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
1the number of carbons and
2whether aldoses or ketoses
most (99%) are straight chain compounds
D-glyceraldehyde is the simplest of the aldoses
(aldotriose)
all other sugars have the ending ose (glucose,
galactose, ribose, lactose, etc…)
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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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Structure of a simple aldose and a simple ketose

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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 asymmetric CH2OH CH2OH
C in glyceraldehyde. D-glyceraldehyde L-glyceraldehyde
The lower
CHO CHO
representations are
Fischer Projections. H C OH HO C H

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 carbon
(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 R R
form a aldehyde alcohol hemiacetal
hemiacetal.
R R

A ketone can C O + "R OH "R O C OH

react with an R' R'
alcohol to ketone alcohol hemiketal
form a
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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
-anomer!

On the opposite
side as
attacking OH, is
-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 36
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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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(in starch)

(in cellulose)
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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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Structure of cellulose
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Linear structures of cellulose and chitin

(2 most abundant polysaccharides)
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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 2
3
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.
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Starches

carbon and energy (glucose) storage molecules

more branching
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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 NH2 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
 Too much …..
Carbohydrate will be converted
into fat and stored under the
skin leading to weight gain!
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