BIOMOLECULES

Carbohydrates
Carbohydrates: Topic
• Biological polymers

• Carbohydrates, definition and structure

• Monosaccharides

• Monosaccharide derivates

• Oligosaccharides

• Polysaccharides
– Homopolysaccharide
– Heteropolysaccharide
Carbohydrates: Biological polymer

• In biological systems three chemical compounds can form

polymers:

– a polymer is

a large molecule formed by the union of at least five identical

monomers; it may be natural, such as cellulose or DNA, or
synthetic, such as nylon or polyethylene; polymers usually
contain many more than five monomers, and some may contain
hundreds or thousands of monomers in each chain

• Nucleic acids
• Amino acids
• Carbohydrates
Carbohydrates: Biological polymer
• Monomers to Polymers

MONO-MER UNIT

DI-MER UNIT
2 mono units linked by
condensation reaction

OLIGO-MER UNIT n= 3-10

POLY-MER UNIT
Many monomer units linked together
Carbohydrates: definition and structure
• Cn(H2O)n is the general chemical formula of these
molecules
– n is commonly 3 - 6
• Carbohydrates are also called saccharides from
the Greek word sakcharon, meaning sugar

• Key functional groups :

– alcohol
– aldehyde or ketone

• Monosaccharides are the simplest sugars

• Oligosaccharides composed of 2 - 10
monosaccharides
• Polysaccharides composed of 11-X
monosaccharides
Glucose, a C-6 monosaccharide
Carbohydrates: Function

• Store chemical energy

• Structural support (cellulose, chitin, etc)

• Precursors to other biomolecules (amino acids, lipids,

nucleotides)

• Conjugates to other biomolecule classes (glycoproteins,

glycolipids)
Carbohydrates: Properties of their
functional groups
• The key to understanding carbohydrate chemistry is the
knowledge about the properties of their functional groups
– have two of them

• All simple sugars are alcohols

• All simple sugars are aldehydes or ketones

• sugars are polyhydroxy aldehydes or ketones

• The alcohols can react with the own carbonyl group of the
aldehyde or ketone group
– this will be of prime importance
 Carbohydrates: Nomenclature and
structure
• Carbohydrates consist of single or multiple units known as monosaccharides
– oligosaccharide and polysaccharide refer to carbohydrate polymers

• The suffix ‘-ose’ designates a carbohydrate

• According to the number of C atoms

# of Carbons in Name of Example

chain Carbohydrate
3 Triose Glyceralaldehyde
4 Tetrose
5 Pentose Ribose, Deoxyribose
6 Hexose Glucose, Fructose
7 Heptose
9 Nonose

• Carbohydrates which contain an aldehyde group are called

aldoses
• Carbohydrates which contain a ketone group are called ketoses
Carbohydrates: RECAP, stereochemistry

• Enantiomers: stereoisomers that are mirror images of

each other

• Diastereomers: Pairs of isomers that have opposite

configurations at one or more chiral centers but are NOT
mirror images

• Epimers: Two sugars that differ in configuration at only

one chiral/specific carbon atom
Carbohydrates: RECAP, stereochemistry
• Isomers
– same chemical formulae (e.g. C6H12O6), but different
constitution
Carbohydrates: RECAP, stereochemistry
• Enantiomers
– mirror images
Carbohydrates: RECAP, stereochemistry
• Chiral centers
– asymmetric carbons
Carbohydrates: RECAP, stereochemistry
• Epimers
– differ in conformation around one
chiral/specific carbon
Carbohydrates: Nomenclature and
structure
• Dealing with stereochemistry in CHO CHO
sugars: the Fisher Projection
HO H H OH
• Carbon chain runs top to bottom
CH2OH CH2OH
• Carbonyl group gets the lowest
possible number
CHO CHO

• Simplify the drawing by omitting

the bond perspective HO H H OH

– this scheme can be extended to CH2OH CH2OH

longer chains
L-glyceraldehyde D-glyceraldehyde
(levo, left) (dextro, right)
Carbohydrates: Nomenclature and
structure
• D,L designation refers to the configuration of the highest-numbered
chiral center ONLY

