Chemistry of biomolecules

Lecturer 3
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 Reducing Sugars & non-reducing Sugars

 The carbohydrates that are oxidised by oxidizing agents

like Fehling’s solution are reducing sugars.
 The carbohydrates that are not oxidised by oxidizing
agents like Fehling’s solution are non-reducing sugars.
 A reducing sugar bears a free aldehyde groups in its
solution phase.
 A non-reducing sugar not bears a free aldehyde groups in
its solution phase.

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 Reducing Sugars & non-reducing Sugars

 Reducing sugars are small carbohydrates (usually

containing one or two sugar units) that are capable of
acting as reducing agents towards metal salts such as
Ag+ or Cu2+ (Ex: Fehling’s solution ).
 These metal salts have historically been used for
testing purposes because they oxidize aldehydes and
give a clear color change after being reduced.
 The reason sugars can react with these salts is that
their cyclic hemiacetal functional group is in
equilibrium with an acyclic aldehyde. Acetals do not
react.
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This results in a carboxylic acid and red Cu(I) which precipitates out as
copper(I) oxide.

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 During this process, the aldehyde is oxidized and the
oxidizing agent is reduced. Another way of framing this is
to say that the aldehyde is the reducing agent in this
process.

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 Disaccharides

• Definition of disaccharides Disaccharides (C12H22O11) are

sugars composed of two monosaccharide units that are
joined by a carbon - oxygen - carbon linkage known as a
glycosidic linkage.
• This linkage is formed from the reaction of the anomeric
carbon of one cyclic monosaccharide with the OH group of
a second monosaccharide.
• Anomeric carbon: In a cyclic carbohydrate, the carbon that was the carbonyl
carbon in acyclic form.
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Disaccharides

- Disaccharides (C12H22O11) are sugars composed of two monosaccharide

units.
- On hydrolysis give 2 molecules of monosaccharide
- Composed of two monosaccharide molecules joined together by
glucosidic linkage.
- This linkage is formed from the reaction of the anomeric carbon of one
cyclic monosaccharide with the OH group of a second monosaccharide.
- Three naturally occurring glycosidic linkages:
 1-2’ link: The anomeric carbons of the two sugars are bonded through
an oxygen.
 1-4’ link: The anomeric carbon is bonded to oxygen on C4 of second
sugar.
 1-6’ link: The anomeric carbon is bonded to oxygen on C6 of second
sugar.
 Disaccharides
• Comprised of two sugars
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α1, β2 Diglycosidic Links
6 5

1 Glucose 4 1
3 2
5

4
1 2 5
2 6
3 4
3
6
Fructose 5 2

4 3

Glucose Fructose 1

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Sucrose Sucrose

α-D-glucopyranosyl-(1→2)-β-D-fructofuranoside
 Disaccharides
• Lactose and Maltose
Glucose
Glucose Glucose
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Galactose
6 6
5

6 4 1 5 5
2
4 1 4 1
5 3
2 2
4
1 3 3
2
3

β-1,4 Glycosidic Bond α-1,4 Glycosidic Bond

Lactose Maltose
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β-D-galactopyranosyl-(1→4)-D-glucose
α-D-glucopyranosyl-(1→4)-D-glucose
Reducing Versus Non-Reducing Sugars

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 Sucrose
 Glucose + fructose, linked 1-2’ .
 Non-reducing sugar
The sucrose molecule is unique among the common disaccharides
in having an α-1,β-2-glycosidic (head-to-head) linkage.
Because this glycosidic linkage is formed by the OH group on the
anomeric carbon of α-D-glucose and the OH group on the anomeric
carbon of β-D-fructose, it ties up the anomeric carbons of both
glucose and fructose.
Maltose
 Two glucose units linked 1-4’.
 Reducing sugar

Reducing
moiety
 The α-D-glucose units in maltose are joined in a head-to-tail
fashion through an α-linkage from the first carbon atom of one
glucose molecule to the fourth carbon atom of the second glucose
molecule (that is, an α-1,4-glycosidic linkage).
Maltose is a reducing sugar. Thus, its two glucose molecules must be
linked in such a way as to leave one anomeric carbon that can open
to form an aldehyde group.
Lactose
 Galactose + glucose linked 1-4’.
 Reducing sugar

Reducing
moiety
 The α-D-glucose units in maltose are joined in a head-to-tail
fashion through an α-linkage from the first carbon atom of one
glucose molecule to the fourth carbon atom of the second glucose
molecule (that is, an α-1,4-glycosidic linkage).
Maltose is a reducing sugar. Thus, its two glucose molecules must be
linked in such a way as to leave one anomeric carbon that can open
to form an aldehyde group.
Lactose
 Galactose + glucose linked 1-4’.
 Reducing sugar

