BIOCHEMISTRY 1

2nd Lecture
CARBOHYDRATE
Structure and functions

Chemistry Education Department-UPI

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Why do we need carbohydrate?

• To give us energy
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Cx(H2O)y
Hydrated carbon!

Carbohydrates (glycans) have the following

basic composition:

I
(CH2O)n or H - C - OH
I
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Carbohydrates
• Many carbohydrates are soluble in water.
• The usual chemical test for the simpler
carbohydrates is heating with Benedict’s
solution.
• The formula for a carbohydrate is
(CH2O)n
• The n represents the number of times the
CH2O unite is repeated.
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• They are of major importance to both plants and

animals. More than half of all organic carbon
atoms in the world are in carbohydrate
molecules.
• They are made by chlorophyll-containing plants
in the process of photosynthesis.
6CO2 + 6H2O → C6H12O6 + 6O2
• Our bodies use carbohydrates for energy and
also as a source of carbon atoms for the
synthesis of many other compounds.
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• Polyhydroxy aldehydes or ketones, or compounds that

yield polyhydroxy aldehydes or ketones on hydrolysis.
• Carbohydrates Contain the Elements:
Carbon, Hydrogen and Oxygen
• They Are Split Into Three Groups Known As:
 Monosaccharides (Monomers) - simple sugars with multiple
OH groups. Based on number of carbons (3, 4, 5, 6),
a monosaccharide is a triose, tetrose, pentose or hexose.
Oligosaccharides - a few monosaccharides covalently linked.
Polysaccharides (Polymers) - polymers consisting of chains
of monosaccharide or disaccharide units.
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Classification of carbohydrates
• Monosaccharides (monoses or glycoses)
• Trioses, tetroses, pentoses, hexoses
• Oligosaccharides
• Di, tri, tetra, penta, up to 9 or 10
• Most important are the disaccharides
• Polysaccharides or glycans
• Homopolysaccharides
• Heteropolysaccharides
• Complex carbohydrates
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Monosaccharides
• also known as simple sugars
• classified by
1. the number of carbons and
2. whether aldoses or ketoses
• most (99%) are straight chain compounds
• D/L-glyceraldehyde is the simplest of the aldoses
(aldotriose)
• all other sugars have the ending ose (glucose,
galactose, ribose, lactose, etc…)
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Structure of a simple aldose and a simple ketose

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Aldose sugars
H H H H H

C O C O C O C O C O

(H C OH)n H C OH H C OH H C OH H C OH

CH2OH CH2OH H C OH H C OH H C OH

Aldose Aldotriose CH2OH H C OH H C OH

n=1
Aldotetrose CH2OH
n=2 H C OH
Aldopentose
CH2OH
n=3
Aldohexose
n=4
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Ketose sugars
CH2OH CH2OH
CH2OH
CH2OH
C O C O CH2OH
C O
C O
(H C OH)n H C OH C O
H C OH
CH2OH
CH2OH H C OH H C OH
CH2OH
CH2OH H OH
Ketose Ketotriose Ketotetrose
n=1 Ketopentose H C OH
n=0
n=2
CH2OH
Ketohexose
n=3
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CONCEPTS OF ISOMERS

Two or more different compounds which contain the

same number and types of atoms and the same
molecular weights.

Projection formula (spatial arrangement to represent 3-

dimensional structure):
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D vs L Designation
• D & L designations CHO CHO
are based on the
H C OH HO C H
configuration about
the single CH2OH CH2OH
asymmetric C in D-glyceraldehyde L-glyceraldehyde
glyceraldehyde.
CHO CHO
• The lower
representations are H C OH HO C H
Fischer Projections. CH2OH CH2OH
D-glyceraldehyde L-glyceraldehyde
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Sugar Nomenclature
For sugars with more O H O H
than one chiral center, C C
D or L refers to the
H – C – OH HO – C – H
asymmetric C farthest
HO – C – H H – C – OH
from the aldehyde or
H – C – OH HO – C – H
keto group.
H – C – OH HO – C – H
Most naturally occurring CH2OH CH2OH
sugars are D isomers. D-glucose L-glucose
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Enantiomers and epimers

H H
H H C O C O
C O C O HO C H HO C H
H C OH OH C H HO C H HO C H
H C OH OH C H H C OH HO C H
CH2OH CH2OH
H C OH H C OH
these two aldotetroses are enantiomers.
They are stereoisomers that are mirror CH2OH CH2OH
images of each other
these two aldohexoses are C-4 epimers.
they differ only in the position of the
hydroxyl group on one asymmetric carbo
(carbon 4)
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Properties
• Differences in structures of sugars are
responsible for variations in properties
• Physical
• Crystalline form; solubility; rotatory power
• Chemical
• Reactions (oxidations, reductions, condensations)
• Physiological
• Nutritive value (human, bacterial); sweetness;
absorption
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Structural representation of sugars

