CHI-452:

Chemistry of Bio-Molecules
Open Elective and Departmental elective

Dr. Jeyakumar Kandasamy

Department of Chemistry
IIT-BHU

With Prof. Vandana Srivastava

 Objectives of the course
• What are bio-molecules
• Define the bio-molecules such as carbohydrates,
proteins and nucleic acids, may be bit of Lipids
• Classify the carbohydrates, proteins and nucleic acids on
the basis of their structures
• Explain the difference between DNA and RNA
• Synthesis of carbohydrates, proteins and nucleic acids
• Appreciate the role of bio-molecules in biological system
 Objectives of the course

• What are natural products

• Structural features of the natural products such as steroids,
alkaloids, terpenes and carotenoids
• Chemical reactivates of the natural products such as steroids,
alkaloids, terpenes and carotenoids
 What are bio-molecules
• A Bio-molecule is any molecule that is produced by a living
organism
• Other Hand: Any molecule that is involved in the maintenance
and metabolic processes of living organisms.

Humans,
Animals,
Living organism Plants,
Insects,
Algae
Bacteria’s
 Bio molecules are compounds of Carbon.
 Hence the chemistry of living organisms is organized around
carbon, Carbon is the most versatile and the most
predominant element of life.

 In general, Bio-molecules are very large molecules of many

atoms that are covalently bound together.

 Biomolecules are responsible for life of living organisms,

without that we are “No more”
The major bio-molecules are...

• Carbohydrates,
• Proteins, 
• Nucleic acids
• Lipids, 
Elements
Carbohydrates

Starch
Amino acids
Nucleic acids: DNA and RNA
Lipids
 Bio molecules
• All of them are interconnected
• Without any one of them there will be no life
 Well known carbohydrates
Starch OH

O OH
O H
HO
HO O
O
HO HO
OH O

O α- D- glucose polymer
HO OH
HO
HO

D- glucose OH
OH
O
O O
O O
HO HO OH
HO
H

β- D- glucose polymer
 Alpha-glucosidase enzyme

OH

O
HO
HO
HO
H2O OH

α- D-glucose polymer α-D- glucose

Carbohydrates (or) Saccharides
Carbohydrates: Hydrates of carbon
Saccharides: Saccharine or Sweet

On the basis of the number of forming units, three

major classes of carbohydrates can be defined:

1. Monosaccharide
2. Oligosaccharide
3. Polysaccharide
 Monosaccharides
Only one unit of poly-hydroxy
aldehyde or ketone compound.

The most abundant monosaccharide

is D-glucose, also called dextrose.

The General formula of monosaccharide is

Cn(H2O)n
 Oligosaccharides
1. They are small sized compound carbohydrates.
2. An oligosaccharides consists of 2-6, rarely 10 monosaccharide
residues.
3. They are soluble in water.
4. Oligosaccharides are sweet to taste.
5. They are physiologically active.
6. Oligosaccharides are structural components of cell
membranes.
7. Transport occurs in oligosaccharide stage.
 Polysaccharides
1. They are large sized compound carbohydrates.
2. A polysaccharide is made up of numerous (more than 10
units to several hundred) monosaccharide residues.
3. Polysaccharides are insoluble in water.
4. Sweetness is absent.
5. They are physiologically inactive.
6. Polysaccharides are structural components of cell walls.
7. Storage mostly occurs in the polysaccharide.
 Monosaccharides
Carbohydrates: Hydrates of carbon

Saccharides: Saccharine or Sweet

Cn(H2O)n

C1(H2O)1 C2(H2O)2 C3(H2O)3

CHO
CHO CHO
H C OH
H CH2OH
CH2OH

Formaldehyde Glycolaldehyde Glyceraldehyde

First-Carbohydrate
NON-Carbohydrates
 3-Carbon sugar (Triose)
Glyceraldehyde

CHO
H C OH
CH2OH

1 1 1
CHO CHO CH2OH
2 2 2
H C OH HO C H C O
3 3 3
CH2OH CH2OH CH2OH
D-Glyceraldehyde L-Glyceraldehyde Dihydroxy Acetone
 D and L
1 1
CHO CHO
2 2
H C OH HO C H
3 3
CH2OH CH2OH
D-Glyceraldehyde L-Glyceraldehyde

D and L is only based on the Hydroxyl group direction present in the last before
the carbon

The designation D or L has nothing to do with rotational properties of plane

polarized light.

Small d or l only means the rotation of plane polarized

d: dextrorotatory (Clockwise)
l: levorotatory (Anticlockwise)
 D and L
1 1
CHO CHO
2 2
H C OH HO C H
3 3
CH2OH CH2OH
D-Glyceraldehyde L-Glyceraldehyde

 D means hydroxyl group of the last before carbon placed in the Right side
 L means hydroxyl group of the last before carbon placed in the Left side

1
CH2OH
2 Dont have hydroxyl group of the last before carbon
C O
3 Therefore no D and no L
CH2OH
Dihydroxy Acetone
 Aldose vs Ketose

Aldehyde Aldehyde Ketone

1 1 1
CHO CHO CH2OH
2 2 2
H C OH HO C H C O
3 3 3
CH2OH CH2OH CH2OH
D-Glyceraldehyde L-Glyceraldehyde Dihydroxy Acetone

Aldose Ketose
 3-Carbon sugar (Triose)
Glyceraldehyde
1 1 1
CHO CHO CH2OH
2 2 2
H C OH HO C H C O
3 3 3
CH2OH CH2OH CH2OH
D-Glyceraldehyde L-Glyceraldehyde Dihydroxy Acetone

Enantiomers (stereoisomers)

Structural Isomers
 Enantiomer
1 1
CHO CHO
2 2
H C OH HO C H
3 3
CH2OH CH2OH
D-Glyceraldehyde L-Glyceraldehyde

An enantiomer is one of the two molecules that are mirror images

of each other and are non-superposable.

Enantiomers have identical chemical and physical properties except

for their ability to rotate plane-polarized light (+/-) by equal
amounts but in opposite directions.

