CARBOHYDRATE

CHAPTER 1

Learning Objectives:
1. Define basic constituents of carbohydrates
2. Describe the classification, structure and
functions of carbohydrates.

Syllabus content:
1. Monosaccharide
a. Structure and stereochemistry
b. Fischer and Howarth projections
c. Reducing and non-reducing sugars

2. Oligosaccharides
a. Stability and formation of glycosidic bonds
b. Oligosaccharides structures

3. Polysaccharides
a. Structural polysaccharides
b. Storage polysaccharides

CARBOHYDRATE

1. MONOSACCHARIDE

Key words

Carbohydrate- definition
Aldose, ketose
Classification
Stereochemistry: Enantiomer, Diastreomer,
Epimer
Fischer projection, Haworth projection

Carbohydrates
Carbohydrate: most abundant biomolecules (other
biomolecules protein, lipid, nucleic acid)
Suffix ose indicates the molecule is a
carbohydrate
- glucose, fructose, maltose, sucrose, cellulose
Major role in energy metabolism and structural
component

Carbohydrates
Definition: a polyhydroxyaldehyde or
polyhydroxyketone, or a substance that
gives these compounds on hydrolysis

Carbohydrate

Three level number of sugar/saccharide unit

1. Monosaccharide simplest
2. Oligosaccharide consist more than 1
monosaccharide > disaccharide has 2
monosaccharide
3. Polysaccharide has large number of monosaccharide

Monosaccharides
Monosaccharide: simplest carbohydrate,
sometimes referred as sugar / saccharide
Building blocks of all carbohydrates
They have the general formula CnH2nOn, where n
varies from 3 to 8
Aldose: a monosaccharide containing an aldehyde
group
Ketose: a monosaccharide containing a ketone
group

Monosaccharides
Monosaccharides are classified by their
number of carbon atoms
- 3 C = triose
- 4 C = tetrose
- 5 C = pentose
- 6 C = hexose
- 7 C = heptose

Trioses are simplest carbohydrate

monosaccharides

Aldose: containing an aldehyde group

Ketose: containing a ketone group

ketotriose

ketohexose

Fischer Projections and

Haworth Projections

Fischer Projections

Fischer projection: a two dimensional representation for showing the configuration of

tetrahedral stereocenters
vertical lines represent bonds projecting forward
horizontal lines represent bonds projecting to the rear
the carbon atom at the intersection of the lines is not shown
convert to
CHO
a Fischer
CHO
projection
H
OH
H C OH

CH2 OH
D-Glyceraldehyde

CH2 OH
D-Glyceraldehyde

Fischer Projections
Fischer projection: bonds
are written in a two
dimensional
representation showing
the configuration of
tetrahedral stereocenters
horizontal lines represent
bonds projecting forward
vertical lines represent
bonds projecting to the rear
the carbon atom at the
intersection of the horizontal
and vertical lines is not
shown

Stereoisomer
mirror

1. Enantiomer
2. Diastreomer
3. Epimer

Chiral carbon

Chiral molecule

Stereoisomer
Enantiomer =
Stereoisomer that are
nonsuperimposable
mirror images of each
other
Chiral carbon/centre =
carbon atom connected to 4
different groups

mirror
Chiral carbon

Chiral molecule

Isomer:
Each of two or more compounds with the same formula but a different
arrangement of atoms in the molecule and different properties.

Enantiomer
Glyceraldehyde contains a stereocenter and
exists as a pair of enantiomers
Mirror-images stereoisomers are called
enantiomers

Stereoisomer
D,L Monosaccharides
What is D and L?
D = dextrorotary, L = levorotary

Are stereoisomers, due to the rotated

direction of plane polarized light of solution
Enantiomers: stereoisomers that are mirror
images
example: D-erythrose and L-erythrose are
enantiomers

D,L MonosaccharidesFischer Projections

According to the conventions
proposed by Fischer
D-monosaccharide: a
monosaccharide that, when
written as a Fischer projection,
has the -OH on its penultimate
carbon on the right
L-monosaccharide: a
REMEMBER: D,L= enantiomers
monosaccharide that, when
written as a Fischer projection,
has the -OH on its penultimate
carbon on the left