Reducing
moiety
Lactose is a reducing sugar composed of one molecule of β-D-galactose
and one molecule of β-D-glucose joined by a β-1,4-glycosidic bond
(the bond from the anomeric carbon of the first monosaccharide unit
being directed upward).
 Determination of the reducing part of disaccharide

Oxidation of lactose (consists of two different monosaccharides; glucose and galactose) with
bromine water gives lactobionic acid which is then hydrolyzed to give an aldonic acid from the
reducing sugar and a free sugar from the the non reducing component e.g. lactose yields
galactose and gluconic acid denoting that galactose is the non reducing component ( linked in
position 1) and glucose is the reducing one ( linked in position 4).
OH H H COOH CHO
H
C CH COOH CH H C OH H C OH

H C OH H C OH H C OH H C OH HO C H HO C H
Br/H2O acid
HO C H O O +
O HO C H O HO C H HO C H H C OH
O HO C H
oxidn hydr
H C HO C H H C HO C H H C OH H C OH

H C H C H C OH H C CH 2OH CH 2OH

CH2OH CH 2OH CH2OH CH2OH

Glucose part Galctose part D-Gluconic acid D-Galctose

lactobionic acid
Lactose
 CH2 OH .
O
CH 2OH

O
CH 2 OH

O
CH2 OH

OH
OH OH
Br/H2O acid
O O COOH
OH OH oxidn OH OH
hydr
OH

OH OH OH OH

Glactopyranose part Glucopyranose part Glactopyranose Glucopyranose

lactobionic acid
Lactose
CH 2OH CH 2OH

OH OH
Haworth
OH
+ projection
CHO COOH
OH OH

OH

OH OH

D-Galctose D-Gluconic acid

 .
 Summary

Disaccharide source structure bond Reducing

property

Sucrose= (α-D- cane sugar α-D-glucose + α-1,β-2 glycosidic not

glucopyranosyl- beat sugar β-D- bond. reducing
β-D-fructo table sugar Fructose sugar
furanoside
Maltose= 4-O- Malt sugar 2 molecules of α-1,4 glycosidic Reducing
(α -D-gluco α-D- bond. sugar
pyranosyl)-D- glucose
glucopyranose
Lactose= 4-O- milk sugar β-D-galactose β-1,4 glycosidic Reducing
(β -D-galcto + α-D-glucose bond sugar
pyranosyl)-D-
glucopyranose
 OH
HO
OH
HO O O
O OH
 Sucrose
HO HO OH
α-D-glucopyranosyl-β-D-fructofuranoside
HO
OH
HO O OH
O
 Maltose HO O OH
4-O-(α -D-glucopyranosyl)-D-glucopyranose OH OH

HO
OH
 Lactose HO O OH
O
4-O-(β -D-galctopyranosyl)-D-
glucopyranose HO O OH
OH OH
Polysaccharides
- On hydrolysis give large number of
molecules of monosaccharide
- The monosaccharide molecules joined
together by glucosidic linkage.
 Cellulose
 Polymer of D-glucose, found in plants.
 Mammals lack the -glycosidase enzyme.
 Structurally, cellulose is a polysaccharide composed of several
thousand of D-glucose units by β-(1,4-) glycosidic linkage.
Industrial applications of Cellulose

Esters of cellulose are important objects of commerce. Cellulose forms

esters with both organic and inorganic acids.
 Cellulose nitrate: obtained by nitrating cellulose with nitric acid in
presence of sulphuric acid, according to the degree of esterification we
obtain cellioid ( in plactics), collodion (used as a covering) and gum
cotton (explosive).
 Cellulose acetate: which is not inflammable as cellulose nitrate and is
used for the preparation of fibers and now is used for the manufacturing
of films.
 Rayon: this is regenerated cellulose. It is best prepared by treating
cellulose such as cotton, with 18% NaOH solution to convert it to alkali
cellulose.
- The alkali cellulose is treated with carbon disulphide to convert it to
xanthate.
-The cellulose xanthate solution is then "ripened ‫ "ينضج‬by letting ‫ ترك‬it
to stand several days, during which time it changes to a viscous yellow
liquid called viscose.
-The viscose is passed through a spinneret into a bath of dilute acid,
which decomposes the xanthate and regenerates the cellulose.
 Rayon: The regenerated cellulose

NaOH

cellulose
CS2

alkali
cellulose
HCl

cellulose xanthate (viscose)

Amylose
 Soluble starch, polymer of D-glucose units
connected by α-(1,4-) glycosidic linkage.
 Starch-iodide complex, deep blue.
Amylopectin
Branched(α-1,6 glucosidic linkage), insoluble
fraction of starch.
 Glycogen

 Glucose polymer, similar to amylopectin,

but even more highly branched.
 Energy storage in muscle tissue and liver.
 The many branched ends provide a quick
means of putting glucose into the blood.

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 Chitin
 Polymer of N-acetylglucosamine.
 Exoskeleton of insects.
2-Amino acids and proteins
Chemistry of biomolecules

Lecturer 4
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