Carbohydrates

Class:
JC1
Module: Concepts & Principles of
Biomedicine (CPB)
Code:
CPB4
Lecturer: Prof. Tin Tun
Date:
1/10/2012

Learning Outcomes

To understand the basic properties and functions of

carbohydrates.
Describe the key structural features of monosaccharides
( aldose/ketose, L&D isomeric forms and cyclisation).
Describe Glycosidic bonds and the structure of common
disaccharides.
Describe the structure and function of polysaccharides:
glycogen, starch and cellulose.
Describe constituents of the extracellular matrix:
glycosaminoglycans and proteoglycans and hereditary
disorders of glycosaminoglycan breakdown
(mucopolysaccharidoses).
Discuss glycoproteins.

Carbohydrates
One of our most Important foodstuffs
One of the two ways our body has to store food (fuel)

Cell membranes
Intercellular communication

Empiric Formula
(CH2O)n
i.e. hydrate of carbon

Carbohydrates
(CH2O)n

????

What are they?

Sugars / Sugar Polymers
What are Sugars:
Important Chemical groups to consider:
Hydroxyl group (-OH) Hydrogen linked to oxygen +
one spare valency for oxygen to link to another atom
Carbonyl group (-C=O) Carbon atom linked to oxygen
by a double bond, two carbon valencies free to link to
other atoms

Sugars:
Carbon compounds :
At least two carbon atoms linked to an OH group and at least one
carbonyl group (not linked to anOH) at least three carbon
atoms = triose
Glyceraldehyde
O
H
C
H

Carbonyl group

OH
H

H C
H
C3H6O3

OH

H C
C

H C
dihydroxyacetone
H

Aldehyde
One of
the two
spare
positions
on
carbonyl
carries a
H atom

C
O

formaldehyde

H3 C
C

acetaldehyde

OH

O
OH

Ketone
Both
Carbonyl
positions
linked to
other carbon
atoms

CH3

H3 C
C

O
acetone

Monosaccharides simple sugars

3 7 carbon atoms
Each carbon atom contains a hydroxyl group
except the one that forms a carbonyl group
(either aldehyde or keto)
Classification:
Number of carbons
Nature of carbonyl group

No. of Carbons Generic Names

3 Carbons:
4 Carbons:
5 Carbons:
6 Carbons:
7 Carbons:
9 Carbons:

Trioses
Tetroses
Pentoses
Hexoses
Heptoses
Nonoses

Examples

Glyceraldehyde
Erythrose
Ribose
Glucose
Sedoheptulose
Neuraminic acid

Most Important sugars in Human Biology:

Pentoses & Hexoses

Isomers, Epimers & Enantiomers

Isomers:
Same chemical formula but different structures
e.g. C6H1206 glucose, fructose, mannose, galactose
H
Aldehyde

OH

HO

H C

OH

OH

H C OH
H

Glucose

CH2OH

H
H

C OH
C

Isomers

HO

C H

H C

OH

OH

H C OH
H

Fructose

Ketone

Epimers two monosaccharides differing in configuration

around one specific carbon atom
H
H

C OH

H C OH

HO C H
HO C

HO C
C-4 Epimer

H C

C-2 Epimer

H
OH

HO C H
HO C H
H C

OH

H C OH

H C OH

H C OH

H C OH

H C OH

H C OH

Galactose
e.g.

Glucose

glucose + galactose (C-4 epimers)

glucose + mannose (C-2 epimers)

Mannose

Enantiomers
Structures mirror images D- and L- sugars

Humans vast majority D- sugars

Cyclization of monosaccharides
Molecules can twist and rotate around their bonds,
making possible a feature of sugars: Cyclization
>99.99% in ring form
(Rapidly reversible so sugars can flick in & out of ring)

C2 H

C5

H C6

OH
OH

D-Glucose

H C4 OH

C4

OH

C6
C5

OH
O

H
HO

HO C3 H

D-Glucopyranose
C1

C1

Aldehyde (or ketone) group reacts with an

alcohol group (hydroxyl attached to a carbon) on the
same sugar

C3

C2

OH

OH

Anomers ring creates anomeric carbon at C-1 of an aldose (or

C-2 of a ketose)
Designation or configuration
H

H
H

HO
C3

C2

OH

C1

C4

OH

OH

C5

OH
O

H
HO

C6

C1
H

H
OH

C5

OH
H

C4

C6

HO

C3

C2

OH

and anomers are in equilibrium and can be spontaneously

interconverted (mutarotation)
Importance: Enzymes are able to distinguish between anomers
Reducing sugars oxygen on the anomeric carbon is not
attached to another structure

Pentoses
Important Molecules in Biology:
Ribose
Deoxyribose

Nucleotides
(e.g. ATP, NAD)

Ribulose
Xylulose

Hexose-monophosphate
Shunt

Xylose

Glycoproteins

Nucleic Acid:
DNA / RNA

Hexose Dietary Sources

Glucose:

Fructose:

Fruit juices, starch, glycogen,

lactose, maltose, cane sugar
(sucrose)
Fruit juices, honey, cane sugar

Galactose: Lactose
Mannose:

