Carbohydrates

Carbohydrates : Energy molecules

 Carbohydrates
Building blocks of carbohydrates = sugar

sugar - sugar - sugar - sugar - sugar

sugar sugar sugar sugar sugar sugar

 Functions of carbohydrates

• Energy in the diet

• Storage form of energy in the
body
• Structural component
 Cell surface and sugar molecules
Component of the cell membrane

5
 Carbohydrates

Simple Complex

Fruits, milk, vegetables Starch, fibres

 Carbohydrates

• Compounds contain C, H and O

I
(CH2O)n or H - C - OH
I
• All have C=O and -OH functional groups.

• Classified based on
- Number of sugar units
- Location of carbonyl groups, C=O
- Size of base carbon chain
- Stereochemistry
 Carbohydrate classification

1. Number of sugar units

• Monosaccharides - single sugar unit

• Disaccharides - two sugar units
• Oligosaccharides - 2 to 10 sugar units
• Polysaccharides - more than 10 units
 Carbohydrate classification
2. Based on location of carbonyl group C=O

H CH2OH
| |
C=O C=O
| |
H-C-OH HO-C-H
| |
H-C-OH H-C-OH
| |
H-C-OH H-C-OH
| |
CH2OH CH2OH

Aldose Ketose
- aldehyde C=O - ketone C=O
 Carbohydrate classification
3. Number of carbon atoms in the chain
H
|
H C=O
| |
H C=O H-C-OH
H | | |
| C=O H-C-OH H-C-OH
C=O | | |
| H-C-OH H-C-OH H-C-OH
H-C-OH | | |
| H-C-OH H-C-OH H-C-OH
CH2OH | | |
CH2OH CH2OH CH2OH

triose tetrose pentose hexose

 Carbohydrate classification

Stereochemistry
Study of the spatial arrangement of molecules

Stereoisomers have
• Types of bonds
• different spatial arrangements
• different properties
 Sterioisomers
Pairs of stereoisomers

• They are mirror images that can’t be overlapped

• Designated by D- or L- at the start of the name
• The D or L designation is based on the chiral
carbon furthest from the carbonyl carbon
 Sterioisomers
Chiral center
Asymmetric carbon - 4 different things are attached to
it.
Cl
|
I- C - F
|
Br Chiral center
You must have at least one asymmetric carbon to have
stereoisomers
 L- and D- glyceraldehyde

CHO CHO
HO H H OH

C C

CH2OH CH2OH

CHO CHO

HO H H OH

CH2OH CH2OH
D- and L- glucose

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 Cyclic structures

Cyclization - chains can bend and rotate.

 Cyclic structures
6 CH2OH 6 CH2OH
5 O 5 O
H H H OH
H H
4 H 1 4 H 1
OH OH
OH OH OH H
3 2 3 2
H OH H OH
-D-glucose -D-glucose

Cyclization of glucose produces a new asymmetric center at C1

The 2 stereoisomers are called anomers, α & β
cyclic sugars have essentially planar rings, with the OH at the
anomeric C1:
• α (OH below the ring)
• β (OH above the ring)
 Monosaccharides

• Monosachccharides are aldoses or ketoses

• Cyclize to form α or β isomers
• Derivatives includes aldonic acids, uronic acids,
deoxysugars and amino sugars
• They can be linked to each other or to other
molecules by glycosidic bonds
• Examples – Glyceraldehyde, Glucose, fructose,
Mannose
 Derived monosaccharides
• Sugar acids – Oxidation of the aldose and conversion
of aldehyde to carboxylic acid (eg. D glucoronic acids)
• Sugar alcohols – Reduction of the carbonyl group to
the hydroxyl group (eg. sorbitol, xylitol)
• Amino sugars – Replacement of the hydroxyl group to
the amine group (eg. D-Glucosamine)
• Deoxysugars – Replacement of OH by H group (eg.
Deoxyribose)
 Disaccharides
• Sucrose
(glucose+fructose)
• Lactose
(glucose+galactose)
• Maltose (glucose+glucose)
 Formation of disaccharides

glucose fructose
sucrose
R- OH + HO - Rʹ R-O-Rʹ + H 2O

(1 2) linkage
Glycosidic bond
 Polysaccharide

• Homopolysaccharides: Composed of single type of

monosaccharide unit
• Storage forms of food and energy
• Structural components of the cells
• Many polysaccharides are insoluble in water
 Storage polysaccharides
• Starch: energy storage used by plants
• long repeating chain of α-D-glucose
• Chains up to 4000 units

Starch is composed of a mixture of two major substances

Amylose: straight chain
Amylopectin: branched structure
 Amylose starch
CH2OH CH2OH CH2OH
CH2OH
O O H H O H
H O H H H H
H H H
H OH H
OH H OH H OH H

O O O
O

H OH H OH H OH
H OH

• Straight chain that forms coils α (1 4) linkage

• Most common type of starch
• 200-20,000 glucose units, which form a helix as a
result of the bond angles between the glucose units
 Amylopectin starch
CH2OH CH2OH CH2OH
CH 2 OH
O H O H H O H
H O H H H
H H H
H H
H OH H OH H OH
OH
O O O
O

CH2OH H OH CH2OH H OH CH2

H OH CH2OH H OH

O O H H O H
H O H H H H
H H H
H OH H
OH H OH H OH H

O O O
O

H OH H OH H OH
H OH

• Highly branched
• Glucose residues linked by α (1 4) and α (1 6)
linkage
• Branch points occur about every 12-25 residues along α
(1 4) chain
 Glycogen
• Energy storage of animals
• Stored in liver and muscles as granules
• Similar to amylopectin
• Highly branched, with branch points occuring
about every 8-10 residues along α (1 4) linkage
O
O
O
O

