BIOMOLECULES AND

POLYMERS

Classification - mono-, di-and polysaccharides (glucose, sucrose and starch only),

Hydrolysis of Sucrose. Amino acids and Peptides: General structure and physical
properties. Polymers: Natural rubber, cellulose, nylon, teflon and PVC

CONTENTS INTRODUCTION
 Carbohydrates Biomolecules are the organic compounds
 Amino acids present as essential constituents of living
organism in different cells. Biomolecules
 Peptides and proteins
build up all the living systems and are
 Polymers responsible for their growth and
maintenance. In the present chapter, we
shall briefly study the composition,
structures and also the different functions
which they are to form.

Polymers are one of the most important

substances which have a great impact on
our modern life. In this chapter, we shall
also study the different classes of
polymers, and their mode of synthesis.
 Chemistry : Biomolecules and Polymers

1. CARBOHYDRATES
Carbohydrates received their name because of their general formula Cx(H2O)y, according to which
they appear to be hydrates of carbon.
Carbohydrates are widespread in nature. In plants, they constitute upto 80% of the dry weight.
Carbohydrates occurring in plants include cellulose (which gives structural support to plants),
starch (which serves as the reserved energy source) and sugars (like sucrose and glucose).
Glucose is an essential constituent of blood in higher animals and occurs in polymeric form as
glycogen, in liver and in muscles. Carbohydrates also occur in adenosine triphosphate which is
involved in biological energy storage and transport systems. They are also present in the nucleic
acids which control in production of enzymes and the transfer of genetic information.
In nature, carbohydrates are synthesised by a process called photosynthesis. In this process,
sunlight impinging on chlorophyll present in the green plants is absorbed and the photochemical
energy thus obtained is used to convert carbon dioxide and water into carbohydrates and oxygen.
The overall process can be represented as follows.
Sunlight, chlorophyll
xCO 2  yH 2O   C x (H 2 O) y  xO 2
carbohydrate

1.1 CLASSIFICATION AND STRUCTURE OF CARBOHYDRATES

Carbohydrates are polyhydroxy aldehydes and ketones and substances which hydrolyse to
polyhydroxy aldehydes and ketones.
The simplest carbohydrates are called sugars or saccharides, (Latin: Saccharum, sugar).
Carbohydrates can be classified as monosaccharides, oligosaccharides and polysaccharides.
Monosaccharides : Monosaccharides are the simplest carbohydrates which cannot be hydrolysed
into smaller and simpler carbohydrates. A monosaccharide may be further classified as an aldose
or a ketose if it contains an aldehyde or a keto group, respectively. The simplest monosaccharides
being 2,3-dihydroxypropanal (glyceraldehyde) and 1,3-dihydroxypropanone. Their structures are
as shown below:
CHO CH2 OH

H C OH C O

CH2 OH CH2 OH
2,3-dihydroxypropanal 1,3-dihydroxypropanone
(an aldose) (an ketose)

Depending upon the number of carbon atoms in the chain, sugars are called trioses (3 carbons),
tetroses (4 carbons), pentoses (5 carbons), hexoses (6 carbons) and so on. Therefore, 2,3-
dihydroxypropanal is an aldotriose and 1,3-dihydroxypropanone is aketotriose.
Oligosaccharides: Carbohydrates that hydrolyse to yield 2-10 molecules of monosacchardies are
called oligosaccharides.
Disaccharide is an oligosaccharide which yield 2 molecules of monosacchardides on hydrolysis.
Similarly those that yield 3 molecules of monosaccahride are called trisaccahrides and so on.
Maltose and sucrose are examples of disaccharides. On hydrolysis, 1 mol of maltose yields 2 mols
of the monosaccharide of glucose. Sucrose undergoes hydrolysis to yield 1 mol of glucose and 1
mol of the monosaccharide fructose.
Polysaccharides: Carbohydrates that yield a large number of molecules of monosaccharides (
10) are known as polysaccharides.
Chemistry : Biomolecules and Polymers

