Biochemistry

Lecture no. 12-13

Carbohydrates
 Carbohydrates

 More than half of all organic carbon on

plant earth is stored in just two
carbohydrate molecules;
 Starch
 Cellulose
 Both are polymers of sugar monomer;
glucose.

12:03‫م‬ Lect 12-13: carbohydrates 2

 Carbohydrates

 Glucose, made by green plants, stored as starch as

energy reserves.
 Animal [human] have enzyme that recognize the
helical conformation of starch and
 Degrade it into CO2 and H2O.
 Cellulose, major component of plant cell wall,
cotton, wood, is a polymer of glucose monomers
 Human don’t possess the enzyme cellulase, which is
needed to breakdown cellulose, but termites do and
protozoan
 Wooden houses are damaged by termites.

12:03‫م‬ Lect 12-13: carbohydrates 3

 General characteristics
 The term carbohydrate is derived from the french:
hydrate de carbone
 Compounds composed of C, H, and O
 General formula for CHO;
 Cn(H2O)n or (CH2O)n when n = 5 then C5H10O5
 Only the simple sugars or monosaccharides, fit this
formula exactly.
 Not all carbohydrates have this empirical formula:
deoxysugars, aminosugars
 Carbohydrates are the most abundant compounds
found in nature (cellulose: 100 billion tons
annually)
12:03‫م‬ Lect 12-13: carbohydrates 4
 Functions
 Sources of energy
 Intermediates in the biosynthesis of other basic
biochemical entities (fats and proteins)
 Associated with other entities such as
glycosides, vitamins and antibiotics)
 Form structural tissues in plants and in
microorganisms (cellulose, lignin, murein)
 Participate in biological transport, cell-cell
recognition, activation of growth factors,
modulation of the immune system

12:03‫م‬ Lect 12-13: carbohydrates 5

 Classification of carbohydrates
 Monosaccharides;
 The simplest type of sugar and consist of one monomers
of sugar unit (mannose or glucose)
 Trioses, tetroses, pentoses, hexoses
 Oligosaccharides
 Few monosaccharides (2-10 molecules) are linked
together by glycosidic bonds.
 Di, tri, tetra, penta, up to 9 or 10
 Most important are the disaccharides
 Polysaccharides or glycans
 Many monosaccharides (›10 molecules) are linked

together by glycosidic bonds

 Homopolysaccharides
 Heteropolysaccharides
 Complex carbohydrates
12:03‫م‬ Lect 12-13: carbohydrates 6
 Monosaccharides
 Also known as simple sugars
 Classified by
1. the number of carbons and
2. whether aldoses or ketoses
 Building blocks of all CHO
 Can be polyhydroxy aldehyde (aldose) or
polyhydroxy ketone (ketose)
 Most (99%) are straight chain compounds
 All other sugars have the ending ose
(glucose, galactose, ribose, lactose, etc…)
12:03‫م‬ Lect 12-13: carbohydrates 7
 Aldose sugars

H H H H H

C O C O C O C O C O

(H C OH)n H C OH H C OH H C OH H C OH

CH2OH CH2OH H C OH H C OH H C OH

Aldose Aldotriose CH2OH H C OH H C OH

n=1
Aldotetrose CH2OH
n=2 H C OH
Aldopentose
CH2OH
n=3
Aldohexose
n=4

12:03‫م‬ Lect 12-13: carbohydrates 8

 Ketose sugars

CH2OH CH2OH
CH 2OH
CH2OH
C O C O CH2OH
C O
C O
(H C OH)n H C OH C O
H C OH
CH2OH
CH2OH H C OH H C OH
CH 2OH
CH2OH H OH
Ketose Ketotriose Ketotetrose
n=1 Ketopentose H C OH
n=0
n=2
CH2OH
Ketohexose
n=3

12:03‫م‬ Lect 12-13: carbohydrates 9

 Monosaccharides
 The simplest of the monosaccharides
contain 3C atom triose (aldotriose); D-
glyceraldehyde

 The simplest of the monosaccharides

contain 3C atom triose (ketotriose);
Dihydroxyacetone

12:03‫م‬ Lect 12-13: carbohydrates 10

 Structure of a simple aldose and a simple ketose

12:03‫م‬ 11
 Enantiomers and epimers
H H
H H C O C O
C O C O HO C H HO C H
H C OH OH C H HO C H HO C H
H C OH OH C H H C OH HO C H
CH2OH CH2OH
H C OH H C OH
these two aldotetroses are enantiomers.
They are stereoisomers that are mirror CH2OH CH2OH
images of each other
these two aldohexoses are C-4 epimers.
they differ only in the position of the
hydroxyl group on one asymmetric carbo
(carbon 4)

12:03‫م‬ Lect 12-13: carbohydrates 12

 Enantiomers

 Some molecules are not superimposable on their

mirror images and these mirror images are optical
isomers [stereoisomer's] of each other {chiral
molecule}.

Note;
Glyceraldehyde exist in two isomeric forms
that are mirror imagers of each other, differ
in position of OH group.

Mirror image stereoisomer's are called

enantumers.
D,L glyceraldehyde are enantiomers to each
other.
12:03‫م‬ Lect 12-13: carbohydrates 13
 Enantiomers

12:03‫م‬ Lect 12-13: carbohydrates 14

 Enantiomers
 The two enantiomers of glyceraldehyde are the
only possible stereoisomer's of 3-Carbon sugars,
but the possibilities for stereoisomerism increases
as no of carbon atoms increases.
Fischer-projection method
o Most common sugars are aldoses rather than ketoses
o D or L depends depends on the arrangement at the
chiral carbon with the highest number
o In fisher projection of D-conformation, OH on the
right of the highest numbered chiral carbon,
o Where the hydroxyl group on the left of the highest
numbered chiral carbon in the L-Conformation.