Enantiomers interact differently with other chiral molecules i.e.

biologically active molecules as aminoacids, sugars, steroids etc.
Naturally occurring sugars exhibit mostly “D”
configuration

1
1 CHO
CHO
2
H
2
C OH
HO C H
3
3
CH2OH CH2OH

D-Glyceraldehyde L-Glyceraldehyde

Naturally occurring Un-Natural

Also mostly Aldehyde (aldose) sugars were found

4-Carbon sugars (Tetrose)
C4(H2O)4 = C4H8O4
CHO Aldose CHO
H C OH HO C H
H C OH HO C H
CH2OH CH2OH

CHO CHO
HO C H H C OH
H C OH HO C H
CH2OH CH2OH
4-Carbon sugars (Tetrose)
1 CHO CHO 1
2 H C OH HO C H 2
3 H C OH H C OH 3
4 CH2OH CH2OH 4

D-Erythrose D-Threose
Natural

CHO CHO
HO C H H C OH
HO C H HO C H
CH2OH CH2OH

L-Erythrose L-Threose
Un Natural
 Enantiomers vs Diastereomers
1 CHO CHO
If a pair of stereoisomers are non-
2 H C OH HO C H
3 H C OH
superimposable mirror images of each other,
HO C H
CH2OH
then they are enantiomers.
4 CH2OH

D-Erythrose L-Erythrose

Enantiomers Diastereomers

CHO 1 CHO
Chiral molecules that possess two (or more) 
HO C H 2 H C OH
chirality centers  have stereoisomers that may
H C OH 3 HO C H
be either enantiomers or diastereomers.
CH2OH 4 CH2OH
Diastereomers are stereoisomers that are not
D-Threose L-Threose mirror images.

Enantiomers
 Triose to tetrose
1
CHO
2
H C OH
3
CH2OH
D-Glyceraldehyde

1CHO 1CHO

H 2C OH HO 2C H

H 3C OH H 3
C OH
4 CH2OH 4 CH2OH

D-Erythrose D-Threose

Naturally occurring aldose

 5-carbon sugars (Pentose)
Only 4 types with D-Configuration

Cn(H2O)n

C5(H2O)5= C5H10O5

1CHO 1CHO 1CHO 1CHO

H 2C OH HO 2C H H 2C OH HO 2C H

H 3C OH H C OH HO 3
C H HO C H
3 3

H 4C OH H 4C OH H 4C OH H 4C OH
5 5
5
CH2OH 5 CH OH
2
CH2OH CH2OH
 5-carbon sugars (Pentose)
C3(H2O)3= C3H6O3
D-Glyceraldehyde
1
CHO
2 3
H C OH
3
CH2OH
C4(H2O)4= C4H8O4 C4(H2O)4= C4H8O4
D-Erythrose D-Threose
1CHO
1CHO
H 2C OH
HO 2C H
H 3C OH
H 3
C OH 4
4 CH2OH
4 CH2OH

C5(H2O)5= C5H10O5

1CHO 1CHO 1CHO 1CHO

H 2C OH HO 2C H H 2C OH HO 2C H

H 3C OH H C OH HO C H HO C H
3 3 3
5
H 4C OH H 4C OH H 4C OH H 4C OH
5 5
5
CH2OH 5 CH OH
2
CH2OH CH2OH

D-Arabinose D-Xylose D-Lyxose

D-Ribose

RAXL
 D vs L sugars
1CHO 1CHO 1CHO 1CHO

H 2C OH HO 2C H H 2C OH HO 2C H

H 3C OH H C OH HO 3
C H HO C H
3 3

H 4C OH H 4C OH H 4C OH H 4C OH
5 5
5
CH2OH 5 CH OH
2
CH2OH CH2OH
D-Arabinose D-Xylose D-Lyxose
D-Ribose

RAXL

1CHO 1CHO 1CHO 1CHO

HO 2C H H 2C OH HO 2C H H 2C OH

HO 3C H HO C H H 3
C OH H C OH
3 3

HO 4C H HO 4C H HO 4C H HO 4C H
5 5
5
CH2OH 5 CH OH
2
CH2OH CH2OH
L-Arabinose L-Xylose L-Lyxose
L-Ribose

RAXL
 Pentose exists in Cyclic Form

HO H This is not a carbon

1CHO C
1
H 2C OH H 2C OH Just for a convenient
O
H 3C OH H 3C OH
H 4C OH H 4C
5
CH2OH 5
CH2OH This is not a carbon

D-Ribose D-Ribofuranose

Open form Cyclic form

Fischer projection
 Pentose exists in Cyclic Form

HO H

1
C up 5
CH2OH
O O O OH
H 2C OH
O = 4 1 4 1 4
1
H 3C OH 3 2 3 2 3 2

H 4C down
OH OH
5
CH2OH D-Ribofuranose
D-Ribofuranose  Haworth projection

Cyclic form
Fischer projection
 Pentose exists in Cyclic Form

HO H
1CHO 1C

HO 2C H HO
HO 2C H 5
O O OH
H C OH H
3 3C OH 4 HO 1
H 4C OH H 4C =
3 2
5 CH
2OH 5
CH2OH OH
D-Arabinose D-Arabinofuranose D-Arabinofuranose

Cyclic form

 Haworth projection
 Pentose exists in Cyclic Form

HO H

1CHO 1C
HO
H 2C OH H 2C OH 5
O O OH
HO C H HO 3C H 4
3 OH 1

H H 4C = 2
4C OH 3
5
5
CH2OH CH2OH OH
D-Xylofuranose D-Xylofuranose
D-Xylose
Cyclic form
 Haworth projection
Pentose exists in Cyclic Form

H
HO
1CHO C
1
HO 2C H HO
HO 2C H 5
HO C H O O OH
3 HO 3C H 4
OH HO 1
H 4C OH
H 4C =
5 3
CH2OH 2
5
CH2OH
D-Lyxose D-Lyxofuranose D-Lyxofuranose

Cyclic form

 Haworth projection
 Why???
HO H
1CHO
1C

H 2C OH H HO
2C OH 5
O O OH
H 3C OH H 3C OH 4
1
H 4C OH H 4C = 3 2
5
CH2OH 5
CH2OH OH OH
D-Ribose D-Ribofuranose D-Ribofuranose

Open form Cyclic form

 1
CHO

H 2C OH
H 3C OH
H 4C OH
5
CH2OH
H
OH 1
D-Ribose
1 HO C
H C
H 2C OH
H 2C OH O
O
H 3C OH
H 3C OH
H 4C
H 4C
5
5 CH2OH
CH2OH
D-Ribofuranose Cyclic form D-Ribofuranose

HO
5 HO
O OH
1 Down 5
O
4
2 4
Up
3 1
OH 3 2

OH OH
OH OH
-D-Ribofuranose
-D-Ribofuranose
 In solution
HO
5
O 1
4
3 2
OH
1
CHO OH OH
-D-Ribofuranose HO
H 2C OH 5
O OH
H 3C OH
= 4
3 2
1

H 4C OH
HO
5
CH2OH 5 OH OHOH
O D-Ribofuranose
4
D-Ribose 1
3 2

OH OH
-D-Ribofuranose

Why it is Ribofuranose ???