Starch and cellulose are examples of polysaccharides. Both are the polymers of glucose.
Glyceraldehyde contains one asymmetric CHO CHO
carbon atom (marked by an asterisk) and can
thus exist in two optically active forms, called H C OH HO C H
the D-form and the L-form. Clearly, the two
forms are mirror images that cannot be H2C OH H2C OH
superimposed, that is they are enantiomers. D-Glyceraldehyde L-Glyceraldehyde

HC O D Means on HC O
1 the right 1

H C OH HO C H L Means on
2 2 the left
H2C OH H2C OH
3 3
D-Glyceraldehyde L-Glyceraldehyde

The two forms of glyceraldehyde are especially important because the more complex
monosaccharides may be considered to be derived from them. They serve as a reference point for
designating and drawing all other monosaccharides. In carbohydrate chemistry, the Fischer
projection formulas are always written with the aldehyde or ketone groups at the top of the
structure. By definition, if the hydroxyl group on the asymmetric carbon atom farthest from
aldehyde or ketone group projects to the right, the compound is a member of the D-family. If the
hydroxyl group on the farthest asymmetric carbon projects to the left, the compound is a member
of the L-family. The maximum number of optical isomers of a sugar is related to the number of
asymmetric carbon atoms in the molecule and may be calculated by the following simple
equation.
Maximum Number of Optical Isomers = 2n, where n = the number of asymmetric carbon atoms.
Since glyceraldehyde contains only one asymmetric carbon atom, the number of optical isomer is
21. We know that 21 is = 2, and we have seen that there are indeed two different glyceraldehydes.
Aldotetroses : If we examine the general formula of an 1. CHO
aldotetrose, we see that they contain two asymmetric carbon |
2. *CHOH
atoms (marked by asterisks). |
This means that 22 or 4 optical isomers are possible. They may be 3. *CHOH
represented as the following two pairs: |
an aldotetrose
4. CH2OH

CHO CHO CHO CHO

| | | |
H – C – OH HO – C – H HO – C – H H – C – OH
| | | |
H – C – OH HO – C – H H – C – OH HO – C – H
| | | |
CH2OH CH2OH CH2OH CH2OH
Mirror images (recemic pair) Mirror images (recemic pair)
D (–)-erythrose L (+)-erythrose D (–)-threose L (+)-threose
All four isomers have been prepared synthetically. The D- and L-erythrose are mirror images, that
is, they are enantiomers. They have exactly the same degree of rotation but in opposite directions.
Equal amounts of the two would constitute a racemic mixture, that is, a mixture that would allow
a plane-polarised light to pass through the solution unchanged but could be separated into
dextrorotatory and laevorotatory isomers. The same comments hold for D- and L-threose.
However, D-erythrose and L-threose are not images, that is, they are diastereomers (optical
 Chemistry : Biomolecules and Polymers

isomers that are not mirror images are called diastereomers), and the degree of rotation of each
would probably differ.
Aldopentoses: If we examine the general formula of an aldopentose, we 1. CHO
|
see that they contain three asymmetric carbon atoms. 2. *CHOH
3
This means that 2 or 8 optical isomers are possible. |
3. *CHOH
These are:- D(–) lyxose, L(+)-lyxose, D(–) xylose, L(–)xylose, |
D(–) arabinose, L(+)-arabinose, D(–)-ribose, L(+)-ribose 4. *CHOH
|
5. CH2OH
an aldopentose

Aldohexoses: If we examine the general formula of aldohexose, we see 1. CHO

that it contains four asymmetric carbon atoms. |
This means that 24 or 16 optical isomers are possible. D and L forms of 2. *CHOH
altrose, allose glucose, mannose, galactose, talose, arabinose and idose |
Only three of the sixteen possible aldohexoses are found in nature (all 3. *CHOH
sixteen isomers have been prepared synthetically). They are D-glucose, D- |
mannose, and D-galactose. No one of these three optical isomers is a 4. *CHOH
mirror image of any of the others, so all three are diastereomers of each |
other. 5. *CHOH
|
6. CH2OH
an aldohexose

