Fundamentals

of
Biochemistry
BCHE 2030
Carbohydrates
Prof Kwok Fai LAU
School of Life Sciences 1
CUHK
 Carbohydrates (or Saccharides)
• are the most abundant biomolecules in nature
• Range from as small as glyceraldehyde (MW = 90 g/mol)
to as large as amylopectin (MW = 200,000,000 g/mol)
• are a direct link between solar energy and the chemical
bond energy of living organisms

Other
carbohydrates
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The USDA's food guide pyramid

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Functions of Carbohydrates
• Energy source for plants and animals (e.g. Glucose)

• Storage form of energy (e.g. glycogen in animals ,

starch in plants)

• Structural elements of cells and tissues e.g. cellulose in plant

cell walls, chitin in insect exoskeleton

• Precursors for the production of other biomolecules

glycolysis
Glucose Acetyl CoA Fatty acid synthesis

Also amino acids, purines and pyrimindines

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• Complex carbohydrate polymers covalently attached to
proteins or lipids act as signals that determine the
intracellular location or metabolic fate of these hybrid
molecules (glycoconjugates)

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Classification of carbohydrates
• A carbohydrate is composed of carbon, hydrogen and oxygen
• General formula (CH2O)n n = no. of carbon (3 or more)
• Few Exceptions : e.g. Deoxyribose (C5H10O4)

Monosaccharides (Simple sugar)

• One sugar unit
• are usually colourless, water-soluble, crystalline solids
• Building blocks of other sugars
• Glucose (C6H12O6) is the most abundant monosaccharide in
nature
• Other examples : fructose, ribose
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Oligosaccharides
• Short chains of monosaccharide units (2-10 or more sugar
units) joined by glycosidic bonds
• The most abundant oligosaccharides are the disaccharides
(double sugars) – two simple sugars joined together
e.g. Maltose = Glucose ---- Glucose

Polysaccharides (complex carbohydrates)

• Long chains of simple sugars joined together

Glucose----Glucose……..
e.g. Glycogen =
……….Glucose----Glucose----Glucose………..
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 Monosaccharides (simple sugars)

Two classes - aldose and ketose

Aldose Ketose

Aldehyde group
Ketone group

R
R
R

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Number of carbon Class
---------------------------------------------------------------
3 Triose
4 Tetrose
5 Pentose
6 Hexose

an aldotriose a ketotriose

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Properties of Monosaccharides
• See slide 6
• Monosaccharides are reducing sugars
• All the monosaccharides (except dihydroxyacetone)
contain one or more asymmetric (chiral) carbon atoms >
thus they have optical isomers
• Asymmetric carbon - carbon atom that is attached to
four different atoms or four different groups of atoms
1
CH3
2
C
C Cl 3
H
Br
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Stereoisomers (optical isomers)
• Stereoisomers are isomeric molecules whose atomic
connectivity is the same but whose atomic arrangement
in space is different

(1) Enantiomers are stereoisomers that are non-superimposable

complete mirror images of each other

(2) Diastereomers are stereoisomers that are not mirror image

of each other

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Stereoisomers
C4H8XY

A B C D

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Enantiomers
• Enantiomers are stereoisomers that are mirror images of
each other
• They have identical chemical properties but differ in their
interaction with polarized light

• Two forms for carbohydrates

D – rotates polarized light to the clockwise
L – rotates polarized light to anticlcokwise

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A wire-grid polarizer converts an unpolarized beam into one with a single linear polarization
• D and L refer to the configuration of the asymmetric carbon
atom furthest from the aldehyde or ketone group
• asymmetric carbon - carbon atom that is attached to four
different atoms or four different groups of atoms
• When the hydroxyl group on the reference carbon is on the
right in the projection formula, the sugar is the D isomer

• D-forms of monosaccharides predominate in mammalian

carbohydrates 14
Epimers
• Epimers are diastereromers that differ only in the configuration
at a single asymmetric carbon