12:03‫م‬ Lect 12-13: carbohydrates 15

 Enantiomers

:Attention
The carbons are
.numbered
The designation of
D or L depends on
the configuration at
the highest
numbered chiral
carbon atom

12:03‫م‬ Lect 12-13: carbohydrates 16

 The possible stereoisomer of an aldotetrose

 The aldotetroses have two chiral carbons, C-2,

C-3 and there are 22 or 4 possible stereoisomer.
 2D isomers have same configuration at C3, differ
in OH arrangement at C2

12:03‫م‬ Lect 12-13: carbohydrates 17

 The possible stereoisomer of an aldotetrose

 They are not superimposable on each other but

neither are they mirror images of each other.
 Nonsuperimposable, non mirror image
stereoisomer called diastereomers.

12:03‫م‬ Lect 12-13: carbohydrates 18

 The possible stereoisomer of an aldotetrose

 2-L isomers are L-erythrose and L-threose

 L-Erythrose is enantiomer [mirror image] of D-erythrose.
 L-threose is enantiomer [mirror image] of D-threose.

12:03‫م‬ Lect 12-13: carbohydrates 19

 The possible stereoisomer of an aldotetrose

oDiastereomers that differ from each other in conformation

at only one chiral carbon called epimers

o So D-erythrose, D-therose aer epimers

12:03‫م‬ Lect 12-13: carbohydrates 20

 Epimers
Sugars that differ only in their
stereochemistry at a single chiral carbon.

12:03‫م‬ Lect 12-13: carbohydrates 21

 Enantiomers and epimers
H H
H H C O C O
C O C O HO C H HO C H
H C OH OH C H HO C H HO C H
H C OH OH C H H C OH HO C H
CH2OH CH2OH
H C OH H C OH
these two aldotetroses are enantiomers.
They are stereoisomers that are mirror CH2OH CH2OH
images of each other
these two aldohexoses are C-4 epimers.
they differ only in the position of the
hydroxyl group on one asymmetric carbo
(carbon 4)

12:03‫م‬ Lect 12-13: carbohydrates 22

 The possible stereoisomer of an aldotetrose

o aldopentoses ---- 3 chiral C --- 23 or 8 possible

stereoisomer; 4D, 4L form.

o aldohexoses ---- 4 chiral C --- 24 or 16 possible

stereoisomer; 8D, 8L form.

o Note that; most sugar encounter in nature, especially

food , contain 5 or 6C atom.

12:03‫م‬ Lect 12-13: carbohydrates 23

 Structural representation of sugars
 Fisher projection:
 straight chain representation
 Haworth projection:
 simple ring in perspective
 Conformational representation:
 chair and boat configurations

12:03‫م‬ Lect 12-13: carbohydrates 24

 Rules for drawing Haworth projections
 Cyclization takes places as results of interaction
between the functional groups on distant
carbons, such as C-1 and C-5 in aldohexoses.
 Or C-2 and C-5 in ketohexoses
 Draw either a six or 5-membered ring including
oxygen as one atom
O O

 Most aldohexoses are six-membered

 Aldotetroses, aldopentoses, ketohexoses are 5-
membered
12:03‫م‬ Lect 12-13: carbohydrates 25
12:03‫م‬ Lect 12-13: carbohydrates 26
 Rules for drawing Haworth projections
 First is the names that we assign to rings of
different sizes. We name the cyclic sugars by
comparing them to simple cyclic either's, furan
and pyran:

 Therefore, sugars with five-membered rings will

be called furanoses (D-glucofuranose, D-
mannofuranose, etc.) and
 those with six-membered rings pyranoses (D-
glucopyranose, D-mannopyranose, etc.). .

12:03‫م‬ Lect 12-13: carbohydrates 27

12:03‫م‬ Lect 12-13: carbohydrates 28
 Rules for drawing Haworth projections
 Next 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 (Down-Right
Rule)
12:03‫م‬ Lect 12-13: carbohydrates 29
12:03‫م‬ Lect 12-13: carbohydrates 30
 Rules for drawing Haworth projections

 For D-sugars the highest numbered

carbon (furthest from the carbonyl)
is drawn up. For L-sugars, it is
drawn down.
 For D-sugars, the OH group at the
anomeric position is drawn down for
and up for . For L-sugars is up
and  is down

12:03‫م‬ Lect 12-13: carbohydrates 31

 Rules for drawing Haworth projections
The cyclic sugar take either of two different
forms alpha and beta and they are called
anomers of each other.

Lect 12-13: carbohydrates 32

 Rules for drawing Haworth projections
The cyclic sugar take either of two different forms alpha
and beta and they are called anomers of each other.

Haworth for stereochemistry more realistic than fisher

projection.

12:03‫م‬ Lect 12-13: carbohydrates 33

12:03‫م‬ Lect 12-13: carbohydrates 34
 Chair projections
Chair and haworth projections are alternative ways of
expressing the same information.

12:03‫م‬ Lect 12-13: carbohydrates 35

12:03‫م‬ Lect 12-13: carbohydrates 36