1.2 GENERAL CHARACTERISTIC OF MONOSACCHARIDES

The important characteristics of monosaccharides as follows:
i) All monosaccahrdes are water soluble due to the presence of hydrogen bonding between the
different OH groups and surrounding water molecules.
ii) Monosaccharides have sweet taste and upon heating they get charred and give the smell of
burning sugar.
iii) Monosaccharides are optically active in nature due to the presence of chiral carbon atoms.
iv) The chemical characteristics of monosaccharides are due to OH groups and carbonyl group
which may be either aldehydic (or) ketonic group.

1.3 D(+) GLUCOSE, DEXTROSE (OR) GRAPE SUGAR

D(+) glucose is a monosaccharide with the formula C6H12O6. It occurs in the free state in the ripe
grapes (grape sugar) in honey and also in many sweet fruits. It is also present in human blood to
the extent of about 0.1%. In the combined state, glucose is present in many disaccharides and
polysaccharides. It is optically active in nature and is also dextrorotatory (+).
Glucose can easily be prepared by hydrolyzing sucrose with hydrochloric acid in ethanolic
medium.

H
C12 H 22O11  H 2O   C6 H12 O6  C6 H12 O6
Sucrose D  (  )  Glu cos e D  (  )  Fructose

Since glucose is less soluble in ethanol, it separates out on cooling the reaction mixture.
Commercially, it is obtained by the hydrolysis of starch which is available from relatively
inexpensive sources such as maize, potatoes and rice.

Constitution of Glucose
Chemistry : Biomolecules and Polymers

1. Molecular Formula: By the usual analytical methods, the molecular formula of glucose is
found to be C6 H12O6.
2. Straight chain of six carbon atoms:
i) Reduction of glucose with conc. HI and phosphorus gives 2-iodohexane and
n-hexane. This indicates that six carbon atoms in glucose are present in a straight chain.
HI / P
C 6 H12O6   CH3  (CH 2 ) 4  CH3
Glucose prolonged n  hexane
heating

ii) Glucose when oxidized with bromine water gives gluconic acid which when reduced with
excess of HI gives n-hexanoic acid, CH3(CH2)4COOH, confirming the presence of a straight
chain of six carbon atoms in glucose.
3. Presence of five hydroxyl groups: When treated with acetic anhydride, glucose forms penta-
acetate indicating the presence of 5 – OH groups and since glucose is a stable compound, the
five –OH groups must be attached to 5 different carbon atoms.
C 6 H5 NHNH 2
C6 H12 O 6 C6H5N
 CHO
Glu cos e
|
(CHOCOCH3)4
|
CH2OCOCH3
Glucose pentaacetate
4. Presence of an aldehydic groups:
i) Glucose forms a cyanohydrin with hydrogen cyanide and a mono-oxime with hydroxylamine
suggesting the presence of a carbonyl group.
HCN
C 6 H12 O6   CN
Glu cos e |
(CHOH)5
|
CH2OH
Glucose cyanohydrin

ii) Glucose reduces Fehling solution and Tollen’s reagent indicating that the carbonyl group is
aldehydic in nature.
iii) The presence of aldehydic group in glucose is confirmed by its oxidation to gluconic acid
having the same number of carbon atoms.
Br2
C5 H11  CHO  (O)   C5H11O5  COOH
Glu cose Gluconic acid

Now since aldehydic group is monovalent, it must be present on the end of the chain.
5. Open chain structure: On the basis of the above points, glucose may be assigned following
part structure.
C C C C C CHO

OH OH OH OH OH
Supplying hydrogen atoms to the five carbon atoms to satisfy their tetravalency, following
structure (open chain) may be assigned to glucose: (* indicates asymmetric carbon atom).
H H H H H