Why not just Ribose ???
Furanose = 5 member ring
 Furanose Vs PyranoseH
1
HO C
HO 5

Cyclic form H 2C OH O OH
O 1-4 connection 4
1

H 3C OH 3 2

H 4C HO OH
D-Ribofuranose
5
CH2OH
1CHO
D-Ribofuranose
H 2C OH
5
H O
H 3C OH
1 4 1
HO C
H 4C OH 3 2
O
5
CH2OH H 2C OH
H 3C OH
O 1-5 connection OH =
D-Ribose Cyclic form
4
H C OH OH OH 5
O
1
5 OH 4
OH
H C 3 2
HO
H OH OH
D-Ribopyranose
D-Ribopyranose
 α- and β-pyranose
OH
O

HO
OH OH

-D-Ribopyranose

O
OH
Is the only way
HO
OH OH O to write the
D-Ribopyranose
HO
OH OH
OH structure??
-D-Ribopyranose

 Haworth projection
 Chair form

ax
eq ax
5
O O
4 1 4
5 O eq
3 2
2
eq
3 1
eq eq ax
ax ax
Haworth Projection Chair Projection
Chair Form
Ax= axial
Eq= equatorial
 Other way of writing
ax
5 4 eq ax
O 1 5 O
4 OH O
3 OH HO eq
2 2
3 1 eq
HO OH
OH eq
OH OH ax eq
ax
D-Ribopyranose Chair Form ax

OH
O O OH
HO
=
HO
OH
OH OH OH
-D-Ribopyranose

O O
HO
HO =
OH HO OH
OH OH OH
-D-Ribopyranose
 Arabinopyranose

H
1
1CHO HO C
HO 2C H HO 2C H 5 OH
O
H C OH O O
3 H 3C OH 4 HO OH
3 1
H 4C OH = HO
H 4C OH HO 2
OH
5 CH OH OH
2OH H 5
C
H
D-Arabinose D-Arabinopyranose D-Arabinopyranose
 D-Xylopyranose

H
1CHO 1
HO C
5
H 2C OH O
H 2C OH 4 OH OH
O
HO C H 2 1
HO
3
HO 3C H O
= HO 3 HO OH
OH
H 4C OH OH
H 4C OH
5
CH2OH 5
H C
D-Xylopyranose
D-Xylose H
D-Xylopyranose
 D-lyxopyranose

H
1
1CHO HO C
HO 2C H
HO 2C H 5 HO
O O
HO C H
3 H 3C OH 4 HO OH
H 4C OH 1 HO
H 4C OH HO 3 2 OH
5
CH2OH 5 OH OH
H C O
D-Lyxose H
D-Lyxopyranose D-Lyxopyranose
Cyclic form
 6-carbon sugars (Hexose sugars)
C5(H2O)5= C5H10O5

1CHO 1CHO 1CHO 1CHO

H 2C OH HO 2C H H 2C OH HO 2C H
H 3C OH H C OH HO 3 C H HO 3 C H
3

H 4C OH H 4C OH H 4C OH H 4C OH
5 5
5
CH2OH 5 CH
2OH
CH2OH CH2OH

D-Ribose D-Arabinose D-Xylose D-Lyxose

C6(H2O)6= C6H12O6

1CHO 1CHO 1CHO

1CHO 1CHO 1CHO 1CHO 1CHO
HO 2 H H2 OH HO 2 H
H2 OH HO 2 H H2 OH HO H H2 OH
2
H 3C OH HO 3C H HO 3C H
H 3C OH H 3C OH HO 3C H HO 3C H H 3C OH
HO 4C H HO 4C H HO 4C H
H 4C OH H 4C OH H 4C OH H 4C OH HO 4C H
H 5C OH H 5C OH H 5C OH
H 5C OH H 5C OH H 5C OH H 5C OH H 5C OH
6 CH OH 6 CH2OH 6 CH OH
6 CH OH 6CH OH 6CH2OH 6 CH2OH 6 CH2OH 2 2
2 2

D-Allose D-Altrose D-Glucose D-Mannose D-Gluose D-Idose D-Galactose D-Talose

 1CHO 1CHO

H 2C OH HO 2C H
H 3C OH H 3
C OH
H 4C OH H 4C OH
5
CH2OH 5 CH
2OH

D-Ribose D-Arabinose
C6(H2O)6= C6H12O6

1CHO 1CHO 1CHO 1CHO

H2 OH HO H H2 OH HO H
2 2
H 3C OH H 3C OH HO 3C H HO 3C H
H 4C OH H 4C OH H 4C OH H 4C OH
H 5C OH H 5C OH H 5C OH H 5C OH
6 CH2OH 6 CH2OH 6CH2OH 6 CH2OH

D-Allose D-Altrose D-Glucose D-Mannose

 1CHO
C5(H2O)5= C5H10O5 1CHO

H 2C OH HO 2C H
HO 3 C H HO 3 C H
H 4C OH H 4C OH
5 5
CH2OH CH2OH

D-Xylose D-Lyxose
C6(H2O)6= C6H12O6

1CHO 1CHO 1CHO

1CHO
HO 2 H H2 OH HO 2 H
H2 OH
H 3C OH HO 3C H HO 3C H
H 3C OH
HO 4C H HO 4C H HO 4C H
HO 4C H
H 5C OH H 5C OH H 5C OH
H 5C OH
6CH OH 6CH2OH 6CH OH
6CH2OH 2 2

D-Gulose D-Idose D-Galactose D-Talose

 1CHO 1CHO 1CHO 1CHO
H2 OH HO 2 H H2 OH HO 2 H
H 3C OH H 3C OH HO 3C H HO 3C H
H 4C OH H 4C OH H 4C OH H 4C OH
H 5C OH H 5C OH H 5C OH H 5C OH
6 CH OH 6CH OH 6CH2OH 6 CH2OH
2 2