• D,L do not specify the sign of rotation of plane-polarized light

CHO

• D-sugars predominate in nature

H OH
H OH
H OH
H OH

CH2OH
Carbohydrates: Monosaccharides
• The simplest sugars are the three carbon varieties
Cn(H2O)3
– start from glycerol
• one gets two possibilities
• the first:

CH2OH CHO
...and convert one
HO CH of the hydroxyl groups HO CH
to a carbonyl group
CH2OH CH2OH
An aldotriose
Glyceraldehyde

Chiral Centre!
Carbohydrates: Monosaccharides
• The other variation Cn(H2O)3
– start again from glycerol

CH2OH CH2OH
...and convert one
HO CH of the other hydroxyl groups
O
to a carbonyl group
CH2OH CH2OH

A ketotriose
Dihydroxyacetone
 Carbohydrates: Monosaccharides
• Monosaccharides are simple sugars with multiple OH groups
• Categorized by the number of carbons, typically 3 – 8 carbons
– Most abundant monosaccharides are hexoses

Monosaccharides

Aldoses Ketoses
(Polyhydroxy aldehydes) (Polyhydroxy ketoses)

H
C C=O
OH
Aldehyde group Ketone group
Carbohydrates: Monosaccharides
• Fisher projections of the three to six carbon D-aldoses

Emil Fisher
(1852-1919)
Carbohydrates: Monosaccarides
• Fisher projections of the three to six carbon D-ketoses
Carbohydrates: Ring formation
• An aldehyde can react with an alcohol to form a
hemiacetal
• A ketone can react with an alcohol to form a hemiketal
 Carbohydrates: Ring formation
• In the straight chain form several
chemical features of the molecules are
O
more apparent H C1
C H 2OH
1
H C2 OH
– Molecules contain free carbonyl C
2
O
HO C3 H
groups (- C=O) making glucose an HO C H
3
aldehyde and fructose a ketone H C 4 OH
H C OH
– Carbonyl groups subject to H C OH
4
5 H C OH
nucleophilic attack, since carbonyl 5
C H 2 OH
carbon is electron deficient 6 6C H 2OH

• -OH groups on the same D-glucose D-fructose

molecule act as nucleophile, add (an aldohexose) (an ketohexose)

to carbonyl carbon to create ring

form
• Leads to hemiacetal formation
• Reversible reaction in both acid or
base solution
Carbohydrates: Ring formation
• Pentoses and hexoses can form stable 5-atom and 6-atom
ring structures

• The six-membered ring is the most stable form, then the five
membered ring

• Six-membered carbohydrate rings are designated pyranose

based on their similarity to pyran

• Five-membered rings are designated furanose

O O

Pyran Furan
Carbohydrates: Ring formation
• Pentoses and hexoses can cyclize as the aldehyde or ketone
reacts with distal OH
• Glucose forms an intra-molecular hemiacetal, as the C1 aldehyde
and C5 OH react to form a 6-member pyranose ring, named after
pyran
• These representations of the cyclic sugars are called Haworth
projections
Carbohydrates: Ring formation
• Transformation of Fisher projection to Haworth projection
– e.g. cyclization of D-glucose to form D-glucopyranose

Norman Haworth
(1883-1950)

The two possible anomers

Carbohydrates: Ring formation
• Cyclization of glucose produces a new asymmetric center at C1.
The two stereoisomers are called anomers, α and β.
• Haworth projections represent the cyclic sugars as having
essentially planar rings, with the OH at the anomeric C1
• α (OH below the ring)
• β (OH above the ring)
Carbohydrates: Ring formation
• Fructose can form either:
• a 6-member ring by reaction of the C2 keto group with the OH on
C6 or
• a 5-member furanose ring by reaction of the C2 keto group with
the OH on C5
Carbohydrates: Ring formation
• Cyclisation of D-ribose to form D-ribofuranose and D-ribopyranose
Carbohydrates: Ring formation
• The nearly correct 3-D structures for carbohydrate ring structures are the
chair form structures
– somewhat difficult to draw correctly, so the Haworth structures are
used