• Fisher projection: straight chain

representation
• Haworth projection: simple ring in
perspective
• Conformational representation: chair and
boat configurations
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Cyclic Structure of Monosaccharides

Hemiacetal Formation

anomer anomer

The specific rotation of pure a-D-glucose or b-D-glucose

changes over time to reach an equilibrium (mutarotation)
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Hemiacetal & hemiketal formation

H H
An aldehyde can
react with an
C O + R' OH R' O C OH

alcohol to form R R
a hemiacetal. aldehyde alcohol hemiacetal

R R
A ketone can
react with an C O + "R OH "R O C OH
alcohol to form R' R'
a hemiketal. ketone alcohol hemiketal
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Pentoses and hexoses 1

CHO

can cyclize as the H

2
C OH

ketone or aldehyde HO
3
C H D-glucose
reacts with a distal H C OH (linear form)
4
OH. H C OH
5
Glucose forms an 6
CH2OH
intra-molecular 6 CH2OH 6 CH2OH
hemiacetal, as the C1 5 O 5 O
H H H OH
aldehyde & C5 OH H H
4 H 1 4 H 1
OH OH
react, to form a 6-
OH OH OH H
member pyranose ring, 3 2 3 2
H OH H OH
named after pyran.
a-D-glucose b-D-glucose

These representations of the cyclic sugars are

called Haworth projections.
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On the same
side as
attacking OH, is
a-anomer!

On the opposite
side as
attacking OH, is
b-anomer!

Intramolecular hemiacetal formation results in two

C(1) stereoisomers called anomers.
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Ring Forms (Glucose)

These are all Glucose

Memorize this structure

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Reactions of monosaccharides
• Carbonyl reactions:
• Osazone formation
• Cyanohydrin reaction
• Reduction
• Oxidation
• Action of base
• Action of acid
• Ring chain tautomerism
• Alcohol reactions
• Glycoside formation
• Ether formation
• Ester formation
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Formation of osazones
• once used for the identification of sugars
• consists of reacting the monosaccharide with
phenylhydrazine
• a crystalline compound with a sharp melting point
will be obtained
• D-fructose and D-mannose give the same osazone
as D-glucose
• seldom used for identification; we now use HPLC
or mass spectrometry
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Disaccharide Synthesis

The reactions, the names of the sugars, and

whether they are mono- or disaccharides is what
you should know (also, “Glycosidic linkage”)
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Disaccharides: 6 CH2OH 6 CH2OH

Maltose, a cleavage H
5 O H H
5 O H
H H
product of starch 4 OH H 1 4
OH H 1

(e.g., amylose), is a OH O OH
3 2 3 2
disaccharide with an H OH H OH
a(1  4) glycosidic maltose
link between C1 - 6 CH2OH 6 CH2OH

C4 OH of 2 5 O 5 O OH
H H
glucoses. H
1
H
4
OH H O 4
OH H 1
It is the a anomer H H
OH
(C1 O points down). 3 2 3 2

H OH H OH
cellobiose

Cellobiose, a product of cellulose breakdown, is the otherwise

equivalent b anomer (O on C1 points up).
The b(1  4) glycosidic linkage is represented as a zig-zag, but one
glucose is actually flipped over relative to the other.
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Other disaccharides include:

 Sucrose, common table sugar, has a glycosidic bond
linking the anomeric hydroxyls of glucose & fructose.
Because the configuration at the anomeric C of glucose
is a (O points down from ring), the linkage is a(12).
The full name of sucrose is a-D-glucopyranosyl-(12)-
b-D-fructopyranose.)
 Lactose, milk sugar, is composed of galactose &
glucose, with b(14) linkage from the anomeric OH of
galactose. Its full name is b-D-galactopyranosyl-(1 4)-
a-D-glucopyranose
BIOKIMIA1-2007 37
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Sucrose
 a-D-glucopyranosido-b-D-fructofuranoside
 b-D-fructofuranosido-a-D-glucopyranoside
• also known as tablet sugar
• commercially obtained from sugar cane or sugar
beet
• hydrolysis yield glucose and fructose (invert
sugar) ( sucrose: +66.5o ; glucose +52.5o; fructose
–92o)
• used pharmaceutically to make syrups, troches
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Sugar cane