D-Allose D-Altrose D-Glucose D-Mannose

HO HO HO HO
O O O
5 5
HO 5 O
4 4 OH 4 5
OH 2 OH 2 OH 4 OH HO OH
2 1 1 1 1
3 HO 3 3
HO HO HO 3 2
OH OH OH OH

HO HO OH HO OH
HO
O O O
OH OH HO O
HO HO OH HO OH
OH HO OH HO
OH OH

D-Allopyranose D-Altropyranose D-Glucopyranose D-Mannopyranose

 1CHO 1CHO 1CHO
1CHO
HO 2 H H2 OH HO 2 H
H2 OH
H 3C OH HO 3C H HO 3C H
H 3C OH
HO 4C H HO 4C H HO 4C H
HO 4C H
H 5C OH H 5C OH H 5C OH
H 5C OH
6 CH OH 6 CH OH 6 CH OH
6CH OH 2 2 2
2

D-Gluose D-Idose D-Galactose D-Talose

HO HO
HO HO
HO
O HO HO HO
5 O O O
4 5 5 5
OH HO 4
2 1
4 OH OH 2 OH 4 OH HO OH
2 1 1 1
3
3 3 3 2
OH OH OH
OH

OH OH
OH OH OH OH OH
OH OH
O OH
O O O
OH OH HO OH
HO OH
OH OH
OH OH
D-Gulopyranose D-Idopyranose D-Galactopyranose D-Talopyranose
What (which) is anomeric carbon?

C1-cabon is called anomeric Carbon or Hemiacetal Carbon

HO
HO
O
O
5
4 OH 2 OH HO OH
1 HO
HO 3 OH
OH
D-Glucose D-Glucose
 What (which) is anomeric carbon?

The first carbon of the cyclic sugar is anomeric carbon

HO HO HO
HO 5
5 5 5
O OH O OH O OH
O OH
4 4 4 OH HO
4
1 HO 1 OH 1 1
2 3 2 3 2
3
3 2

OH OH OH OH

HO HO
HO HO
HO
O HO HO HO
5 O O O
4 OH 5 5 5
2 4 HO 4 OH OH 4
1 OH 2 OH HO OH
2 1 1 1
3
3 3 3 2
OH OH OH
OH

OH OH
OH OH OH
OH OH OH OH
O OH
O O O
OH OH HO OH
1 HO OH
OH 1 1 OH 1
OH OH
 Significant of anomeric carbon:
α and β anomers

HO
5
O 1
4
3 2
OH
1
CHO OH OH
H 2C OH HO 5 -D-Ribofuranose
O OH
H 3C OH 4
1
3 2
H 4C OH
5
OHOH HO
CH2OH D-Ribofuranose 5 OH
O
D-Ribose 4 1
3 2

OH OH
-D-Ribofuranose

HO HO
HO HO
OH O
O 5
4
5 4 OH 2
O O
OH 2 1
1 HO OH HO
HO 3 HO
HO 3 OH OH HO
HO OH
OH OH
-D-Glucose D-Glucose -D-Glucose D-Glucose
 Mutarotation
Mutarotation is the change in the optical rotation because of the change in the
equilibrium between two anomers, when the corresponding stereocenters
interconvert.

The α and β anomers are diastereomers of each other and usually have different 
specific rotations. A solution or liquid sample of a pure α anomer will rotate 
plane polarised light by a different amount than the pure β anomer. 
Optical rotation of D-Glucose (α Vs β anomers)

α-anomer is (αD)= +112.2° β-anomer is (αD)= +18.7°

Optical rotation is denoted as: αD

In concentration= 10% in water at 20 °C

Melting Point
α-D-glucose: 146 °C
β-D-glucose: 150°C
 Mutarotation of D-Sugar

When D-glucose is dissolved in water, the optical rotation gradually changes

(mutarotates) with time and approaches a final equilibrium value of +52.7° (c =
10%, 20 °C) due to the formation of an equilibrium mixture consisting of
approximately one-third α- and two-thirds β-D-glucose
Optical activity: D vs L-Glyceraldehyde
1
CHO
2 (αD)= +8.7° in H2O (2 molar concentration at 25 oC)
H C OH
3
CH2OH
D-Glyceraldehyde
Enantiomers
1
CHO
2
HO C H
3 (αD)= -8.7° in H2O (2 molar concentration at 25 oC)
CH2OH
L-Glyceraldehyde
 Question:1

Given a Fischer projection of a monosaccharide, classify it by the

number of carbons it contains
 Question:2

Given a Fischer projection of a monosaccharide, identify chiral carbons and

determine the number of stereoisomers that are possible
 Question:3
Given a Fischer projection of a monosaccharide, classify it as either
aldoses or ketoses.
 Question:4

Given a Fischer projection of a monosaccharide, identify it as a D-sugar

or L-sugar.
 Question:5

Given its Haworth projection, identify a monosaccharide either a pyranose or

a furanose.
 Question:6

Define the term anomer and explain the difference between α and β
anomers.
 Question:7

Understand and describe mutarotation.

 Question:7
• Discuss the optical rotation of enantiomers Vs
diastereomers
 Reaction of monosaccharides

1. Epimerization Reactions
 Epimers
In stereochemistry, an epimer is one of a pair of stereoisomers. The two isomers
differ in configuration at only one stereogenic center. All other stereocenters in the
molecules, if any, are the same in each.

Example 1:
 Epimers
• Other Examples

1CHO 1CHO 1CHO 1CHO

H2 OH HO 2 H H2 OH HO H
2
H 3C OH H 3C OH HO 3C H HO 3C H

H 4C OH H 4C OH H 4C OH H 4C OH

H 5C OH H 5C OH H 5C OH H 5C OH
6CH2OH 6CH OH 6CH2OH 6 CH2OH
2

D-Allose D-Altrose D-Glucose D-Mannose

Epimers
Epimers
1. Epimerization Reactions in the presence of Base
 Ene-diol Rearrangement

NaOH/H2O

Glucose (aldose) Fructose (ketose)

Ene-diol Rearrangement
 D-Fructose (writing patent)

1CH2OH 1CH2OH
6CH2OH OH
2 O HO 2 O
H 3C OH H 3C OH HO 2
5
HO 4C H HO 4C H 1
H 5C OH H 5C O
4 3 CH2OH
6CH2OH 6 CH2OH OH

Fischer projection Haworth form

α-D-Fructose
Reducing sugar and non-reducing sugar

A reducing sugar is any sugar that is capable of

acting as a reducing agent because it has a free
aldehyde group or a free ketone group. All
monosaccharides are reducing sugars
 Tollens Reagent: Ag(NH3)2OH

• Tollens reagent reacts with aldehyde

• Sugars that give a silver mirror with Tollens
are called reducing sugars.
• All monosaccharides are reducing sugars
 Fehling's solution
Fehling's solution is prepared by combining two separate
solutions, known as Fehling's A and Fehling's B.