D,L MonosaccharidesFischer Projections

According to the
conventions
proposed by Fischer
D-monosaccharide:
has the -OH on its
penultimate carbon
on the right
L-monosaccharide:
has the -OH on its
penultimate carbon
on the left

REMEMBER: D,L= enantiomers

Diastereomers
Diastereomers: stereoisomers that are not mirror
images, non-superimposable
example: D-erythrose and D-threose are diastereomers
Epimers-diastereomer differ at only one chiral carbon

Diastereomers - example

 Enantiomers: stereoisomers that are mirror images

example: D-erythrose and L-erythrose are enantiomers
Diastereomers: stereoisomers that are not mirror images
example: D-erythrose and D-threose are diastereomers
Mirror
plane

Mirror
plane
CHO
H
OH
H
OH
CH 2 OH

CHO
HO
H
HO
H
CH 2 OH

CHO
HO
H
H
OH
CH 2 OH

CHO
H
OH
HO
H
CH 2 OH

D-Erythrose

L-Erythrose

D-Threose

L-Threose

L
O

Epimers - example
D-mannose and D-galactose differ
stereochemically from D-glucose at only 1 chiral
D-mannose and Dcenter
galactose are
EPIMERS of glucose
D-galactose is a C-4
Epimer of D-glucose

D-mannose is a C-2
Epimer of D-glucose

STRUCTURE OF MONOSACCHARIDES
Isomer = compound that have same chemical formula
Epimers = differ in configuration around one specific
carbon atom

Carbohydrate

Tutorial

Fructose

Epimers of D-fructose

D-Psicose, D-Tagatose

Enantiomers of D-fructose L-fructose

Diastrereomer of D-fructose D-Psicose, D-Tagatose, D-Sorbose

Fructose

Which structure represents D-Fructose?

Comparison of the Fischer and

Haworth Representations

Lesson outcome

Draw from Fischer to Haworth

Reaction of monosaccharide
Members of disaccharide
Disaccharide formation

What Happens if a Sugar

Forms a Cyclic Molecule?
Cyclization of sugars takes place due to interaction
between functional groups on distant carbons, C1 to C5,
to make a cyclic hemiacetal - aldose

Hemiacetal a cyclic
is formed by the r
aldehyde group with an

Cyclization using C2 to C5 results in hemiketal

formation.- ketose
In both cases, the carbonyl carbon is new chiral center
and becomes an anomeric carbon

Formation of a Cyclic
Hemiacetal

Cyclic Structure
via Haworth Projections
Monosaccharides have -OH and C=O
groups in the same molecule and exist
almost entirely as five- and six-membered
cyclic hemiacetals
anomeric carbon: the new stereocenter
resulting from cyclic hemiacetal formation
anomers: carbohydrates that differ in
configuration only at their anomeric carbons

Haworth Projections
Haworth projections
five- and six-membered hemiacetals are represented
as planar pentagons or hexagons, as the case may be,
viewed through the edge
most commonly written with the anomeric carbon on
the right and the hemiacetal oxygen to the back right
the designation - means that -OH on the anomeric
carbon is cis to the terminal -CH2OH; - means that it is
trans

Haworth Projections
A six-membered hemiacetal ring is shown by
the infix -pyran- (pyranose)
A five-membered hemiacetal ring is shown by
the infix -furan- (furanose)

CONVERTING A FISCHER PROJECTION TO A HAWORTH

Carbon 1 will be the
anomeric carbon

CHO
UP
These groups
OH
are up in
the Haworth HO
OH
This -OH
OH
determines
D- or LCH2OH
This group, which
is carbon 6, will be
up in the Haworth if
D- and down if L-

DOWN
These groups
are down in
the Haworth

This is the
b-anomer because
the anomeric OH is
cis to -CH2OH

D- 6

CH2OH
5
4

OH
OH

down

OH cis

up

1
2

OH

down

Haworth
Projections

Reaction of Monosaccharides
1.

