Carbohydrat

es are
aldehyde or
ketone
derivatives
of polyhydric
alcohols
• Monosaccharides (monoses or glycoses)
• Trioses, tetroses, pentoses, hexoses

• Oligosaccharides
• Di, tri, tetra, penta, up to 10
• Most important are the disaccharides

• Polysaccharides or glycans
• Homopolysaccharides
• Heteropolysaccharides
• Complex carbohydrates
• Also known as simple sugars
• Classified by the number of carbons
and whether aldoses or ketoses
• 99% are straight chain compounds
• D-glyceraldehyde is the simplest of
the aldoses (aldotriose)
• Dihydroxyacetone is the simplest of
the ketoses (ketotriose)
• all other sugars have the ending ose
• Fisher projection: straight chain
representation
• Haworth projection: simple ring in
perspective
• Conformational representation:
chair and boat configurations
 Aldose sugars

Page  10
 Ketose sugars

Page  11
Rule: 2 n

Example: Aldotetrose whichhas2

chiral carbonswill have4

stereoisomers
The designation of the configuration as L or
D depends on the arrangement at the
chiral carbon with the highest number.

• In the Fischer projection

D if the –OH is on the right of the highest-
numbered chiral carbon
L if the –OH is on the left of the highest-
numbered chiral carbon
 Most of the important
sugars found in nature are D
sugars and the enzymes
responsible for their
metabolism are specific for
this configuration.
 Enantomiers and
epimers

Page  17
 The direction of rotation of polarized light is
independent of the stereochemistry of the sugar.

Possibilities: D or
D
L or
 α observed x 100
[α ] D
T
=
lxc
D = Na D line
T = temperature oC
α obs : observed rotation in degree (specify solvent)
l = length of tube in decimeter
c = concentration in grams/100ml
[α ] = specific rotation

Page  21
General reaction for
hemiacetal formation
General reaction for hemiketal
formation
 Furan
α -D-
Ribofuranose

Pyran
α -D-
Glucopyranose
 Draw either a six- or five-
memberedO
ringO
including oxygen as one
atom
Most aldohexoses are six- me
aldotetroses, aldopentoses
ketohexoses are 5-member
• Number the ring
clockwise starting
next to the oxygen
5
O O
4 1 4 1

3 2 3 2
• If the substituent is to the
right in the Fisher projection,
it will be drawn down in the
Haworth projection
• For D-sugars the highest
numbered carbon is drawn
up, for L-sugars, it is drawn
down
 For D-sugars, the -OH group
at the anomeric position is
drawn down for α and up for
β ;
for L-sugars α is up and β is
down.
Fischer to Haworth D-glucose
anomers
D-glucose can
Form either furanose or
pyranose structures
D-ribose and other five-carbon
saccharides can form either
furanose or pyranose structures
Chair and boat conformations of a pyranose sugar

2 possible chair conformations

of β -D-glucose
• Oxidation of sugars provides energy for
organisms to carry out life processes
• Highest yield of energy when sugars are
completely oxidized to CO2 and H2O
• Reduction is reversed process
e.g. photosyntheis
• Aldehyde groups can be oxidized to
give the carboxyl group that is
characteristic of acids
• Aldoses are called REDUCING sugars
because of this type of reaction
• In the cyclic form the product is called
a lactone
Aldoses may be oxidized to 3
types of acids:
• Aldehyde group  Aldonic
acid
• Primary alcohol group 
Uronic acid
• Oxidation at both ends 
Saccharic acid
• Glucose oxidase converts glucose to gluconic
acid and hydrogen peroxide
• When the reaction is performed in the
presence of peroxidase and o-dianisidine a
yellow color is formed
• The basis for the measurement of urinary and
blood glucose
• Testape, Clinistix, Diastix (urinary glucose)
• Dextrostix (venous glucose)
• The resultant product is a
polyol or sugar alcohol (alditol)
• Examples:
glucose  sorbitol (glucitol)
mannose  mannitol
glyceraldehyde  glycerol
• Mannitol is used as an osmotic diuretic
• Glycerol is used as a humectant and can be
nitrated to nitroglycerin
• Sorbitans are converted to detergents
known as spans and tweens (used in
emulsification procedures)
• Sorbitol can also be dehydrated to 1,4,3,6-
dianhydro-D-sorbitol (isosorbide) which is
nitrated to ISDN and ISMN
• The hydorxyl group of sugars
can react with acids and
derivatives of acids to form
esters.
• Phosphate esters are the
usual intermediates in the
breakdown of carbohydrates
to provide energy.
• A hemiacetal carbon can react with
an alcohol to give a full acetal or
glycoside
• The newly formed bond is called a
glycosidic bond, O-glycosides, with
each sugar bonded to an oxygen
atom of another molecule
 Special monosaccharides:
amino sugars
onstituents of mucopolysaccharides
• Common table sugar
extracted from sugarcane
and sugar beets
• α-D-glucose and β–D-
fructose joined by α,β(12)
glycosidic linkage
• β -D-fructofuranosido-α -D-
glucopyranoside
• NOT a reducing sugar
• β -D-galactose joined to D-glucose
via β (1,4) linkage
• Galactose is an epimer of glucose
(C-4)
• Milk contains the α and β anomers
of lactose in a 2:3 ratio
• β -lactose is sweeter and more
soluble than ordinary
α - lactose
• Used in infant formulations,
medium for penicillin production
• Produced by partial hydrolysis of
starch