• The groups attached to the ring carbons can be in axial position or the
equatorial position
– the equatorial position is less sterical hindered and therefore preferred
for bulkier groups
• In the β-D-glucose every bulky group is in the equatorial position
• β-equatorial(up), α-axial (down)
Carbohydrates Reaction
• Reducing Sugar
• Aldoses with free anomeric carbons will reduce oxidising
agents, such as peroxide, ferricyanide and some metals
Cu(II) and Ag(I)
• These redox reactions convert the sugar to a sugar acid
• Glucose is a reducing sugar, so these reactions are the
basis for diagnostic tests for blood sugar
– e.g. Fehling’s reagent (CuSO4 in base)
RCHO + 5 OH- + Cu(II) → RCOOH + CuO2 + 2 H2O
Carbohydrates: Monosaccharide
derivatives
• Sugar acids
– oxidation of aldehyde or hydroxyl group to a carboxylic acid
• Sugar alcohols
– reductiion of aldehyde/ketone to a hydroxyl group
• Deoxy sugars
– constituents of DNA etc
• Sugar esters
– phosphate esters like ATP (energy source) are important
• Amino sugars
- contan an amino group in place of a hydroxyl group
• Acetals, ketals and glucosides
– basis for oligo- and polysaccharides
Carbohydrates: Monosaccharide
derivatives
• Sugar acids
- The aldehyde at C1 or OH at C6 is oxidized to a carboxylic acid
- e.g. gluconic acid, glucuronic acid
Carbohydrates: Monosaccharide
derivatives
• Sugar alcohols
– reduction of aldehyde/ketone to a hydroxyl group
- Frequently used as sweeteners in diet foods

Glucitol (sorbitol)
D-ribitol
Carbohydrates: Monosaccharide
derivatives
• Deoxy sugars
– 2-deoxyribose
• a deoxy sugar is a key
component of DNA
HO HO
OH OH
H O H O
H H

H H H H
OH OH OH H

Ribose Deoxyribose

D-ribofuranose) D-deoxyribofuranose)
Carbohydrates: Monosaccharide
derivatives
• A sugar ester

– ATP (Adenosine triphosphate) NH2

N
N
O O O
-
O P O P O P O N N
O
- - -
O O O

OH OH
Carbohydrates: Monosaccharide
derivatives
• Amino sugars

– components of bacterial cell walls and proteoglycans (a

major component of connective tissue)
Carbohydrates: Oligosaccharides
• Oligosaccharides are glycosides of two or more
sugars

• The nomenclature of these compounds specifies

– the carbohydrates involved

– the carbons connected by the glyocoside bond

– the configuration at the anomeric center (when

the anomeric hydroxyl is modified)
Carbohydrates: Oligosaccharides
• Maltose, a cleavage
OH OH

product of starch H
O H
H O H
H
• Composed of 2 α-D-
H
OH H 1 4 OH H

glucopyranose OH OH
OH OH

sugars H OH H OH

• Glycosidic bond α-D-glucopyranose α-D-glucopyranose

formed between C1 H2O
OH OH
and C4 OH of the 2
glucose H
O H H
H
O H
H
- This bond is an α- OH H OH H

1,4 glycosidic bond, OH O OH

because the
anomeric carbon is H OH H OH
α-D-glucopyranosyl-(1,4)-α-D-
in the α – position glucopyranose
Reducing sugar
- It is a reducing sugar
Carbohydrates: Oligosaccharides
• Cellobiose, a product of cellulose breakdown
• Composed of 2 β-D-glucopyranose sugars
• The β(1,4) glycosidic bond is represented as a zig-zag
• Has reducing properties

β-D-glucopyranosyl-(1,4)-β-D-
glucopyranose
Carbohydrates: Oligosaccharides
• Lactose, also refereed to as milk sugar
• Composed of β-D-galactopyranose and α-D-glucopyranose
• The glycosidic bond is β(1,4) (from the anomeric OH of
galactose)
• Has reducing properties

