1/28/2013

LECTURE 5: CARBOHYRATE

INTRODUCTION
 Photosynthesis:: D-Fructose 6-
Photosynthesis 6-phosphate
1. The carbohydrates of plants are derived originally
from atmospheric CO2 which is converted, through
the process of photosynthesis, into PGA (3 ( 3-
Phosphoglyceric acid)
acid) and then to F-
F-6-P (D
(D-Fructose
6-phosphate
phosphate))
2. A whole range of monosaccharides and
monosaccharide derivatives are synthesized from F-
6-P.
3. Some of these monosaccharide derivatives are the
precursor of oligosaccharides and polysaccharides
polysaccharides..
4. It is important to note that sucrose is the type of
carbohydrates (oligosaccharides) transported around
the plant.

1
 1/28/2013

INTRODUCTION

5. Polysaccharides can be divided into the structural

polysaccharides (e.g. cellulose, pectins
pectins)) and storage
polysaccharides (e.g. starch, fructosans
fructosans).).

 Carbohydrate 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
murein))
 Participate in biological transport, cell-
cell -cell recognition,
activation of growth factors, modulation of the
immune system

DEFINITION
What Is a Carbohydrate?
1. Carbohydrates may be defined as polyhydroxy
aldehydes or ketones
ketones,, or substances that yield one of
these compounds on hydrolysis.
ketone

aldehyde

2
 1/28/2013

DEFINITION

aldehyde

ketone

Aldoses (e.g., glucose) have Ketoses (e.g., fructose) have a

an aldehyde at one end. keto group, usually at C #2

In aldehydes, the carbonyl group has a hydrogen atom

attached to it together with either a second hydrogen
atom or, more commonly, a hydrocarbon group which
might be an alkyl group or one containing a benzene ring.

In ketones, the carbonyl group has two hydrocarbon

groups attached. Again, these can be either alkyl groups
or ones containing benzene rings. Again, we'll concentrated
on those containing alkyl groups just to keep things simple.
Notice that ketones never have a hydrogen atom attached
to the carbonyl group.

3
 1/28/2013

DEFINITION

2. The formula (CH2O)n where n 3 can be used to

represent many carbohydrates which are
regarded originally as the hydrates of carbon
carbon..
3. The formula is not suitable when other
compounds were encountered that had the
general properties of carbohydrates but
contained N (nitrogen) or S (sulfur) in addition
to carbon, hydrogen and oxygen.
4. Moreover, the important simple sugar
deoxyribose,, found in every cell as a component
deoxyribose
of deoxyribonucleic acid, has the molecular
formula C5H10O4 rather than C5H10O 5

CARBOHYDRATE CLASSIFICATION
 The most useful classification scheme divides the
carbohydrates into groups according to the number of
individual simple sugar units
 Monosaccharides
 Trioses,, tetroses
Trioses tetroses,, pentoses
pentoses,, hexoses
 Oligosaccharides
 Di, tri, tetra, penta
penta,, up to 9 or 10
 Most important are the disaccharides
 Polysaccharides.
 Homopolysaccharides
 Heteropolysaccharides
 Complex carbohydrates
 In general, the monosaccharides and disaccharides are
commonly referred to as sugars.

4
 1/28/2013

Monosaccharides
 Monosaccharides also known as simple sugars are
classified based on three characteristics:
A. number of carbon atoms in the molecule
B. location of the carbonyl group
C. the chirality of the carbohydrate

A. Number of carbon atoms

 three carbons: triose
 four carbons: tetrose
 five carbons: pentose
 six carbons: hexose
 seven carbons: heptose
 etc.

1. Triose (3 C)

D-Glyceraldehyde L-Glyceraldehyde

2. Tetrose (4 C)

D-Erythrose D-Threose D-Erythrulose

5
 1/28/2013

3. Pentose (5 C)

D-Ribose D-Arabinose D-Xylose D-Lyxose

• The ring form of ribose is a component ribonucleic acid

(RNA).
• Deoxyribose, which is missing an oxygen at position 2, is
a component of deoxyribonucleic acid (DNA).
• In nucleic acids, the hydroxyl group attached to carbon
number 1 is replaced with nucleotide bases

Ribose Deoxyribose

4. Hexose (6 C)

D-Allose D-Altrose D-Glucose D-Mannose

D-Gulose D-Idose D-Galactose D-Talose

6
 1/28/2013

D-Glucose (an aldose) α-D-Glucose β-D-Glucose

Cyclation of Glucose

5. Heptoses (7C)
Sedoheptulose has the same structure as fructose,
but it has one extra carbon. Sedoheptulose is found
in carrots. Mannoheptulose is a monosaccharide
found in avocados.

D-Sedoheptulose D-Mannoheptulose

7
 1/28/2013

CARBOHYDRATE CLASSIFICATION

B. Location of carbonyl group

 an aldose (aldehyde sugar)
 a ketose (ketone sugar)

Structure of a simple aldose and a simple ketose

aldose

ketose

 For example
− glucose is an aldose
aldose;;
− fructose, a structural isomer of glucose, is a ketose
carbonyl group

8
 1/28/2013

Monosaccharides

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

9
 1/28/2013

Monosaccharides

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

10
 1/28/2013

C. The chirality of carbohydrate

 Chirality is a term derived from the Greek word for
hand (χειρ =cheir
cheir)) or asymmetric carbon atoms
 This causes optical isomerism which is the type of
isomerism commonly found in carbohydrate.
 Isomerism may be divided into structural isomerism
and stereoisomerism
stereoisomerism..
 Structural isomers have the same molecular
formula but differ from each other by having
different structures, and
 Stereoisomers have the same molecular formula
and the same structure, but they differ in
configuration, that is, in the arrangement of atoms
in space. Stereochemisty is the study of the
arrangement of atoms in three-
three-dimensional space