H C C C C C CHO

OH OH OH OH OH
 Chemistry : Biomolecules and Polymers

6. Configuration* of glucose: Since the above structure possesses four asymmetric carbon
atoms (shown by asterisks), it can exist in 24 = 16 optically active forms, i.e., eight pairs of
enantiomers. All these are known and correspond to the D- and L-forms of glucose, mannose,
galactose, allose, altrose, gulose, idose and talose.
The naturally occurring dextrorotatory glucose (+)-glucose is only one of the 16-
stereoisomers.
CHO
1

H C OH
2

HO C H
3

H C OH CHO
4

H C OH H C OH
5

H2C OH H2C OH
6
D-(+)-Glucose (+)-Glyceraldehyde

Notations D- and L- for denoting configuration were given by Rosanoff; according to this
convention any compound whose bottom asymmetric carbon atoms has the configuration
similar to the configuration of dextrorotatory glyceraldehyde (drawn above, i.e. the bottom
carbon atom has –OH to the right and H to the left) is given D-configuration. The other
having –OH to the left and H to the right is given L-configuration. Remember that the
symbols D-and L- have no relation with the specific rotation value, i.e., with (+) or (–)- value.
For example, the natural (–)- fructose belongs to D-series, i.e., it is D-(–)- fructose.
7. Objections to open-chain structure of glucose: Even though open chain structure of (+)-
glucose explains most of its reactions, it fails to explain the following facts about it.
i) Glucose does not restore Schiff’s reagent colour.
ii) Glucose does not form a bisulphite and aldehyde-ammonia compound.
iii) Glucose forms two isomeric penta-acetates neither of which reacts with carbonyl reagents.
iv) The existence of the two isomeric glucoses and the change in specific rotation (mutarotation)
is not explained by an open-chain formula.
v) Glucose reacts with methanol in presence of dry HCl gas to form two isomeric glucosides.

1.4 STRUCTURAL FORMULAS FOR MONOSACCHARIDES

Although many of the properties of D–(+) –glucose can be explained in terms of an open-chain
structure (1, 2, or 3), a considerable body of evidence indicates that the open-chain structure
exists, primarily, in equilibrium with two cyclic forms. These can be represented by structures 4
and 5 or 6 and 7. The cyclic forms of D–(+)–glucose are hemiacetals formed by an intramolecular
reaction of the —OH group at C5 with the aldehyde group. Cyclization creates a new stereogenic
centre at C1, and this stereogenic center explains how two cyclic forms are possible. These two
cyclic forms are diastereomers that differe only in the configuration of C1. In carbohydrate
chemistry diastereomers of this type are called anomers, and the hemiacetal carbon atom is called
the anomeric carbon atom.
Chemistry : Biomolecules and Polymers

CHO CHO
CHO
H C OH H OH H C OH

HO C H HO H HO C H

H C OH H OH H C OH

H C OH H OH H C OH

CH2OH CH2OH
CH2OH
Fischer Wedge-line
projection Circle-and-l dashed wedge
formula ine formula formula
1 2 3

CH2OH CH2OH

O O

H H H H
CH3 CH3

+
OH H OH H
OH OH OH OH

H OH H OH
4 Haworth formulas 5

HOH2C HOH2C
HO HO
O + O
HO HO
OH
OH OH
HO
a-D-(+)-Glucopyranose b-D-(+)-Glucopyranose
6 7
Structures 4 and 5 for the glucose anomers are called Haworth formulas and, although they do not
give an accurate picture of the shape of the six-membered ring, they have many practical uses.
Demonstrates how the representation of each stereogenic centre of the open-chain form can be
correlated with its representation in the Haworth formula.
Each glucose anomer is designated as an  anomer or a  anomer depending on the location of the
—OH group of C1. When we draw the cyclic forms of a D sugar in the orientation shown in the 
anomer has the —OH trans to the —CH2OH group and the  anomer has the —OH cis to the —
CH2OH group.
CH2 OH
HOH2 C
O
H H O
HO
OH H OH

HO HO OH OH

H OH
 Chemistry : Biomolecules and Polymers

H O
1

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

Glucose
(Plane projection formula) When a model
of this is made it will coil as follows:

H C CH2 OH
5 6
OH
C OH H CH O
4 1
C C
HO 3 2
H OH
If the group attached to C4 is
pivoted as the arrows indicate, we
have the structure below.