• D-glucose, D-galactose and D-mannose are diastereomers of each other

• D-glucose and D-galactose are epimers of each other
• D-glucose and D-mannose are epimers of each other
• D-galactose and D-mannose are not epimers of each other 15
In general, a simple sugar with n asymmetric carbons can
have 2n stereoisomers

e.g. aldohexose – number asymmetric carbon = 4

 24 = 16 stereoisomers 16
e.g. ketohexose – number asymmetric carbon = 3
 23 = 8 stereoisomers
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The common monosaccharides have cyclic
structures

• The aldehyde and ketone group

can react with a hydroxyl group to
form covalent bond 18
 (a-D-Glucose)

Figure 11.4
Biochemistry 6th Ed
©2007 WH Freeman (b-D-Glucose)

• A new asymmetric centre (anomeric carbon) is formed during ring

formation (C1 in glucose). Two isoforms are exist : a and b (anomers)
• The a form and b form are interconvertible
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Figure 11.5
Biochemistry 6th Ed
©2007 WH Freeman

OH O OH

OH O

Figure 6
Instant Notes in Biochemistry 20
©1997 BIOS
Monosaccharides are reducing sugars
• Reducing sugars - sugars that contain a free aldehyde
or ketone group which can reduce ferric (Fe3+) or cupric
( Cu2+)

• Benedict’s solution
Reducing sugar
Blue Orange / Red
copper II sulfate Boil copper I oxide
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Oxidation of Monosaccharides
Aldose Blue Benedict’s soln carboxylate Red copper (I) oxide

O O

R C H + 2 Cu2+ + 5 OH- R C O- + Cu2O + H2O

Ketose hydroxy carboxylate

O OH

R C CH2OH + 2 Cu2+ + 5 OH- R C COO- + Cu2O + H2O

H
Colorimetric glucose analysis and diabetes
• Diabetes is a metabolic disorder results in abnormally high
blood glucose level
• Modern measurement : add a drop of blood to a test strip
containing the enzyme glucose oxidase
b-D-Glucose -D-Gluconolactone

CH2OH CH2OH
O OH Glucose oxidase O
OH + O2 OH O + H2O2

HO HO
OH OH
peroxidase
H2O2 + Dye Colored product

• Because blood glucose levels change with the timing of meals

and exercise, single-time measurements do not necessarily
reflect the average blood glucose over hours and days 23
Hemoglobin glycation
• Hemoglobin in RBC is constantly exposed to blood glucose

• The rate of the reaction is proportional to the concentration

of glucose
• The amount of glycated hemoglobin (GHB) at any time
reflects the average blood glucose concentration over
the circulating life time of the RBC (about 120 days)
Normal GHB values : about 5%
Diabetes GHB values : as high as 13%
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Modified Monosaccharides

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Oligosaccharides
• Oligosaccharides are short chains of monosaccharide (2-
10 or more sugar units)

• The most abundant oligosaccharides are the disaccharides

• Oligosaccharides can attach to proteins and lipids to form

glycoproteins and glycolipids respectively, which are
important in cell-cell interaction, cell adhesion, cell
migration etc.

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Disaccharides
Disaccharides consist two molecules of monosaccharide
joined by a glycosidic bond

H2O condensation

b-D-galactose D-glucose

b1→4 glycosidic bond

a1→4 glycosidic bond 27

Non-reducing end Reducing end

Lactose

Anomeric carbon involves in glycosidic bond formation

Free anomeric carbon 28

Sucrose is not a reducing sugar

a-D-Glucose b-D-Fructose

H2O condensation

Anomeric carbons
involve in glycosidic
bond formation

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Trehalose is also a non-reducing disaccharide

• Can be found in animals, plants, and microorganisms.