• Consists of two residues of D-

glucose joined via α (1,4) linkage

• Known as malt sugar used in

beverages such as malt milk
• Produced by hydrolysis of
cellulose

• Differs from maltose only in

the glycosidic linkage, 2
residues of D-glucose joined
by β(14) linkage
• Galactose-β -(1,4)-fructose
• A semi-synthetic disaccharide
• not absorbed in the GI tract
• Used either as a laxative or in
the management of portal
systemic encephalopathy
• Metabolized in distal ileum and
colon by bacteria
to lactic acid, formic acid and
• Trisaccharide: raffinose (glucose,
galactose and fructose)
• Tetrasaccharide: stachyose (2
galactoses, glucose and
fructose)
fructose
• Pentasaccharide: verbascose (3
galactoses, glucose and
fructose)
fructose
• Hexasaccharide: ajugose (4
galactoses, glucose and
fructose)
fructose
Structures of some oligosaccharides
Honey also contains glucose and fructose along with
some volatile oils
 Structures
An enzymatic of (Beano)
product some oligosaccharides
can be used to prevent
the flatulence
Oligosaccharides occur widely as components of
antibiotics derived from various sources
• Homopolysaccharide – a polymer
that consists of only one type of
monosaccharide
• Heteropolysaccharide – a polymer
that consists of more than one
type of monosaccharide
• GLUCOSE is the most common
monomer
• Linear homopolymer of β -D-glucose all
linked by β (1,4) glycosidic bonds
• Most abundant of all carbohydrates
• Cotton flax: 97-99% cellulose
• Wood: ~ 50% cellulose
• Individual polysaccharide chains are
hydrogen bonded giving plant fibers
mechanical strength
• Animals lack the enzyme cellulase which
attack β-linkages
• Cellulases are found in bacteria
including those that inhabit the digestive
tracts of grazing animals and insects
• Yields glucose upon complete hydrolysis
• Partial hydrolysis yields cellobiose
• Gives no color with iodine
Polymers of D-glucose
α-linkage in starch, β-linkage in cellulose
Types of starches distinguished by
degree of chain branching:
Amylose and amylopectin are the 2 forms
of starch. Amylopectin
is a highly branched structure, with
branches occurring every
12 to 30 residues
 (in
starch)

(in cellulose)
Linear structures of cellulose and chitin
(2 most abundant polysaccharides)
ntains α (1,4), α (1,6) and α (1,3) linkages
• Complex carbohydrates containing amino
sugars and uronic acids
• May be attached to a protein molecule to
form a proteoglycan
• Proteoglycans provide the ground or
packing substance of connective tissue
E.g. Hyaluronic acid, chondroitin sulfate,
and heparin
acteristic of glycosaminoglycans is the pr
Glycosaminoglycans
c functionalities (carboxylate and/or sulf
Glycosamin
oglycans
• Contain carbohydrate residues in
addition to the polypeptide chain
• Important role in immune
response
E.g. Antibodies which bind to and
immobilize antigens
• Also found in eukaryotic cell
membranes
• Major components are heteropolysaccharides,
cross-linked by peptides
• Repeating unit consists of two residues, N-
acetyl-D-glucosamine and N-acetylmuramic
acid held together by β(1,4) glycosidic link
• Extensive cross-linking results to mechanical
strength; bacterial cell walls are extremely
difficult to disrupt
Cell wall of Gram-
positive bacteria
 Structure of
peptidoglycan
• Consist largely of cellulose
• Pectin is the other important
polysaccharide component, a polymer of
mostly D-galacturonic acid
• Pectin is extracted from plants for use as
a gelling agent in food processing
• Lignin is the major nonpolysaccharide
component, particularly in woody plants
rine or threonine O-linked saccha
sacch
Aspargine N-linked glycoprotein
Involved in a variety of extracellular
Glycosaminoglycans
functions; chondroitin
is found in tendons, cartilage and
other connective tissues