CH2 OH CH2 OH
CH2 OH 6 H
C O O
O H 5 H H OH
H H H H
C OH H CH O OH H
OH H 4 1
C C HO H
HO OH 3 2
HO
H OH H OH
H OH
-D-(+)-Glucopyranose (Starred Open-chain form of D-glucose (The -D-(+)-Glucopyranose (Starred
—OH) is the hemiacetal —OH, proton transfer step occurs between —OH) is the hemiacetal —OH,
which in -glucose is on the separate molecules. It is not which in -glucose is on the same
opposite side of the ring from the intramolecular or concerted.) side of the ring as the —CH2OH
—CH2OH group at C5. group at C5)

1.5 MUTAROTATION
Ordinary D–(+)-glucose has a melting point of 146°C. However, when D–(+)-glucose is
crystallized by evaporating an aqueous solution kept above 98°C, a second form of
D–(+)-glucose with a melting point of 150°C can be obtained. When the optical rotations of these
two forms are measured, they are found to be significantly different, but when an aqueous
solution of either form is allowed to stand, its rotation changes. The specific rotation of one form
decreases and the rotation of the other increases, until both solutions show the same value. A
solution of original D–(+)-glucose (mp 146°C) has an initial specific rotation of + 112°, but,
ultimately, the specific rotation of this solution falls to +52.7°. A solution of the second form of
D–(+)-glucose (mp 150°C) has an initial specific rotation of +18.7°, but, slowly, the specific
rotation of this solution rises to +52.7°. This change in rotation toward an equilibrium value is
called mutarotation.
The explanation for this mutarotation lies in the existence of an equilibrium between the open-
chain form of D–(+)-glucose an the  and  forms of the cyclic hemiacetals:
Chemistry : Biomolecules and Polymers

O H

H OH
HOH2C HOH2 C
O HO H O
HO HO OH
H OH
HO OH OH
HO OH
H OH

H 2C OH
-D-(+)-Glucopyranose (mp Open-chain form of -D-(+)-Glucopyranose (mp
25 D-(+)-glucose 25
146°C; []D = +112°) 150°C; []D = +18.7°)

1.6 GLYCOSIDE FORMATION

When a small amount of gaseous hydrogen chloride is passed into a solution of D–(+)-glucose in
methanol, a reaction takes place that results in the formation of anomeric methyl acetals:
O H
C
OH
H OH
H2 C
O
HO H HO CH3 OH

HCL

(– HOH)
H OH OH
HO OH
H OH D-(+)-Glucose

H2 C OH

HOH2C
HOH2C O
O HO OCH3
HO 
OCH3 HO OH
HO OH
Methyl-D-glucopyranoside Methyl-D-glucopyranoside
(mp 165°C; []D25 = +158°) (mp 107°C; []D25 = –33°)
Carbohydrate acetals, generally, are called glycosides (see the following mechanism), and an
acetal of glucose is called a glucoside. (Acetals of mannose are mannosides, acetals of fructose
are fructosides, and so on.) the methyl D-glucosides have been shown to have six-membered rings
so they are properly named methyl -D-glucopyranoside and methyl -D-glucopyranoside.
The mechanism for the formation of the methyl glucosides (starting arbitrarily with -D-
glucopyranose) is as follows:

Formation of a Glycoside
 Chemistry : Biomolecules and Polymers

HOH2 C
HOH2 C O
O – H2 O
 H —A HO OH2
HO OH – H —A
 H2 O

HO OH
HO OH

:A HOH2 C
HOH2 C H O
O HO
OCH3
HO – HA
OCH3  HA
HOH2 C +  (a ) HO OH
O (a)
HO
 HO OH
 Methyl-D-glucopyranoside
 HOCH 3 
HOH2 C
HO OH  O HOH2 C
(b)  O
HO – HA
Attack by the alcohol  (b)
 HA
HO
oxygen on either face of the OCH3
resonance-stabilized HO OH OCH3
HO OH
carbocation
H :A Methyl-D-glucopyranoside