Oxidation-reduction
i.
ii.
iii.
iv.

2.

Oxidation of aldoses to acid

Reduction of ribose to deoxyribose
Reduction of L-galactose to L-fucose (L-6deoxygalactose)
Reduction of carbonyl group to hydroxyl group forming
sugar alcohol/alditols

Esterification
i.

Formation of phosphate esters-intermediate in energy

metabolism

Oxidation
Reducing sugar: a sugar that has a
free carbonyl group (anomeric
carbon) one that can reduces an
oxidizing agent
Tollens reagent oxidizing agent

Reduction

Reduction to sugar alcohol/alditols

ribose to deoxyribose

Esterification Phosphoric Esters

Phosphoric esters are particularly important in the
metabolism of sugars to provide energy
phosphoric esters are frequently formed by transfer of a
phosphate group from ATP

Monosaccharide derivatives

Amino sugars

CARBOHYDRATE

2. DISACCHARIDE

Disaccharides
Sucrose
Table sugar; obtained from the juice of sugar cane and sugar beet
One unit of D-glucose and one unit of D-fructose joined by an -1,2glycosidic bond

Lactose
Made up of D-galactose and one unit of D-glucose joined by a -1,4glycosidic bond
Galactose is a C-4 epimer of glucose

Maltose
Two units of D-glucose joined by an -1,4-glycosidic bond
Formed from the hydrolysis of starch

Cellobiose
Two units of D-glucose joined by an b-1,4-glycosidic bond
Formed from the hydrolysis of cellulose

Sucrose
Anomeric carbons of glucose carbon C1 in
configuration is linked to the anomeric carbon of
fructose C2 in b configuration
anomeric carbon is tied into a
glycosidic bond and none of it
able to form an open chain
containing free aldehyde and
ketone sucrose is NOT a
reducing sugar

Lactose
Galactose in a (1-4) linkage with glucose
Principal sugar present in milk
Galactose is converted by the body to glucose and glucose used for
energy
Reducing sugar?

Maltose
Products from hydrolytic
breakdown of starch
Can be easily digested by
humans because of the
presence of enzymes
catalyzes the hydrolysis of
(1-4) glycosidic bonds

Reducing sugar?

Cellobiose
Cellobiose hydrolysis product of cellulose major
component of plants
Differs from maltose at glycosidic bond
Humans do not have the capacity to
digest cellobiose or cellulose lack
the enzyme cellulase that break (1-4)
glycosidic linkages between glucose
monomers
Ruminants animals can have
bacteria in the rumen in gastrointestine
tract and secrete cellulase

Disaccharides

Formation of glycosidic bond condensation (-H2O)

Haworth Projections

Anomeric
carbon

If OH is free at the
anomeric carbon =
the monosaccharide is
reducing sugar

Glycosidic Bond Formation

Glycosidic bond: form between the hemiacetal of
monosaccharide (saccharide) and the hydroxyl group of
organic compound such as alcohol.
A substance containing a glycosidic bond is a glycoside
Glycosidic bond due to dehydration/condensation

Disaccharide: glycosidic bond formation between the

hemiacetal of monosaccharide and hydroxyl group from
another hemiacetal

Glycosidic Bond Formation

Type of bond: O-glycosidic bond

Two Different Disaccharides of

-D-Glucose
Glycosidic linkages
can take various
forms; the anomeric
carbon of one sugar
to any of the -OH
groups of another
sugar to form an - or
b-glycosidic linkage
Type of bond: O-glycosidic bond

N-glycosidic bond
The -NH group of amine
substitute for hydroxyl groups
and react at the anomeric
carbon center of
carbohydrates.
New linkage is called Nglycosidic bond
Importance in the construction
ATP and in nucleic acids RNA
and DNA

ATP

Disaccharides

Formation of glycosidic bond condensation (-H2O)

Disaccharides = O-glycoside

CARBOHYDRATE

3. POLYSACCHARIDE

Key words

Definition
Function
Homopolysaccharide and heteropolysaccharide
Cellulose, Chitin, Pectin, Peptidoglycan
Starch, glycogen
Glycoaminoglycan, glycoprotein