Fehling's A is aqueous solution of copper(II) sulfate, which

is deep blue.

Fehling's B is a colorless solution of aqueous 

Potassium sodium tartrate (also known as Rochelle salt)
made in a strong alkali, commonly with sodium hydroxide
 Benedict's reagent
It is a complex mixture of sodium carbonate, sodium citrate and copper(II) sulfate
 pentahydrate

Generally, Benedict's test detects the presence of aldehydes and alpha-hydroxy-

ketones, also by hemiacetal, including those that occur in certain ketoses
 Non-reducing Sugars

Non-reducing Sugars: Sugar that is not capable of acting as a reducing agent

• Glycosides are acetals, which stable in base, so they do not react with Tollens
reagent, Fehling's solution, Benedict's reagent.
Oxidation and reduction reactions
Oxidation Reaction with Br2/H2O
Example: Oxidation of Glucose
Example: Oxidation of Mannose
 Oxidation by Nitric Acid

Nitric acid oxidizes both the aldehyde and the terminal alcohol.
Example: Oxidation of Glucose
Example: Oxidation of Mannose
Example: Oxidation of Erythrose

Tartaric acid
 Reduction reactions

CHO CH2 OH
OH H OH H OH
O HO H HO H
NaBH4
OH H OH H OH
OH H OH H + , H 2O H OH
yranose CH2 OH CH2 OH
D-Glucose D-Glucitol
(D-Sorbitol)
Other examples
H2:Pd/C Reduction
Osazone formation with Phenyl Hydrazine
Glucose or Mannose Reacts with 3 equiv. phenyl hydrazine produces Osazone

H+
H+

Osazones are a class of carbohydrate derivatives found in organic

chemistry formed when sugars are reacted with excess of phenylhydrazine.

The famous German chemist Emil Fischer developed and used the reaction to
identify sugars whose stereochemistry differed by only one chiral carbon.
Osazone formation: Glucose Vs Fructose
Osazone formation: Gulose Vs Idose
 Carbohydrate Synthesis
Ascending synthesis of monosaccharides: Increasing the carbon
1
CHO
2
H C OH
3
CH2OH
D-Glyceraldehyde

1CHO 1CHO

H 2C OH HO 2C H

H 3C OH H 3
C OH
4 CH2OH 4 CH2OH

D-Erythrose D-Threose
 Hydrocyanation reaction of aldehydes
NaCN+HCl
CN CN
1
CHO H C OH HO C H
2
HCN +
H C OH H C OH H C OH
3
CH2OH CH2OH CH2OH

D-Glyceraldehyde

C N CH=NH CH=O

H C OH H2:Pd/BaSO4 H C OH H2O H C OH
D-Erythrose
H C OH H C OH H C OH

CH2OH CH2OH CH2OH

C N C=NH CH=O

HO C H H2:Pd/BaSO4 HO C H H2O HO C H D-Threose

H C OH H C OH H C OH

CH2OH CH2OH CH2OH

Other Examples
 Carbohydrate Synthesis
Descending synthesis of monosaccharides: Decrease the carbon

1CHO
H2 OH CHO CHO
HO 3C H HO C H H C OH CHO
H 4C OH H C OH H C OH H C OH
H 5C OH H C OH CH2OH CH2OH
6CH2OH CH2OH
D-Erythrose D-Glyceraldehyde
D-Glucose D-Arabinose
 Ruff Degradation
Aldose chain is shortened by oxidizing the aldehyde to -COOH, then decarboxylation.

Glucose to Arabinose
Arabinose to Erthrose
D-Erythrose to Glyceraldehyde
 Acetylation of Glucose

(Or)

CHO CH2 OH
H OH H OH
HO H HO H
NaBH4
H OH H OH
H OH H OH
CH2 OH CH2 OH
D-Glucose D-Glucitol
(D-Sorbitol)
Methylation of Glucose
Protections of Anomeric position
 Disaccharides

When two monosaccharide are combined by glycosidic

linkage, a disaccharide is formed. Therefore they yield two
molecules of same or different monosaccharide on
hydrolysis.

General formula of Disaccharides : Cn(H2O)n-1

The disaccharides just like monosaccharides are white

crystalline, sweet solids. However, even though they are
soluble in water, they are too large to pass through cell
membranes.
 Disaccharides
• Disaccharides are formed when two
monosaccharides are joined together and a
molecule of water is removed, a process known as
dehydration reaction

• Maltose
• Lactose
• Sucrose
• Trehalose
 Maltose
• Maltose is a disaccharide formed from two molecules of D-glucose.
Maltose is the basic molecule of starch. Maltose can be produced
from starch by hydrolysis in the presence of the enzyme diastase
glycosidic bond

glycosidic bond

glycosidic bond
It has a 1,4-α- glycosidic linkage, acts as a reducing sugar
 Lactose
• Lactose is a disaccharide derived from the condensation of
Galactose and Glucose.
• It possess β-1→4 glycosidic linkage
• Lactose is commonly called Milk Sugar 
• Lactose requires you have an enzyme called lactase to digest
the disaccharide

It has a 1,4- glycosidic linkage, acts

as a reducing sugar

Applications • Widely used in food industry. • Also used as filler in tablets.