The chirality of the carbohydrate

 Saccharides with identical functional groups but

with different spatial configurations have
different chemical and biological properties.
properties.
 Compounds that are mirror images of each
other but are not identical, comparable to left
and right shoes,
shoes, are called enantiomers
 Any carbon atom which is connected to four
different groups will be chiral and will have
two nonsuperimposable mirror images; it is a
chiral carbon or a center of chirality
 Monosaccharides contain one or more
asymmetric C-C-atoms
atoms:: D-
D- and L-
L-forms
 D-form: OH group is attached to the right of the
asymmetric carbon
 L-form: OH group is attached to the left of the
asymmetric carbon

11
 1/28/2013

The chirality of the carbohydrate

 If there is more
more than one chiral C-atom:
absolute configuration of chiral C furthest
away from carbonyl group determines whether
D- or L-
 D and L designations are based on the
configuration about the single asymmetric
carbon in glyceraldehyde
glyceraldehyde..
 Glyceraldehyde is a
chiral molecule — it
cannot be superimposed
on its mirror image.
 The two mirror-
mirror-image
forms of glyceraldehyde
are enantiomers of each
other

Two carbohydrates are said to be enantiomers if the

two carbohydrates are complete mirror images of
one another.

An example of an
enantiomer is the D and L
isomers of glucose

The blue indicates the D-isomer and the red

indicates the L-isomer

12
 1/28/2013

CH2O CH2O
C=O C=O
HO-C-H Enantiomers H-C-OH
H-C-OH Mirror image HO-C-H
configurations
H-C-OH HO-C-H
CH2O CH2O

CH2O
CH2O
C=O
C=O
H-C-OH
H-C-OH
HO-C-H
HO-C-H
HO-C-H
HO-C-H
CH2O
CH2O

The differing
Diastereoisomers. Two carbohydrates stereogenic centers.
are said to be diastereoisomers if
they have the opposite configuration
at one or more of the chiral centers
present in the carbohydrate but the
two carbohydrates are not mirror
images of one another.

Epimers are a special type of An example of two

carbohydrates that are
diastereoisomers in that diastereoisomers are D-
they only differ at one of the Glucose and D-Altrose
stereogenic centers.

An example of epimers
that differ at one
stereogenic center is D-
Glucose and D-Mannose,

13
 1/28/2013

Enantiomers and epimers

The chirality of the carbohydrate

 For sugars with more than one chiral center, the

D or L designation refers to the asymmetric
carbon farthest from the aldehyde or keto group
group..
 Most naturally
occurring sugars
are D isomers.
 D & L sugars are
mirror images of
one another. They
have the same
name. For example,
D-glucose and L-
L-
glucose are shown
at right.

14
1/28/2013

15
 1/28/2013

Fischer Projections
 Fischer projections are a convenient way to
represent mirror images in two dimensions.
 Place the carbonyl group at or near the top and
the last achiral CH2OH at the bottom.

 When there is more than one chiral center in a

carbohydrate, look at the chiral carbon farthest
from the carbonyl group: if the hydroxy group
points to right when the carbonyl is “up” it is the
D-isomer
isomer,, and when the hydroxy group points to
the left, it is the L-isomer
isomer..

16
1/28/2013

17
 1/28/2013

 When a molecule has more than one chiral

carbon,, each carbon can possibly be arranged in
carbon
either the right-
right-hand or left-
left-hand form,
form, thus
if there are n chiral carbons, there are 2n
possible stereoisomers
stereoisomers..
Maximum number of possible stereoisomers = 2n

• D-Glucose have four asymmetric carbon atoms (No. 2,

3, 4 & 5)2n = 24 = 16

D-Glucose
(an aldose)

3 examples of chiral Carbon atoms:

from http://ntri.tamuk.edu/cell/carbohydrates.html)

18
 1/28/2013

Exercise
 How many isomers are there of

 How many chiral carbon atoms

are there in

Ring formation / Ring structure

An aldose: Glucose

from http://ntri.tamuk.edu/cell/carbohydrates.html

19
 1/28/2013

A ketose: Fructose

from
http://ntri.tamuk.edu/cell/carbohydrates.html

POLARIMETRY
 Measurement of optical activity in chiral or asymmetric
molecules using plane polarized light
 Molecules may be chiral because of certain atoms or
because of chiral axes or chiral planes
• Measurement uses an instrument
called a polarimeter (Lippich
type)
• Rotation is either (+)
dextrorotatory or (-)
levorotatory

20
 1/28/2013

Polarimetry

– Magnitude of rotation depends upon:

1. the nature of the compound
2. the length of the tube (cell or sample container)
usually expressed in decimeters (dm)
3. the wavelength of the light source employed;
usually either sodium D line at 589.3 nm or
mercury vapor lamp at 546.1 nm
4. temperature of sample
5. concentration of analyte in grams per 100 ml

 observed x 100
[ ] D
T
=
lxc
D = Na D line
T = temperature oC
aobs : observed rotation in degree (specify solvent)
l = length of tube (dm, decimeter)
c = concentration in grams/100ml
[a] = specific rotation

21
 1/28/2013

Specific rotation of various carbohydrates at 20oC

 D-glucose +52.7
 D-fructose -92.4
 D-galactose +80.2
 L-arabinose +104.5
 D-mannose +14.2
 D-arabinose -105.0
 D-xylose +18.8
 Lactose +55.4
 Sucrose +66.5
 Maltose+ +130.4
 Invert sugar -19.8
 Dextrin +195

THANK YOU
Спасибо

謝謝
ً ‫ﺷﻛرا‬

22