Polysaccharides
Polysaccharide- When many monosaccharides
are linked together
Divided into 2 type of monosaccharide or
function
Two main function: energy storage and structure
Type of monosaccharide homopolysaccharide
and heteropolysaccharide

Structural Polysaccharides
Cellulose
Plant cell wall
Pectin
Chitin component of the exoskeleton
of invertebrates and in cell walls of
algae, fungi and yeast

Cellulose
the major structural component of plants,
especially wood and plant fibers
a linear / unbranched polymer of approximately 2800
b-D-glucose units joined by b-1,4-glycosidic bonds
extensive intra- and intermolecular hydrogen bonding
between chains-strength
Cellobiose is the repeating disaccharide
hydrolysis by cellulase

Polymeric Structure of Cellulose

Pectin
Important component of
plant cell walls
Monomer D-Galacturonic
acid, derivative of galactose
Commercially importantfood processing industry
- as gelling agent in jams
and jellies

Chitin
the major structural component of the
exoskeletons of invertebrates and crustaceans;
and in cell walls of algae, fungi, and yeasts
b-1,4-glycosidic bonds similar with cellulose

linear polymer, each chain held together by

hydrogen bonds
composed of units of N-acetyl- -Dglucosamine differ with cellulose

Chitin
Differ with glucose

Peptidoglycan
Bacterial cell walls:
prokaryotic cell walls
are constructed on
the framework of
the repeating unit
NAM-NAG joined by
b-1,4-glycosidic
bonds
Presence of peptide
bond

Storage Polysaccharides
Starch
Glycogen

Starch
Starch is used for energy storage in plants
amylose: continuous, unbranched chains of up to 4000 a-Dglucose units joined by -1,4-glycosidic bonds
amylopectin: a highly branched polymer consisting of 24-30 units
of D-glucose joined by -1,4-glycosidic bonds and branches
created by -1,6-glycosidic bonds
amylases catalyze hydrolysis of -1,4-glycosidic bonds
* b-amylase is an exoglycosidase and cleaves from the nonreducing
end of the polymer
* -amylase is an endoglycosidase and hydrolyzes glycosidic
linkages anywhere along the chain to produce glucose and
maltose
debranching enzymes catalyze the hydrolysis of -1,6-glycosidic
bonds

Starch

Amylose and Amylopectin

 Amylose occurs as a helix

with 6 residues per turn
- able to give the dark-blue color
complex with iodine.

Glycogen
Glycogen is used for energy storage in animals
Has amylose and amylopectin similar to starch
Differ with starch the amylopectin is highly branched

- branch point: occur about every 10 residues

in starch, about
every 25 residues

Polysaccharides
Homopolysaccharide: consists of one type of
monosaccharide
Heteropolysaccharide: consists of more than
one type of monosaccharide

Polysaccharides

Heteropolysaccharide:
Glycosaminoglycans
Glycosaminoglycans: polysaccharides based on a
repeating disaccharide where one of the
monomers is an amino sugar and the other has a
negative charge due to a sulfate or carboxylate
group
Heparin: natural anticoagulant
Hyaluronic acid: a component of the vitreous humor of
the eye and the lubricating fluid of joints
Chondroitin sulfate and keratan sulfate: components
of connective tissue

Heteropolysaccharide:
Glycosaminoglycans

Glycoproteins
Glycoproteins contain carbohydrate units covalently
bonded to a polypeptide chain
antibodies are glycoproteins
Oligosaccharide portion of glycoproteins act as antigenic
determinants
Among the first antigenic determinants discovered were the
blood group substances
In the ABO system, individuals are classified according to four
blood types: A, B, AB, and O
At the cellular level, the biochemical basis for this classification is
a group of relatively small membrane-bound carbohydrates

Tutorial 1
1. Give two important functions of polysaccharide.
2. Name 2 structural polysaccharide and 2 storage
polysaccharide.
3. Give one example of heteropolysaccharide.