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Carbohydrate

Carbohydrate
Referred to compounds of the general formula CnH2nOn.
Carbohydrate are major energy source in human body.
There are three types of carbohydrate : Monosaccharides,
Oligosaccharides and polysaccharides.
Building blocks of all carbohydrates are the simple sugar called
monosaccharides.

A monosaccharides can be a aldehyde or ketone.


Aldose: a monosaccharide containing an aldehyde group
Ketose: a monosaccharide containing a ketone group

For example :

D, L system is used for carbohydrate


Fischer projection :
bonds written VERTICALLY on 2D paper = bonds directed BEHIND
the paper in 3D.
Bonds written HORIZONTALLY on 2D paper = bonds directed IN
FRONT of the paper in 3D

D and L configuration
How to differentiate between D and L configuration ?
* Depends on the arrangement at the chiral carbon with the HIGHEST
number

-The

highest-numbered

chiral

carbon

atom

is

C5

in

glucose.

**When the -OH group is located at right, it is a D-Glucose


**When the -OH group is located at left, it is a L-Glucose

Mirror images , nonsuperimposable stereoisomers are called

enantiomers.

Non-superimposable and non-mirror image stereoisomers are called diastereomers.


For example :

Aldotetroses
Has 2 chiral carbon, C2 and C3. Therefore, there are 4 possible stereoisomers (2 2 =4)
2 of the isomers have D configuration while the other 2 have L configuration
The 2 D isomers have the SAME configuration at C3 but DIFFER in configuration at the
another chiral carbon, C2.
D-Erythrose and D- threose are nonsuperimposable and non- mirror image stereoisomers
(diastereomers)

- The L isomers are L-Erythrose and L-Threose.


- L-erythrose is the enantiomer of D-erythrose.
- L-threose is the enantiomer of D-threose.
- L-threose is a diastereomer of both D- and L-erythrose.
- L-erythrose is a diastereomer of both D- and L-threose.

Stereisomers that differ only in configuration around one of several


chiral carbon atoms is called epimers.
For example :

Cyclization of sugar
Sugars normally exist as cyclic molecule rather than as the open-chain
form.
The interaction between the functional groups on distant carbons, such as
C-1 and C-5 form a cyclic hemiacetal (aldohexoses)
C-2 and C-5 form a cyclic hemiketal (ketohexoses)
The carbonyl carbon which becomes the new chiral centre is called
anomeric carbon.
Anomers: carbohydrates that differ in configuration only at their
anomeric carbons

-anomer and -anomer


In the -anomer, the hydroxyl on the anomeric carbon is on the trans /
opposite side of the ring from the terminal CH2OH. (pointing down)
In the -anomer, it is on the cis / same side of the ring (pointing up)

Haworth projection
Five-membered ring furanose
Six-membered ring pyranose
Furanose is nearly planar where pyranose exist in the chair
conformation

Haworth projection
For D sugar, any group that is written to the right of the carbon in a
Fischer projection has a downward direction in a Haworth projection; any
group that is written to the left of the carbon in a Fischer projection has a
upward direction in a Haworth projection.
The terminal CH2OH group, which contains the highest number of
carbon atom, is shown in an upward direction.

Reactions of
Monosaccharides

Oxidation

Reduction

Oxidation

Aerobic process : Glucose

oxidise

CO2 + H2O

Reaction use to identify sugars

Oxidising agent Tollens reagent

Reducing sugar
Sugars that reduces an oxidising agent
Sugars that give a silver mirror with Tollens
1) Aldoses (carbohydrates with aldehyde group)
- Aldehyde group can be oxidise to carboxyl group
- Oxidising agent is reduced
2) Ketoses (carbohydrates with ketone functionality)
-Isomerise to aldoses
3)

Tollens reagent
Detect the presence of reducing sugars
Silver mirror (silver precipitate) is deposited on the wall of the test tube if a reducing
sugar is present.
Both aldoses and ketonses are oxidise to aldonic aldonic acid .

Negative test : If anomeric carbons involve in glycosidic linkage


Positive test : If anomeric carbon is not bonded and is free

Reduction
The carbonyl group of a monosaccharide reduced by a reducing agent,
such as NaBH4 .
Reduction of monosaccharide gives a polyhydroxy
compound called an alditol.

Phosphate Ester
-formed by the transfer of a phosphate group from ATP
-intermediates in the breakdown of carbohydrates to provide energy

Formation of Glycosidic
Linkage
Glycosides
-carbohydrate in which the OH group of anomeric carbon is
replaced by OR
-derived from furanose -> furanosides
-derived from pyranoses -> pyranosides
-give rise to oligosaccharides and polysaccharides
Glycosidic Linkage ( R-O-R )
-NOT an ether
-can be hydrolyzed to the original alcohols

Formation of Glycosides

-Glysocidic linkages can take various forms: the anomeric carbon of the one sugar

can be bonded to any one of the OH groups on second sugar to form an - or


-glycosidic linkage

Glycosidic Linkage
-Chemical natures of oligosaccharides and polysaccharides depends on
i)

Types of monosaccharides linked together

ii)

Particular glycosidic bond formed

-linear and branched-chain polymers formed due to the variation in the glycosidic
linkages
Test for reducing sugar
-requires a reaction of the group at the anomeric carbon
-internal anomeric carbon are not free to give the test for reducing sugar
*only if the end residue is a free hemiacetal -> positive test

Amino Sugar
- -NH2 group or one of its derivatives is substituted for the OH group of the parent sugar
- Examples :

-components of bacterial cell walls

Disaccharides
Sucrose
Table sugar, extracted from sugarcane and sugar beets
Made up of D-glucose and D-fructose and joined together by a-1,2-glycosidic bond
Non-reducing sugar, both anomeric groups are involved in the glycosidic linkage
Lactose
Made up of D-galactose and D-glucose joined by b-1,4-glycosidic bond
Galactose is inversion of configuration of glucose at C-4
Maltose
Made up of two D-glucose joined by a-1,4-glycosidic bond
Differs from cellobiose (hydrolysis of cellulose),joined by b-1,4-glycosidic bond
Mammals can digest maltose but not cellobiose

Glycoprotein
Glycoprotein contains carbohydrate residues which covalently bonded to the
polypeptides chain
Example : antibodies in immune responses
Bind to and immobilize antigens (the substances attacking the organisms)

Oligosaccharides portion of glycoproteins acts as antigenic determinants (the


portions of an
antigenic molecule that antibodies recognize and to which they bind)
Common example : human blood group systems
Glycoprotein
Plays an important role in eukaryotic cell membranes

Glycoprotein

Proteoglycans
glycoproteins with an extremely high carbohydrate content
Constantly being synthesized and broken down
Hurlerss syndrome (genetic disease)
Lack of the lysosomal enzymes

Proteoglycans accumulate

Leads to skeletal deformities, severe mental retardation, and death in early childhood