β-D-galactopyranosyl-(1,4)-α-D-
glucopyranose
Carbohydrates: Oligosaccharides
• Sucrose, also refereed to as table sugar
• Composed of α-D-glucopyranose and α-D-fructofuranose
• The glycosidic bond links the anomeric OHs of glucose and fructose
• Because the configuration at the anomeric C of glucose is α (O points down
from the ring), the linkage is α(1,2)
• Has no reducing properties

α-D-glucopyranosyl-(1,2)-α-D-fructofuranose
Carbohydrates: Oligosaccharides
• Know the important features

– be able to identify anomeric carbons, reducing

and non-reducing ends

– Sucrose is not a reducing sugar

– Note carefully the nomenclature of links. Be

able to recognize alpha(1,4), beta(1,4) etc
Carbohydrates: Polysaccharides
• Two classes:

• Homopolysaccharide

– Starch, glycogen and dextran

• energy storage molecules

– Chitin and cellulose

• structural molecules

• Heteropolysaccharides

– Cell surface polysaccharide

Carbohydrates: Homopolysaccharides
• Starch
- A homopolymer of glucose joined by α-(1-4) glycosidic bonds found in plants
– Two forms: amylose and amylopectin
– Most starch is 10-30% amylose and 70-90% amylopectin
– Amylose is linear; has α-(1,4) links, adopts a helical conformation, the end with an
anomeric C1 not involved in a glycosidic bond is called the reducing end
– Amylopectin is a glucose polymer with α-(1,4) linkages and α-(1,6) branches after
every 20-30 residues, many non reducing ends
– The branches produce a compact structure and provide multiple chain ends at
which enzymatic cleavage can occur

Amylose

Amylopectin
Carbohydrates: Homopolysaccharides
• Why is some starch branched ?

– Consider the phophorylase reaction whereas

• Phosporylase releases glucose-1-phosphate products from

the amylose or amylopectin chains, only acts at non
reducing ends

• The more branches, the more sites for phophorylase attack

• Branches provide a mechanism for fast releasing (or

storing) glucose units for (or from) metabolism
Carbohydrates: Homopolysaccharides
• Glycogen
• The glucose storage carbohydrate in animals (humans)

– Glycogen constitutes up to 10 % of liver mass and 1-2 % of

muscle mass

– Glycogen is stored energy for the organism

– Only difference from starch: number of branches

• Alpha (1,6) branches every 8-12 residues

– The highly branched structure permits rapid release of glucose

from glycogen stores e.g. in muscle during exercise

– The ability to rapidly mobilize glucose is more essential to

animals than to plants
Carbohydrates: Homopolysaccharides
• Dextran

• A storage polysaccharide of bacteria

• Also a polymer of glucose, but with alpha(1,6) glucosidic bonds

• Branches can be (1,2),(1,3) or (1,4)

• Dextrans formed by bacteria are components of dental plaque

www.polydex.com/v2/products/ dextran-defined.html
Carbohydrates: Homopolysaccharides
• Cellulose
– A structural polysaccharide and the most abundant
natural polymer on earth

– Cellulose is the principle strength and support of trees

and plants (major constituent of plant cell walls)

– Linear homopolymer of β-glucose with β (1-4) linkages

– Every glucose is flipped over due to the β linkages.

This promotes intra-chain and inter-chain H bonds and
van der waals interactions that cause cellulose chains
to be straight and rigid, pack with crystalline
arrangement in thick bundles called microfibrils
Carbohydrates: Homopolysaccharides

β (1-4) linkages

microfibrils
Carbohydrates: Homopolysaccharides
• Chitin
– Component of exoskeletons of crustaceans, insects and spiders
and cell walls of fungi
– Resembles cellulose, but uses N-acetylglucosamine connected
by β-(1-4) linkages

www.swisscorporation.com/ chitin.htm
Carbohydrates: Heteropolysaccharides
• Oligosaccharids are important components
of many proteins and lipids

– both have structural and regulatory

functions

• Heteropolysaccharides contain modified

sugars or different sugars in straight or
branched chains

– Often linked to peptides or proteins

(peptidoglycans, proteoglycans or
glycoproteins) or lipids (glycolipids or
lipopolysaccharides)

Glycoprotein
www.funhousefilms.com/ sciencpg.htm