Hydrolysis of a Glycoside
HOH2C H
HOH2 C H O
+ – CH3OH
O H O H HO OCH3
HO OCH3  CH3OH

HO OH
HO OH
Methyl-D-glucopyranoside
O H
HOH2 C
O
HOH2 C H H HO
O 
OH
HO + – H3 O
O H  H3 O 
HOH2 C +  (a) HO OH
O (a) H  HO OH
HO -D-Glucopyranose

O H
HOH2 C
HO OH  O HOH2 C
(b)  O
HO – H3 O
Attack by water on either  ( b) HO
 H3 O
face of the
HO OH + OH
resonance-stabilized O H HO OH
carbocation
-D-Glucopyranose
H O H

H
Glycosides may be as simple as the methyl glucosides that we have just studied or they may be
considerably more complex. Many naturally occurring compounds are glycosides. An example is
salicin, a compound found in the bark of willow trees:
Carbohydrate moiety Aglycone moiety
    
OH
HOH2 C H2 C
O
HO
O

HO OH

Salicin
Chemistry : Biomolecules and Polymers

1.7 CONVERSION TO ESTERS

Treating a monosaccharide with excess acetic anhydride and a weak base (such as pyridine or
sodium acetate) converts all of the hydroxyl groups, including the anomeric hydroxyl, to ester
groups. If the reaction is carried out at a low temperature (e.g., 0°C), the reaction occurs
stereospecifically; the  anomer gives the -acetate and the  anomer gives the -acetate. Acetate
esters are common protecting groups for carbohydrate hydroxyls.
O
H3C

O O
H2 C
HOH2 C H3C O
O (CH 3 CO)2 O O
HO 
pyridine, 0 C

H3C O
OH O O
HO OH O
H3C
O CH3
O

1.8 BENEDICT’S OR TOLLENS’ REAGENTS: REDUCING SUGARS

Benedict’s reagent (an alkaline solution containing a cupric citrate complex ion) and Tollens’
solution [Ag  (NH 3 ) 2 OH] oxidize and thus give positive tests with aldoses and ketoses. The
tests are positive even though aldoses and ketoses exist primarily as cyclic hemiacetals.
H2 C OH
O H
C
C O
2
Cu (Complex)  (CHOH)n or 
 Cu 2 O   oxidation product
(CHOH)n
H2 C OH
H2 C OH
Benedict's Aldose Ketose (brick-red
solution reduction
(blue) product)

Sugars that give positive tests with Tollens’ or Benedict’s solutions are known as reducing sugars,
and all carbohydrates that contain a hemiacetal group give positive tests. In aqueous solution
these hemiacetals exist in equilibrium with relatively small, but not insignificant, concentrations
of noncyclic aldehydes or -hydroxy ketones. It is the latter two that undergo the oxidation,
perturbing the equilibrium to produce more aldehyde or -hydroxy ketone, which then undergoes
oxidation until one reactant is exhausted.
Carbohydrates that contain only acetal groups do not give positive tests with Benedict’s or
Tollens’ solutions, and they are called non-reducing sugars. Acetals do not exist in equilibrium
with aldehydes or -hydroxy ketones in the basic aqueous media of the test reagents.
 Chemistry : Biomolecules and Polymers

Reducing Sugar Nonreducing Sugar

Alkyl group or
O H O R another sugar
C O C O

C R' C R'

Hemiacetal (R' = H or = Acetal (R' = H or = CH2OH)

CH2OH) (gives positive (does not give positive
Tollens' or Benedict's test Tollens' or Benedict's test

1.9 BROMINE WATER : THE SYNTHESIS OF ALDONIC ACIDS

Monosaccharides do not undergo isomerization and fragmentation reactions in mildly acids
solution. thus, a useful oxidizing reagent for preparative purposes is bromine in water (pH 6.0).
Bromine water is a general reagent that selectively oxidizes the —CHO group to a —CO2H
group. It converts an aldose to an aldonic acid:
CHO CO H