 Lactose intolerance

• Lactose intolerance is a condition in which

people have symptoms due to the decreased
ability to digest lactose, a sugar found in milk
products.
• Lactose intolerance is due to the lack
of enzyme lactase in the small intestines to
break lactose down into glucose and galactose.
 Sucrose
• Sucrose is the common table sugar
• Is obtained commercially from sugar cane
or sugar beets.
• The anomeric carbon atoms of a glucose
unit and a fructose unit are joined in this
disaccharide;
• The configuration of this glycosidic linkage
is α for glucose and β for fructose.
• Sucrose can be cleaved into its component
monosaccharides by the enzyme sucrase.
 Trehalose

Trehalose is a sugar,
a disaccharide composed
of two glucose molecules join
ed by an alpha-alpha (1,1)
glycosidic bond
Trehalose is a non-reducing
sugar with similar chemical
structure and characteristics
to those of sucrose.
How to prepare Disaccharides
Maltose preparation
Maltose
 Sucrose

H+
 Oligosaccharides

1. They are small sized compound carbohydrates.

2. An oligosaccharides consists of 3-6, rarely 10 monosaccharide
residues.
3. They are soluble in water.
4. Oligosaccharides are sweet to taste.
5. They are physiologically active.
6. Oligosaccharides are structural components of cell
membranes.
7. Transport occurs in oligosaccharide stage.
 Examples of Oligosaccharides
• Trisaccharide: Raffinose (glucose, galactose and
fructose)
• Tetrasaccharide: Stachyose (2 galactose, glucose
and fructose)
• Pentasaccharide: Verbascose (3 galactose,
glucose and fructose)
• Hexasaccharide: Ajugose (4 galactose, glucose
and fructose)
 Trisaccharide: Raffinose

Raffinose is
a trisaccharide composed
of galactose, glucose,
and fructose.

It can be found
in beans, cabbage, brussels
sprouts, broccoli, asparagus,
other vegetables, and
whole grains.

Raffinose can be hydrolyzed to D-galactose and sucrose by the

enzyme α-galactosidase (α-GAL), an enzyme not found in the
human digestive tract.
Stachyose is a tetrasaccharide
• Stachyose is a tetrasaccharide consisting
of two α-D-galactose units, one α-D-
glucose unit, and one β-D-fructose unit
sequentially linked.
• Stachyose occurs naturally in
numerous vegetables (e.g. green
beans, soybeans and other beans) and
other plants.
• Stachyose is less sweet than sucrose.
• It is mainly used as a bulk sweetener or
for its functional oligosaccharide
properties.
•  Stachyose is not completely digestible by
humans and delivers 1.5 to 2.4 kcal/g (6 to
10 kJ/g).
 Pentasaccharide: Verbascose
Verbascose, the
pentasaccharide of the
raffinose family of
oligosaccharides, consists of
galactose units joined to
sucrose. 
It is the substrate for bacterial
fermentation process.

(3 galactose, glucose and fructose)

Hexasaccharide: Ajugose
 Polysaccharides
1. They are large sized compound of carbohydrates.
2. A polysaccharide is made up of numerous (more
than 10 units to several hundred) monosaccharide
residues through glycosidic linkage .
3. Polysaccharides are insoluble in water.
4. Sweetness is absent.
5. They are physiologically inactive.
 Polysaccharides
• Polysaccharides contain 1–5 different
monosaccharide (sugar) units. 
• Polysaccharides may be linear or branched.
• Most polysaccharides are structurally complex.  
• Polysaccharides are present in all living
organisms where they carry out one or more of
their diverse functions. 
 Classification
• Chemically, the polysaccharides may be
classified into …………..
a) Homopolysaccharides (or homoglycanes),
made up of a single monosaccharide
b) Heteropolysaccharides (or heteroglycanes),
madeup of a mixture of monosaccharides on
hydrolysis.
 Examples of Homo-Polysaccharides:

• Cellulose
• Starch
• Glycogen
 Polysaccharides: Cellulose

It is a liner homopolymer composed of D-glucose

units linked through b-1,4 linkage.

It is made-up of linear chain of several hundred to

many thousands of  glucose unit.

The repeating disaccharide unit of cellulose is known

as b-cellobiose.

Cellulose is the major structural polymer in plants.

 Cellulose
• Animals lack the enzymes necessary to hydrolyze cellulose.
However, the bacteria in cows can digest cellulose so that they
can eat grass, etc.

• Cellulose is mainly used to produce paperboard and paper.

• Cellulose has no taste, odorless, insoluble in water and most

organic solvents, but, it is biodegradable.

• It was shown to melt at 467 °C. It can be broken down

chemically into its glucose units by treating it with concentrated
mineral acids (HCl or H2SO4) at high temperature.
Structure of Cellulose

b-cellobiose unit
 Polysaccharides: Starch
• Starches are storage forms of glucose found in
rice, wheat, potato and vegetables, etc.

• Two type of structures are known for the

Starch

• 1) Amylose and
• 2) Amylopectin
 Amylose
• If the polymer is linear and made-up of only α-1,4
linkage glucose unit, is called amylose
• Amylose usually assumes a helical configuration
with six glucose units per turn.

CH2OH CH2OH CH2OH CH2OH

O H O H O H H O H
H H H
H H H H
OH H OH H OH H O OH H O
O O O
H OH H OH H OH H OH
 Amylopectin

It contains α-(1-4) bonds, as

well as α-(1-6) branch points.

CH2OH CH2OH
O H O H
H H
H H
OH H O OH H
O
O
H OH H OH
CH2OH CH2OH CH2 CH2OH

O O H O H O H
H H H H H
H H H H
OH H OH H OH H O OH H O
O O O
H OH H OH H OH H OH
 Polysaccharides: Starch
Starch contains 20-25% of amylase and 75-80% of
amylopectin molecules.

First amylose and amylopectin are hydrolyzed into small

fragments through the action of alpha-amylase enzyme, secreted
by salivary glands  and pancreas.

Maltose (disaccharide), Maltotriose (trisaccharide), Dextrins are

obtained at first by the amylase enzyme.

Second, maltose, maltotriose and dextrins are hydrolyzed to

glucose by sucrase-isomaltase (also often referred to as maltase)
enzyme.
 Polysaccharides: Glycogen
• Glycogen is the analogue of Starch
• Similar to Starch, Glycogen is also made up of only α-D-
glucose units.
• It is fully branched structure
• Glycogen also known as animal starch that can be found
only in animals.
• The animal liver and muscles are responsible in the
creation of glycogen.
• The glycogen act as an emergency reserves when a
human body suddenly need a an ample amount of energy.
 HETEROPOLYSACCHARIDES
• Polymer of different monosaccharide units
compained together
Ex: Glycosaminoglycans(GAGs) (or) Mucopolysaccharides

Hyaluronic acid
Chondroitin sulfate
Heparin Sulfate
Dermatan sulphate
Keratan sulfate
Glycosaminoglycans
Applications of Glycosaminoglycans (GAGs)

• Its essential components of the extra cellular

matrix.