• Trehalose is the major carbohydrate storage molecule used by insects for
flight

• a1-a1 glycosidic bond keeps nonreducing sugars in closed-ring form

 the aldehyde group does not react with other molecules (such as
lysine or arginine residues of proteins)
Polysaccharides
• Also called glycans
• Long chain polymer of monosaccharides

(1) Homopolysaccharides
• contain only a single type of
monosaccharide

(2) Heteropolyaccharides
• contain two or more different
kinds of monosaccharides

e.g. Arabinoxylans- polymers of arabinose

and xylose (found in plant cell wall).
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• Storage form of energy

e.g. glycogen in animals

→ glucose → metabolic processes → energy production

starch in plants
dextran in yeast and bacteria

• Structural elements of cells and tissues

e.g. cellulose in the plant cell walls,
chitin in the exoskeleton of animals

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Glycogen
• is mainly stored in liver

Glycogen granules in a liver cell

• is a branched polysaccharide of D-glucoses, contain both

a1→4 and a1→6 glycosidic bonds

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Starch
• is produced in chloroplasts of plants
• contains two types of glucose polymers
Amylose - linear polymer of D-glucose
linked by a1→4 bonds

Amylopectin - branched polymer of D-glucose joined by

a1→4 and a1→6 bonds

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A cluster of amylose and amylopectin
 Amylopectin vs Glycogen

Degree of
about every 25 residues about every 10 residues
branching:

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Cellulose
• Cellulose is a tough and insoluble polysaccharide
• in the cell walls of plants
• unbranched linear polysaccharide,
consisting of 10,000 to 15,000 D-
glucose units -- joined by b1-4
glycosidic bonds

• Intermoleular hydrogen bonds are largely responsible for the

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great strength of cellulose
• To break down cellulose into glucose molecules require harsh
condition > concentrated acids + high temperature

• Many mammals do not have enzyme to digest cellulose

• Cellulose and other indigestible plant polysaccharides

constitute the dietary fibers which are important for
maintaining proper gut movement and function

• Ruminant animals such as cattle have cellulase-producing

bacteria in their digestive tracts and so can digest cellulose

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Glycosaminoglycans (GAGs)
• a family of linear polysaccharides
• composed of repeating dissaccharide units
• one of the sugars is an amino sugar
• at least one of the sugars
has a negative charged
group

Keratan sulfate - component of

connective tissues

Heparin - anticoagulant

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Glycoconjugates
Carbohydrates can be attached to other biomolecules to
form glycoconjugates

Glycoproteins

• have one or several oligosaccharides joined covalently to a

protein
• The carbohydrate may constitute from 1% to 70% or more
of the glycoprotein by mass
• Many glycoproteins are components of cell membranes
• Functions e.g. cell adhesion , the binding of sperm to eggs

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• Carbohydrates can be linked to proteins through
asparagine or through serine / threonine residues

O-linkage – attached to the oxygen atom

in the side-chain of serine / threonine

N-linkage – attached to the amide nitrogen

atom in the side-chain of asparargine

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Proteoglycans
• are distinguished from glycoproteins by their extremely high
carbohydrate content > up to 95% of the dry weight
• are found mainly in the extracellular matrix of tissues
• have one or more sulfated GAGs attached covalently to a
membrane protein or secreted protein

Tetrasaccharide bridge

Proteoglycan

• Large amount of water and cations are trapped within

proteoglycan structure
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• Proteoglycan aggregates
 Extracellular Matrix (ECM)
• Material outside the cell
• Strength, elasticity, and physical barrier in tissues
• Main components
– Proteoglycan aggregates
– Collagen fibers
– Elastin (a fibrous protein)
Interactions between cells and extracellular matrix

• Multiadhesive protein
eg. fibronectin contains
separate domains for fibrin,
heparin sulfate (a GAG) and
collagen and a family of
plasma membrane proteins
called integrins.
• Functions
- allow binding of cells to
extracellular matrix
- provide paths that direct cell
migration in developing tissues
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Carbohydrates as informational molecules:
The sugar code
The many possible way that carbohydrates can be linked
together to form branched structures gives them the
potential to carry more biological information than nucleic
acids or proteins of similar size.

e.g. 2 different nucleotides > form 2 different dinucleotides

2 different hexoses > form 36 different combinations

(not all possibilities exist in nature)

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• Lectins are proteins that read the sugar code

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• P-selectins recognize and bind specific oligosaccharides on the
surface glycoproteins of lymphocyte
• Endothelial cells expressed P-selectins (a lectin) transiently in
response to tissue damage from infection or mechanical injury

Blood
capillary Blood flow

Site of inflammation
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Role of oligosaccharides in recognition events at
the cell surface and in endomembrane system

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