(CHOH)n Br2

H2O
 (CHOH)n

H2 C OH H2 C OH
Aldose Aldonic acid

CHO CO2 H
H OH H OH
HO H HO H
Br2

H 2O

H OH H OH
H OH H OH
CH2 OH H2 C OH
D-Gluconic acid

1.10 NITRIC ACID OXIDATION : ALDARIC ACIDS

Dilute nitric acid —a stronger oxidizing agent than bromine water —oxidizes both the —CHO
group and the terminal —CH2OH group of an aldose to —CO2H groups. These dicarboxylic acids
are known as aldaric acids:
Chemistry : Biomolecules and Polymers

O C OH O C OH

HC OH O C HC OH
O
HC OH or
HC OH HC
– H2 O

 HC OH Corners such
HC OH HC OH O as this do not
HC represent a
HC OH HC OH CH2 group.
HC OH

C C C
O OH O OH O

Aldaric acid (from -Lactones of an aldaric acid

an aldohexose

This aldaric acid obtained from D-glucose is called D-glucaric acid.

O H O H

HOH2C H OH H OH
O
HO HO H HNO 3
  HO H
H OH H OH
HO OH OH
H OH H OH
H2 C OH
O OH


 D-Glucaric acid
D  Glu cos e

1.11 PERIODATE OXIDATIONS: OXIDATIVE CLEAVAGE OF POLYHYDROXY

COMPOUNDS
Compounds that have hydroxyl groups on adjacent atoms undergo oxidative cleavage when they
are treated with aqueous periodic acid (HIO4 ). The reaction breaks carbon-carbon bonds and
produces carbonyl compounds (aldehydes, ketones, or acids).

C OH O

 HIO4 
2 C  HIO3  H 2 O
C OH

Since the reaction usually takes place in quantitative yield, valuable information can often be
gained by measuring the number of molar equivalents of periodic acid that is consumed in the
reaction as well as by identifying the carbonyl products.
Periodate oxidations are thought to take place through a cyclic intermediate:
 Chemistry : Biomolecules and Polymers

C O
C OH C O O

(–H 2 O)
 IO 4–   I O 
  IO3–

C OH C O O
C O

Before we discuss the use of periodic acid in carbohydrate chemistry, we should illustrate the
course of the reaction with several simple examples. Notice in these periodate oxidations that for
every C—C bond broken, a C—O bond is formed at each carbon.
1. When three or more —CHOH groups are continuous , the internal ones are obtained as formic
acid. Periodate oxidation of glycerol, for example, gives two molar equivalents of
formaldehyde and one molar equivalent of formic acid:
O

C
H
H H
(formaldehyde)

H C OH
O
–
H OH  2 IO 

4
(formic acid)
C
H OH
H C OH 
O
H
C
(formaldehyde)
H H
2. Oxidative cleavage also take place when an —OH group is adjacent to the carbonyl group of
an aldehyde or ketone (but not that of an acid or an ester). Glyceraldehyde yields two molar
equivalents of formic acid and one molar equivalent of formaldehyde, while
dihydroxyacetone gives two molar equivalents of formaldehyde and one molar equivalent of
carbon dioxide:
O

C
H OH
(formic acid)
O H 
C
O
–
H OH  2 IO 
 4 (formic acid)
C
H OH
H C OH 
O
H
C
(formaldehyde)
Glyceraldehyde H H
Chemistry : Biomolecules and Polymers

O
H
C
H H
(formaldehyde)
H C OH

–
C O  2 IO 
4O C O (carbon dioxide)

H C OH O

H C
(formaldehyde)
Dihydroxyacetone H H
3. Periodic acid does not cleave compounds in which the hydroxyl groups are separated by an
intervening —CH2—group, nor those in which a hydroxyl group is adjacent to an ether or
acetal.
H2 C OH H2 C O CH3