• GAGs play an important role in mediating cell-

cell interactions

• GAGs stabilize and support cellular and fibrous

components of tissue while helping maintain the
water and salt balance of the body.
 Heparin
Heparin is an anticoagulant (blood thinner) that prevents the formation of blood
clots.

Heparin is used to treat and prevent blood clots caused by certain medical
conditions or medical procedures.
CHEMISTRY OF LIPIDS
 Lipids

• Chemically, lipids are defined as the esters of

alcohol and fatty acids.

• Lipids are water insoluble, oily or greasy

organic compounds soluble in non-polar
organic solvents.
 Functions of lipids
• Storage form of energy

• Important dietary components because of their high

energy value and also because of the fat-soluble
vitamins

• Structural components of bio-membranes

• Serve as thermal insulators in the subcutaneous

tissues and around certain organs
 Functions of lipids
• Provide shape and contour to the body

• Act as metabolic regulators

• Combinations of lipid and protein (known as

lipoproteins) are important cellular constituents.

• Similarly, Combinations of lipid and Carbohydrate (known

as Glycolipids) are important cellular constituents.
 Clinical significance of lipids
• Following diseases are associated with
abnormal chemistry or metabolism of lipids-
1. Obesity
2. Diabetes Mellitus (Type 2)
3. Hyperlipoproteinemia
4. Fatty liver
5. Lipid storage diseases
 Classification of the lipids

• Simple Lipids
• Complex Lipids
• Derived lipids
 Classification of the lipids
Simple lipids
Fats and Waxes are called simple lipids

a. Fats: Esters of fatty acids with glycerol.

 Examples of Fatty acids
Fatty acids are hydrocarbon structures (containing carbon and
hydrogen atoms) formed by four or more carbons attached to
an acidic functional group called carboxyl group.

On the other hand, Fatty acids are aliphatic carboxylic acids

Saturated

C18:1, ω-9

Un-Saturated
 Type of fatty acids
a) Saturated
b) Unsaturated
c) Branched fatty acids
d) Substituted Fatty acids
e) Cis-Fatty acid
f) Trans-Fatty acid
Branched and Substituted fatty acids

Branched

Substituted
Cis- and Trans Fatty acid
 Classification of the lipids
Simple lipids:
b) waxes:
• Esters of fatty acids with other than Glycerol is called Waxes.
• Waxe esters are formed by combining one fatty acid with one
fatty alcohol
• Various types of wax esters exist. Some are saturated, and
others contain unsaturated centers
• Both fatty acids and fatty alcohols may have of different carbon
chain length.
• Important for manufacturing of ointments & cosmetics
• Not digested
 Complex lipids
• Lipid with other functional groups in addition to an alcohol and
a fatty acid.
1) Phospholipids: lipids contining a phosphoric acid
residue.

2). Glycolipids: Lipids containing a Carbohydrate moiety

3). Sulfolipids: Lipids containing a sulphur or

4) Aminolipids: Lipids containing a amine moiety
 Structures
Phospholipids:

Glycolipids:
 Derived Lipids
• Derived lipids are the substances produced
from simple and complex lipids through the
process of hydrolysis.

• e.g. Steroids, Terpenes and Carotenoids.

 Steroids
• Steroids are derived lipids that are found
in almost every species of animal and do
not contain fatty acids.
• They are hydrophobic and insoluble in
water, but they do not resemble lipids
since they have a structure composed of Cholesterol
four fused rings.

• Cholesterol is the most common steroid and is mainly

synthesized in the liver;
• It is the precursor to vitamin D.
• Cholesterol is also a precursor to many important steroid
hormones like estrogen, testosterone, and progesterone.
• Therefore, steroids play very important roles in the body’s
reproductive system.
 Terpenes
• Terpenes are found mainly in plants, and this group includes
substances such as natural rubber and many essential oils.
• Terpenes can be cyclic or acyclic, with a large range of
structural variations.
• Some of them are used as spices, perfumes and medicines for
thousands of years 
 Carotenoids
• Carotenoids are a type of
tetraterpene produced only by
plants.
• Carotenoids are plant pigments
responsible for bright red, yellow
and orange hues in many fruits and
vegetables.
• These pigments play an important
role in plant health. People who eat
foods containing carotenoids get
protective health benefits as well.
 Glycolipids
• Glycolipids are lipids with
a carbohydrate attached by a glycosidic bond.
• Their role is to maintain the stability of the cell
membrane and to facilitate cellular recognition,
which is crucial to the immune response and in
the connections that allow cells to connect to
one another to form tissues.
• Glycolipids are found on the surface of
all eukaryotic cell membranes
 Lipoproteins
Lipoproteins are huge multicomponent
complexes containing lipids and proteins.

1.High-density lipoprotein (HDL)

2.Low-density lipoprotein (LDL)
3. Very low-density lipoprotein (VLDL), 
4.Intermediate-density lipoprotein (IDL),
These complexes are essential for the transport of
cholesterol and triglyceride throughout the body. 
 Glycoprotein and Proteoglycans

• Glycoprotein and Proteoglycans are the compounds

where carbohydrates linked to proteins covalently.
 Glycoprotein and Proteoglycans
• Glycoprotein have a very low carbohydrate to
protein ratio, often 40:60.
• Glycoprotein are found in the cellular
membrane of cells .
• Proteoglycans have a very high carbohydrate
to protein ratio, often 95:5.
• Proteoglycans are found in the connective
tissues.
 Functions
• Glycoproteins act as integral membrane
proteins, and play a role in cell-cell recognition
and signaling.