Sugar beet
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Polysaccharides or glycans
• homoglycans (starch, cellulose, glycogen, inulin)
• heteroglycans (gums, mucopolysaccharides)
• characteristics:
• polymers (MW from 200,000)
• White and amorphous products (glassy)
• not sweet
• not reducing; do not give the typical aldose or ketose reactions
• form colloidal solutions or suspensions
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Starch
• most common storage polysaccharide in
plants
• composed of 10 – 30% a-amylose and 70-
90% amylopectin depending on the source
• the chains are of varying length, having
molecular weights from several thousands
to half a million
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Amylose and amylopectin are the 2 forms of starch. Amylopectin

is a highly branched structure, with branches occurring every 12
to 30 residues
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suspensions of amylose
in water adopt a helical
conformation

iodine (I2) can insert in

the middle of the amylose
helix to give a blue color
that is characteristic and
diagnostic for starch
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Cellulose
• Polymer of b-D-glucose attached by b(1,4)
linkages
• Yields glucose upon complete hydrolysis
• Partial hydrolysis yields cellobiose
• Most abundant of all carbohydrates
• Cotton flax: 97-99% cellulose
• Wood: ~ 50% cellulose
• Gives no color with iodine
• Held together with lignin in woody plant tissues
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Glycogen
• also known as animal starch
• stored in muscle and liver
• present in cells as granules (high MW)
• contains both a(1,4) links and a(1,6) branches at
every 8 to 12 glucose unit
• complete hydrolysis yields glucose
• glycogen and iodine gives a red-violet color
• hydrolyzed by both a and b-amylases and by
glycogen phosphorylase
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CH2OH CH2OH
H O O
glycogen
H H H
H H
OH H OH H 1
O
OH
O
H OH H OH

CH2OH CH2OH 6 CH2 CH2OH CH2OH

H O H H O H H 5 O H H O H H O H
H H H H H
H H H 1 4 OH H H
OH OH 4 OH O O
OH
O O OH
OH
3 2
H OH H OH H OH H OH H OH

Glycogen, the glucose storage polymer in animals, is similar in

structure to amylopectin.
But glycogen has more a(16) branches.
The highly branched structure permits rapid glucose release from
glycogen stores, e.g., in muscle during exercise.
The ability to rapidly mobilize glucose is more essential to animals
than to plants.
Storage polysaccharides

carbon and energy (glucose) storage molecules

more branching
Structural polysaccharides

Cellulose and Chitin (2 most abundant polysaccharides)

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(in starch)

(in cellulose)
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Structure of cellulose
 Too much …..
Carbohydrate will be converted
into fat and stored under the
skin leading to weight gain!
CHEK!!!
Jelaskan berdasarkan strukturnya, manakah di antara
Trehalosa (ik. α,11) dan Selobiosa (ik. b,14) yang termasuk
gula pereduksi!
Diketahui struktur monosakarida (glukosa) penyusun kedua
disakarida tersebut sebagai berikut:
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Oligosaccharides occur widely as components of

antibiotics derived from various sources
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Special monosaccharides: deoxy

sugars
• These are monosaccharides which lack one
or more hydroxyl groups on the molecule
• one quite ubiquitous deoxy sugar is 2’-
deoxy ribose which is the sugar found in
DNA
• 6-deoxy-L-mannose (L-rhamnose) is used
as a fermentative reagent in bacteriology
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Starch/Glycogen
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Cellulose
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Sugar derivatives
COOH CHO
CH2OH
H C OH H C OH
H C 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
CH2OH
CH2OH COOH
D-ribitol
D-gluconic acid D-glucuronic acid

 sugar alcohol - lacks an aldehyde or ketone; e.g., ribitol.

 sugar acid - the aldehyde at C1, or OH at C6, is oxidized
to a carboxylic acid; e.g., gluconic acid, glucuronic acid.
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Sugar alcohols are very useful

intermediates
• Mannitol is used as an osmotic diuretic
• Glycerol is used as a humectant and can be nitrated to
nitroglycerin
• Sorbitol can be dehydrated to tetrahydropyrans and
tetrahydrofuran compounds (sorbitans)
• Sorbitans are converted to detergents known as spans and
tweens (used in emulsification procedures)
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Sugar derivatives
CH2OH CH2OH

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

OH OH OH O OH
H NH 2 H N C CH3
H
a-D-glucosamine a-D-N-acetylglucosamine

amino sugar - an amino group substitutes for a hydroxyl.

An example is glucosamine.
The amino group may be acetylated, as in
N-acetylglucosamine.
TERIMA KASIH