O
O
O
O
O
O
O O
O
O
 Dextrans
• Branched chain polysaccharides of D-glucose found in
yeast and some bacteria
• Glucose residues linked by α (1 6) and α (1 3)
linkage
• Chains vary in their length and extent of branching
 Structural polysaccharides
Cellulose :
• Most abundant polysaccharide
• Glucose chains with β (1 4) glycosidic linkages
• Result in long fibers - for plant structure
• Non digestible by humans CH2OH
CH2OH

O
H
CH2OH
O H O
H
CH2OH OH H
O H O
H
CH2OH OH H
H O H O H
OH H
H O H O H
H H OH
H OH H
O
H H OH
OH H
H OH
H
H OH
H OH
 Chitin

• Monosaccharides units linked by β (1 4)

glycosidic bonds to form a linear polymer
• Repeating disaccharide contain N-acetyl-D-
glucosamine
• Chitin is a component of crustacean shells
 Heteropolysaccharides
• Composed of different types of polysaccharides
• Complex structure
• Variety of functions
• Occur frequently in combination with non
carbohydrate material
- Glycosaminoglycans
- Glycoproteins
- proteoglycans
 Glycosaminoglycans
• Repeating disaccharide units
• Contain hexose amine and
generally a residue of uronic
acid and a sulphate group
• Major function – Forming a
matrix that holds together
protein components of skin
and connective tissue
 GAGS

• Skin • Formation of extracellular matrix

• Vitreous body • Interact with various
• Cartilage , bone growth active molecules
• Umbilical cord • Role in central nervous system,
• Blood vessel cartilage
 GAGS
HEPARAN
SULFATE

• Anticoagulant • Wide variety of tissue like dermis,

• Acidic complex vascular wall, cornea
polysaccharide • Cell to cell or cell to matrix
• Found on cell surface interactions
• Extracellular matrix • Anticoagulant activity
 Glycoproteins
• Conjugated proteins having
a covalently linked
carbohydrate component
• The covalently linked
carbohydrate may be N or
O linked glycans
• Extracellular location and
function
• Many proteins are
glycoproteins
 Proteoglycans

• Proteins and GAGS in the

extracellular matrix
aggregate to form
proteoglycans
• The aggregates have
polyanionic character
• Localized to membranes in
endoplasmic reticulum and
golgi
• Serve as lubricant and
support elements
 Proteoglycan structure in cartilage

Healthy Cartilage Degenerated Cartilage

Carbohydrate analysis
 Structural determination of
carbohydrates

• Identification of sugars
• Stereochemistry of each sugar
• Types of linkages
• Types of ring structures
• Anomeric configuration of each sugar
• Sequence of the different sugar residues
 Methods for estimating MW-GAGS

• NMR
• Gel permeation chromatography
• Electrophoresis
Agarose and Polyacrylamide gels
• Mass spectrometry
small fragments and isomers are a challenge
 Conventional glycoconjugate
characterization

1. Isolation of individual glyco conjugates

2. Detachment and purification
3. Structural characterisation
High throughput technologies

Oligosaccharide microarrays-
carbohydrate binding proteins

Arrays of known carbohydrate

binding proteins
Applications
 Glycocoatings for implants and
devices

Functionalization of carbon surface of a biomedical device with

synthetic carbohydrates
Glyconanoparticles
Carbon nanotubes

Biomimetic surface modification

of CNTs using glycosylated polymers
Carbohydrate based vaccines
Carbohydrates and stem cell niche
 Carbohydrates based hydrogels

Hyaluronic acid – Neural progenitor

Cells – β3-tubulin
Seidlits Ak et. al Biomaterials 2010

Alginate – Neural stem cells

Nestin & β3-tubulin
Banerjee RS et.al Biomaterials 2010

182 pa 1028 pa 1735 pa 19700 pa Medium

with growth
factor
 Cartilage tissue engineering

GAGS Chondrocytes

Water Collagen
molecules

It is avascular, aneural and an alymphatic tissue and has

limited self-repair capabilities
 Gellan gum (GG)

• Polysaccharide from microbial fermentation of

sphingomonas paucimobilis microorganism

• Non toxic and is used as an injectable system in a

minimally invasive manner

• Opthalmologic applications

• Structural similarity to native cartilage

 Glycomics

'We envisage that the collective enterprise of glycomics

over the next decade will begin the process of decoding
the glycome, thereby yielding many new insights into its
myriad functions and producing diverse advances in the
biomedical arena.'
Nature Chemical Biology
 References

• M Marandi, M Martin, Glyconanoparticles: polyvalent tools to study

carbohydrate based interactions. Advances in carbohydrate chem and
biochemistry, 2010 vol 64, 211
• DL Fuente, glyconanoparticles- types, synthesis and applications in
glycoscience, biomedicine and materials science. Biochemica and
biophysica acta general subjects, 2006 vol 1760 issue 4
• DH Dube, K Champasa, Cehemical tools to discover and target beacterial
glycoproteins. Chemical communications, 2011, 47, 87-101

• Foundations of biochemistry II Biomolecules, J Stenesh, Plenum Press

• Biochemistry illustrated, P N, Campbell and A D, Smith

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