• Proteoglycans provide structural support and

mechanical strength to the extracellular matrix,
play a role in the modulation of cell growth
processes, and provide padding in joints.
 Blood group determination
• The human blood groups A, B, AB, and O
depend on the oligosaccharide part of the
glycoprotein on the surface of red blood cells
(erythrocyte cells).
• The terminal monosaccharide of the
glycoprotein at the non-reducing end
determines blood group.
 Blood group determination
Type Terminal sugar
• A N-acetylgalactosamine
• B a-D-galactose
• AB both the above
• O neither of the above
• O is the “universal donor”
• AB is the “universal acceptor”
Blood group determination
 Carbohydrates in Bacteria
• Gram Negative and Gram Positive
 Carbohydrates in medicine
Tamiflu and Zanamivir

Tamiflu (1) and Zanamivir (2) are the monosaccharides frequently used for
preventing and treating viral infection caused by the Influenza A. Both of these
drugs are known as reversible competitive inhibitor of influenza neuraminidase

OH
NH2 OH
H
N H
HO O CO2H
O O
HN
HN
O
HN NH2
H3C O
Tamiflu (1) NH
Zanamivir (2)
 Antibiotics: Aminoglycosides
1. Aminoglycosides are highly potent, broad-spectrum antibiotics used for the
treatment of gram negative bacteria.
2. It exert antibacterial activity by binding to the bactrial ribosomal and inhibit
the protein synthesis.
3. The first drug from this family, streptomycin (isolated from Streptomyces
griseus) was discovered by Selman Waksman in 1944. In fact, streptomycin
was the first effective antibiotic drug against Mycobacterium tuberculosis
(TB).
R1
O NH2
HO R2
HO O R1
NH2 R1
H2N R3 O
O NHR2 R2 NH2
O R3 R4
HO O H2N NH2
O OH NHR4 O
HO NH2
Neamine O HO
OH NH2 Paromamine OH O
HO O
O OH OH HO O
HN O OH H2N Me
Ribostamycin AHB =
NH
OH OH
Butirosin B NH2 Me
O
R1 R2 R1 R2
R1 R2 R3 R4
Neamine NH2 H Kanamycin A OH OH OH H Gentamicin C1 NHCH3 CH3
Ribostamycin NH2 H Kanamycin B OH OH NH2 H Gentamicin C1a H NH2
Neomycin B NH2 H Amikacin OH OH OH AHB Gentamicin C2 NH2 CH3
Paromomycin OH H Tobramycin OH H NH2 H Gentamicin C2a CH3 NH2
Paromamine OH H Debekacin H H NH2 H Gentamicin C2b NHCH3 H
Arbekacin H H NH2 AHB Geneticin (G418) CH3 OH
Butirosin B NH2 AHB

Neomycin family Kanamycin family Gentamicin family

 Anticoagulant drug: Heparin
Heparin belongs to the family of glycosaminoglycans (GAGs), is widely used as an
anticoagulant drug over the last 50 years.
It is a sulfated linear polymer composed of disaccharide repeating units that
predominantly containing alternative iduronic acid and glucosamine moieties.
Synthetic heparin (SH) such as Fondaparinux (4) and Idraparinux (5) are
structurally well defined and completely free of chemical as well as biological
contaminations.17 These synthetic analogs showed better activity, bioavailability
and lower side effects than natural polymer and therefore, nowadays natural
heparins are slowly replaced by the synthetic constructs.

- OH OSO3-
O OH
O O OSO3- OSO3-
HO
O HO HOOC O HO2C OH O
O OSO3- - O O O
- O3SHN O HO O HO
O3SHN -
HO HO O3SHN O- -
O3SHN OMe
O HO O3SO
- O
O HO
O OSO3- Fondaparinux (4)
n
O OSO3-
O OSO3-
- MeO O
O3SHN 3 MeO OSO3-
HO OSO3-
HO HOOC O
O MeO
O O O HO2C OMe O
O O -
OSO3- MeO - O3SO
MeO O3SO-
O3SO O
-
O3SO OMe
MeO
Idraparinux (5)
 Anti-diabetics drugs: Acarbose
Diabetes describes a group of metabolic diseases in which the person has high level of
blood glucose over a prolonged period.

It is due to either insufficient insulin production in our body (diabetic type 1) or the body's
cells do not respond properly to the produced insulin (diabetic type 2).

Acarbose (6) is a pseudo-oligosaccharide of microbial origin and has become a

blockbuster diabetes drug in last decades.18 Acarbose inhibits alpha-glucosidase and
alpha-amylase enzymes which are needed for digesting carbohydrates into glucose.
OH

HO
HO
OH O
HN
HO OH
OH
O O
HO OH
Acarbose (6) OH
O O OH
HO
OH
 Anti-Rheumatoid arthritis drug: Auranofin

Rheumatoid arthritis (RA) is an autoimmune disease that causes a chronic, systemic

inflammatory disorder that affects many tissues, organs and flexible joints. Auranofin (8)
is a gold incorporated glucose monosaccharide, wieldy used in the treatment of
rheumatoid arthritis.

Au PEt3
O S
HO

HO OH
OH
Auranofin (8)
 Anticonvulsant drug: Topiramate
A convulsion is a medical condition where body muscles contract and relax
rapidly and repeatedly, resulting in an uncontrolled shaking of the body.

Topiramate (9) is an anticonvulsant drug used in the treatment of epilepsy in

children and adults.21 Topiramate is also very effective in treating various
psychological problems including migraines, bipolar disorders, weight loss and
cluster headaches.
NH2
OSO
O
O O

O O
O

Topiramate (9)
 Lactulose: Chronic constipation drug
• Lactulose (11) is a non-digestible synthetic
disaccharide composed of fructose and galactose
moiety, primarily used in the treatment of
chronic constipation in patients of all ages
O OH
HO OH

O O OH
HO

HO OH
OH
Lactulose (11)
 Anti-cancer drug: Streptozotocin
• Streptozotocin (12) is a natural glucose-substituted
N-methyl-N-nitrosourea, a broad-spectrum antibiotic
and an experimental anticancer agent that has
shown diabetogenic activity in animals and clinical
activity in the treatment of malignant insulinomas in
man.
OH
O
HO O
N
HO N N
H O
OH CH3

Streptozotocin (12)
 Summary
• Carbohydrates are complex biochemical structures that
serve vital functions in the human body.
• Composed of a building block of sugar, they are the main
source of energy for the body.
• There are many types of carbohydrates. One or more sugars
will link together to form carbohydrates of different types.
• Complex carbohydrates consist of thousands of repeating
sugar units and are the major constituent of starch.
• Nucleotides such as DNA are also composed of
carbohydrates.
 Summary
• Among the most important are regulation of blood
glucose and provision of energy for the body.
• In addition, carbohydrates spare the use of
proteins for energy until the body is completely
depleted of carbohydrate stores.
• They can be used as flavorings and sweeteners and
are a source of dietary fiber.
• Their composition is complex and their function
essential.