L forms of glucose are mirror images
like mirror images of glyceraldehyde.
• Though both forms of sugars are present in
nature D-isomer is abundant and sugars
present in the body are all D-isomers.
• L-fructose and L-rhamnose are two L-isomers
found in animals and plants.
• To represent three-dimensional sugar
structures on paper, we often use Fischer
projection formulas.
• In these projections, horizontal bonds project
out of the plane of the paper, toward the
reader; vertical bonds project behind the
plane of the paper, away from the reader.
Three ways to represent the two
enatiomers of glyceraldyde
2. Optical Activity
• Monosaccharides except dihydroxyacetone
exhibit optical activity because of the
presence of asymmetric carbon atom.
• If a sugar rotates plane polarized light to right
then it is called as dextrorotatory and if a
sugar rotates the plane polarized light to the
left then it is called as levorotatory.
• Usually ‘+’ sign or ‘d’ indicates dextrorotation
and ‘–’ sign or 1 indicates levorotation of a
sugar.
• For example, D-glucose which is
dextrorotatory is designated as D(+) glucose
and D-fructose, which is levorotatory is
designated as D(–) fructose.
• The letter ‘D’ does not indicate whether a
given sugar is dextro or levorotatory.
3. Epimers
• Are those monosaccharides that differ in the
configuration of –OH group on 2nd, 3rd and 4th
carbon atoms.
• Epimers are also called as diastereoisomers.
• Glucose, galactose and mannose are examples
for epimers.
• Galactose is an epimer of glucose because,
configuration of hydroxyl group on 4th carbon
atom of galactose is different from glucose.
• Similarly, mannose is an epimers of glucose
because configuration of hydroxyl group on
2nd carbon atom of mannose is different from
glucose.
• Ribulose and xylulose are also epimers. They
differ in the configuration of –OH group on
third carbon atom
4. Functional Isomerism
• Functional isomers have same molecular
formulae but differ in their functional groups.
• For example, glucose and fructose have same
molecular formulae C6H12O6, but glucose
contains aldehyde as functional group and
fructose contains keto group.
• Hence, glucose and fructose are functional
isomers. This type of functional isomerism is
also called as aldoseketose isomerism because
aldose is an isomer of ketose and vice versa.
Aldose-ketose isomerism
5. Ring Structures
• In solution, the functional aldehyde group of
glucose combines with hydroxyl group of 5th
carbon atom. As a result a 6 numbered
heterocyclic pyranose ring structure
containing 5 carbons and one oxygen is
formed.
• The linkage between aldehyde group and
alcohol is called as ‘hemiacetal’ linkage.
• Similarly, a 5 numbered furanose ring
structure is formed from fructose when keto
group combines with hydroxyl group on 5
carbon atom.
• The linkage between keto and alcohol group is
called ‘hemiketal’ linkage.
• Both hemiacetal and hemiketal are internal or
intra-molecular linkages.
Glucose ring structure formation
 .

Formation of fructose ring structure

6. Anomers
• If the two sugars which differ in the configuration
at only C-1 in case of aldoses and C-2 in ketoses
are known as anomers and represented as alpha
and beta sugars.
• For examples:
1. α-D-glucose and β-D-glucose
2. α-D fructose and β-D-fructose.
• Those monosaccharides that differ in
configuration of OH groups on carbonyl carbon or
anomeric carbon are called as anomers.
• An additional asymmetric center is created when
a cyclic hemiacetal is formed, creating yet
another diastereoisomeric form of sugars called
anomers.
Two anomers of glucose
• Important monosaccharides in the metabolic
point of view are glucose, fructose, galactose,
ribose, erythrose and glyceraldehyde.
• Glucose is found in several fruit juice, blood of
humans and in honey.
• Galactose is a part of lactose.
• Fructose is found in several fruit juices and honey.
Commonly glucose is referred as dextrose.
• All monosaccharides containing free aldehyde or
keto group reduces ions like Cu2+ under alkaline
conditions.
Biologically Important Sugar (Glucose)
Derivatives (chemical properties)
• Sugar derivatives of biological importance are
sugar acids, sugar alcohols, deoxy sugars, sugar
phosphates, amino sugars and glycosides.
1. Sugar acids
• Oxidation of aldo group of sugars produces
aldonic acids.
• For example, oxidation of glucose produces
gluconic and oxidation of terminal alcohol group
(–OH sixth carbon atom) of glucose produces
glucuronic acid or uronic acid
• Uronic acids are components of
mucopolysaccharides and required for
detoxification.
• Ketoses are not easily oxidized.
• Vitamin C or ascorbic acid is also sugar acid.
2. Sugar alcohols
• Reduction of aldose and keto groups of sugar
produces polyhydroxy alcohols or polyols.
• These polyols are intermediates of metabolic
reactions.
• Other sugar alcohols are glycerol and inositol.
• Glucose on reduction gives sorbitol. Whereas
fructose on reduction gives a mixture of
sorbitol and mannitol.
• Mannose gives mannitol, galactose is reduced
to dulcitol and ribose to ribotol.
• The alcohols formed from glucose, galactose
and fructose are sorbitol, galactitol and
sorbitol, respectively.
4. Sugar phosphates
• Breakdown of sugar in animals involves
formation of sugar phosphates.
• Phosphorylated sugars are key intermediates
in energy generation and biosynthesis.
• the first step in the breakdown of glucose to
obtain energy is its conversion into
glucose 6-phosphate.
• Several subsequent intermediates in this
metabolic pathway, such as dihydroxyacetone
phosphate and glyceraldehyde 3-phosphate,
are phosphorylated sugars.
• Phosphorylation makes sugars anionic; the
negative charge prevents these sugars from
spontaneously leaving the cell by crossing
lipid-bilayer membranes.
• Phosphorylation also creates reactive
intermediates that will more readily form
linkages to other molecules.
• For example, a multiply phosphorylated
derivative of ribose plays key roles in the
biosynthesis of purine and pyrimidine
nucleotides
5. Amino sugars
• Those sugars in which an amino group is
substituted for a hydroxyl group.
• The amino sugars occurring most frequently
are glucosamine and galactosamine.
• They occur as N-acetyl compounds.
• Amino sugars are components of
mucopolysaccharides, and antibiotics.
• Glucosamine is present in chitin, shells of
insects and mammalian polysaccharides
whereas galactosamine is present in
polysaccharides of cartilage and chondroitin.
6. Glycosides
Are of two types:
a) O-glycosides. When hydroxyl group on anomeric
carbon of a sugar reacts with an alcohol (sugar)
O-glycoside is formed
• O-glycosidic linkage is present in disaccharides
and polysaccharides.
• So, disaccharides, oligosaccharides and
polysaccharides are O-glycosides.
• Example: Cardiac glycosides; used in cardiac
insufficiency. Ouabain; a sodium pump inhibitor
(b) N-glycosides.
• N-Glycoside is formed when hydroxyl group on
anomeric carbon of sugar reacts with an
amine.
• N-glycosidic linkage is present in nucleotides,
RNA and DNA.
• nucleotides, RNA and DNA are examples for
N-glycosides.