Plants and gums

Complex carbohydrates
Monosaccharides joined together by o-glycosidic bonds
May be or
(o refers to -OH group of next molecule)
n=2

disaccharides
e.g. maltose
cellobiose
lactose
sucrose

glu 1-4 glu

glu 1-4 glu
gal 1-4 glu
glu 1-2 fru

n = 3-12

oligosaccharides

n > 12 hundreds

polysaccharides

Disaccharides

Polysaccharides
1-6
n > 12 hundreds
1-4,

Variation:
Monosaccarides
Glycosidic bonds
Branch points

Sturcture

Amylopectin
branched every 24-30 residues

Functions:
Storage:
Plants starch. Homopolymer of glucose
Amylopectin (80-85%) branched every 24-30 residues (1-4, 1-6)

Amylose (15-20%) non branched helical structure ( 1-4)

Animals Glycogen. Homopolymer of glucose. Branched every
12-14 residues
(1-4, 1-6)

Structural:
Plants cellulose. Homopolymer of glucose. Long straight chains
(1-4).
Insoluble & Indigestible by humans
Invertebrates chitin
Homopolymer of n-acetyl-glucosamine

Glycosaminoglycans (GAGs)
Heteropolysaccharides
repeating disaccharide units of
(acidic sugar aminosugar)n
D-Glucuronic
acid
Or
O
C5 epimer:
L-Iduronic acid

COOH

CH2OH

O
OH

O
OH

OH

Amino group
Acetyl Group

Acidic Sugar
COOat physiological pH

D-Glucosamine
or
D-Galactosamine
O

NH
C=O
CH3

May also be
sulfated on
C4, C6 or on
Amino Group

N-Acetylated amino sugar

Eliminates +ve Charge

GAGs CNTD
Large number of negative charges:
Repel each other, slip past each other
Surrounded by a shell of water molecules
Therefore forming gel-like matrix
Lubrication properties
Mucous secretions / synovial fluid
Gave them their original name: Mucopolysaccarides

GAGs CNTD

Extracellular:

Hyaluronic acid:
Lubricant & Shock abosrber
Synovial Fluid of joints, vitreous humor of eye, loose
connective tissue , cartilage
Chondroitin 4- and 6- sulphate:
Hold fibres in strong network
Cartilage, Aorta, Tendons, Ligaments
Keratan sulphates I & II
Loose Connective issue associated with Chrondroitin
Cornea of eye
Dermatan sulphate:
Skin, Blood vessels, Heart valves
Heparan sulphate:
Basement Membrane, component of cell surfaces
Heparin:
Intracellular, Anticoagulant
Mast cells that line arteries in Liver, Lungs,Skin

Proteoglycans (PG)
All glycosaminoglycans (except hyaluronic acid)
covalently bonded to protein

Proteoglycan aggregates PG monomers associate with a

molecule of hyaluronic acid = Bottle Brush

Proteoglycans - Functions
Found in extra cellular matrix (ground substance)
Structural properties
Polyanions Bind cations (eg Na+, K+)
Attract water into extracellular matrix.
Molecular sieves restricting passage of
macromolecules

Mucopolysaccharidoses
(Lysosomal storage diseases)
Clinically progressive Hereditary disorders
GAGs accumulate in tissues
Skeletal deformities, mental retardation
Deficiency of lysosomal hydrolayses normally involved in the
degradation of heparan slulphate or dermatan sulfate

Oligosaccarides in Urine used to identify specific disease

Mainly Autosomal Recessive

e.g.
Hurlers syndrome Iduronidase deficiency
Hunters syndrome - X linkded Iduronate sulphatase
deficiency

Glycoproteins
Proteins with attached oligosaccharides (2-10 sugars)
often branched

Membrane glycoproteins
Cell surface recognition
Cell surface antigenicity e.g. blood groups
Extracellular matrix
Mucins (80% carbohydrate) of GI and GU tracts act
as protective lubricants
Globular proteins in human plasma

Glycoprotein Oligosaccharides:
Generally branched heteropolymers
Do not have serial repeats
Oligosaccharide attachment to protein through
a) N-glycosidic link (amide group of asparagine)
b) O-glycosidic link (hydroxyl group of serine or
threonine
Contain no glucose
Degradation: by Lysosomal enzymes
Glycoprotein Storage diseases
(oligosaccharidoses)

Study Questions
Following a bout of gastroenteritis a 4-month
old infant was found to be intolerant to milk.
Which of the following disaccharides is likely
to be the cause of the problem?
A. Sucrose
B. Lactose
C. Maltose
D. Isomaltose
E. Cellobiose

Study Questions (Contd.)

Choose the ONE correct answer:

Mucopolysaccharidoses are inherited storage
diseases. They are caused by:
A. An increased rate of synthesis of proteoglycans.
B. The synthesis of polysaccharides with an altered
structure.
C. Defects in the degradation of proteoglycans.
D. The synthesis of abnormally small amounts of
protein cores.
E. An insufficient amount of proteolytic enzymes.

Refs:
Lippincott
- Chapter 7

Carbohydrates

- Chapter 14 Glycosaminoglycans and

Glycoproteins