BIOCHEMISTRY 1

2nd Lecture
CARBOHYDRATE
Structure and functions

Chemistry Education Department-UPI

Biochemistry

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:
(CH2O)n

I
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 Benedicts
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 that 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.

Carbon Cycles
6CO2 + 6H2O

C6H12O6+ 6O2

CO2

C6H12O6+ 6O2

C6H12O6+ 6O2
6CO2 + 6H2O

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They are polyhydroxy aldehydes or ketones, or

compounds that yield polyhydroxy aldehydes or
ketones on hydrolysis.

They Are Split Into Three Groups Known As:

Monosaccharides (Monomers) Oligosaccharides Polysaccharides (Polymers) -

Biochemistry

Classification of carbohydrates
Monosaccharides (monoses or glycoses)
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.
di, tri, tetra, penta, up to 9 or 10
Most important are the disaccharides

Polysaccharides or glycans
polymers consisting of chains of monosaccharide or disaccharide units.
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-glyceraldehyde is the simplest of the aldoses (aldotriose)
all other sugars have the ending ose (glucose, galactose,
ribose, lactose, etc)

Biochemistry

Aldose sugars
H

(H

OH)n

CH2OH
Aldose

H
C

OH

CH2OH
Aldotriose
n=1

OH

OH

CH2OH

OH

Aldotetrose
n=2

OH

OH

OH

OH

OH

OH

CH2OH
Aldopentose
n=3

CH2OH
Aldohexose
n=4

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Ketose sugars
CH2OH

(H

OH)n

CH2OH
C

CH2OH

CH2OH
Ketose

OH

CH2OH
Ketotriose
n=0

CH2OH

CH2OH

Ketotetrose
n=1

CH2OH

OH

OH

OH

CH2OH

Ketopentose
n=2

OH
C

OH

CH2OH
Ketohexose
n=3

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Structure of a simple aldose and ketose

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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 3dimensional structure):

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D vs L Designation
D & L designations are based
on the configuration about the
single asymmetric C in
glyceraldehyde.
The lower representations are
Fischer Projections.

CHO

CHO
H

OH

HO

L-glyceraldehyde

CHO
H

OH

CH2OH

D-glyceraldehyde

CH2OH

CH2OH

D-glyceraldehyde

CHO
HO

CH2OH

L-glyceraldehyde

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Sugar Nomenclature
For sugars with more than one
chiral center, D or L refers to the
asymmetric C farthest from the
aldehyde or keto group.
Most naturally occurring sugars
are D isomers.

C
H C OH
HO C H
H C OH
H C OH
CH2OH
D-glucose

C
HO C H
H C OH
HO C H
HO C H
CH2OH
L-glucose

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Enantiomers and epimers

H

H
H

OH

OH

CH2OH

HO

HO

OH

HO

HO

OH

OH

HO

OH

OH

CH2OH

these two aldotetroses are enantiomers.

They are stereoisomers that are mirror
images of each other

CH2OH

CH2OH

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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Sugar 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 -D-glucose or -D-glucose

changes over time to reach an equilibrium (mutarotation)

Biochemistry

Hemiacetal & hemiketal formation

H

An aldehyde can
react with an
alcohol to form a
hemiacetal.
A ketone can react
with an alcohol to
form a hemiketal.

H
O

R'

OH

R'

OH

aldehyde

alcohol

hemiacetal

R
C

R
O

"R

OH

R'

ketone

"R

C
R'

alcohol

hemiketal

OH

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Pentoses and hexoses

can cyclize as the
ketone or aldehyde
reacts with a distal
OH.
Glucose forms an
intra-molecular
hemiacetal, as the C1
aldehyde & C5 OH
react, to form a 6member pyranose ring,
named after pyran.

H
HO
H
H

2
3
4
5
6

CHO
C

OH

OH (linear form)

OH

D-glucose

CH2OH
6 CH2OH

6 CH2OH
5

H
4

OH

H
OH
3

OH

-D-glucose

OH

H
4

OH

H
OH
3

OH

OH

-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 Formation (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:
Maltose, a cleavage
product of starch (e.g.,
amylose), is a
disaccharide with an (1
4) glycosidic link
between C1 - C4 OH of
2 glucoses.
It is the anomer (C1 O
points down).

6 CH 2OH

6 CH 2OH

H
OH

OH

H
1

maltose

OH

H
1

OH

cellobiose

H
OH

OH

2OH

OH

H
3

6 CH

H
OH

H
OH
3

OH

6 CH 2OH

OH
1

OH

Cellobiose, a product of cellulose breakdown, is the otherwise equivalent anomer

(O on C1 points up).
The (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

points down from ring), the linkage is (1 2).

(O

The full name of sucrose is -D-glucopyranosyl-(1 2)- -Dfructopyranose.)

Lactose, milk sugar, is composed of galactose & glucose, with
(1 4) linkage from the anomeric OH of galactose. Its full name
is -D-galactopyranosyl-(1 4)- -D-glucopyranose

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Sucrose

-D-glucopyranosido- -D-fructofuranoside
-D-fructofuranosido- -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% 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 -D-glucose attached by (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 (1,4) links and (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 and -amylases and by
glycogen phosphorylase

Biochemistry
C H2OH

CH2OH
O

H
H
OH

OH

H
O

OH
CH2OH
H

OH
H

H
OH

OH

CH2OH
O

H
OH

OH

H
O

O
H
OH
H

H
OH

H
O

glycogen

H
1
O

6 CH2
H 5
H
4 OH
3
H

CH2OH
O
H
2
OH

H
1
O

CH2OH
O

H
4 OH
H

H
O
OH

O
H
OH

H
OH

OH

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

amylopectin.
But glycogen has more (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
CHO

COOH
CH2OH
H

OH

OH

OH

CH2OH

D-ribitol

OH

HO

OH

OH

OH

OH

OH

HO

CH2OH

D-gluconic acid

COOH

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
CH 2OH

CH 2OH
O

H
H
OH

H
OH

H
OH

OH
H

NH 2

H
O OH

OH
H

CH 3

-D-glucosamine

-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!