CH2  IO 4– 
 no cleavage H2 C OH  IO –4 
 no cleavage
H2 C OH H2 C R

1.12 REDUCTION OF MONOSACCHARIDES: ALDITOLS

Aldoses (and ketoses) can be reduced with sodium borohydride to compounds called alditols:
CHO H2 C OH

(CHOH)n NaBH 4
or
 (CHOH)n
H 2 , Pt
H2 C OH H2 C OH
Aldose Alditol

Reduction of D-glucose, for example, yields D-gluctiol:

1.13 REACTIONS OF MONOSACCHARIDES WITH PHENYLHYDRAZINE:
OSAZONES
The aldehyde group of an aldose reacts with such carbonyl reagents as hydroxylamine and
phenylhydrazine. With hydroxylamine, the product is the expected oxime. With enough
phenylhydrazine, however, three molar equivalents of phenylhydrazine are consumed and a
second phenylhydrazone group is introduced at C2. the product is called a phenylosazone.
Phenylosazones crystallize readily (unilike sugars) and are useful derivatives for identifying
sugars.
H
O H
C NNHC6 H5

HC OH C NNHC6 H5

(CHOH)n  3 C6 H5 NHNH 2 
 (CHOH)n  C6 H 5 NH 2  NH 3  H 2 O
H2 C OH H2 C OH
Aldose Phenylosazone
 Chemistry : Biomolecules and Polymers

The mechanism for osazone formation probably depends on a series of reaction in which

C N C O

behaves very much like in giving a nitrogen version of an enol.

A Mechanism for the Reaction
Phenylosazone Formation
H A H H

HC N NHC6H5 HC N N C 6 H5
tautomerization (–C6 H 5 NH2 )
A: H C OH C O H  
:A

(formed from the aldose) HC NNHC6H5

HC NH
( 2 C6 H5 NHNH 2 )

 C NNHC6H5  NH 3  H 2 O
C O

Osazone formation result in a loss of the stereogenic centre at C2 but does not affect other
stereogenic carbons; D-glucose and D-mannose, for example, yield the same phenylosazone:
CHO HC NNHC6 H5 CHO
H OH C NNHC6H5 HO H
HO H HO H HO H
C6H5 NHNH 2 C6H5 NHNH 2
H OH   H OH   H OH
H OH H OH H OH
H2 C OH H2 C OH H2 C OH

D-Glucose Same phenylosazone D-Mannose

This experiment, first done by Emil Fischer, established that D-glucose and D-mannose have the
same configurations about C3, C4, and C5. Diastereomeric aldoses that differ in configuration at
only one carbon (such as D-glucose and D-mannose) are called epimers. In general, any pair of
diastereomers that differ in configuration at only a single tetrahedral stereogenic carbon can be
called epimers.

Epimers: Many common sugars are closely related, differing only by the stereochemistry at a
single carbon atom. For example, glucose and mannose differ only at C2, the first asymmetric
carbon atom. Sugars that differ only by the stereochemistry at a single carbon are called epimers,
and the carbon atom where they differ is generally stated. If the number of a carbon atom is not
specified, it is assumed to be C2. Therefore, glucose and mannose are “C2 epimers” or simply
“epimers”. The C4 epimer of glucose is galactose, and the C2 epimer of erythrose is threose.
Chemistry : Biomolecules and Polymers

CHO C2 epimers CHO CHO

1 1 1

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

HO C H HO C H C4 epimers HO C H CHO C2 epimers CHO

3 3 3 1 1

H C OH H C OH HO C H H C OH HO C H
4 4 4 2 2

H C OH H C OH H C OH H C OH H C OH
5 5 5 3 3

H2C OH H2C OH H2C OH H2C OH H2C OH

6 6 6 4 4
D-mannose D-glucose D-galatose D-erythrose D-threose

Cyclic structure of Fructose: Like glucose, 6

O
HO – C2 – 1CH2OH CH2OH OH
fructose also has a cyclic structure. Since 
|
fructose contains a keto group, it forms an H – 3C – OH O 5 2
intramolecular hemiketal. In the hemiketal |
H – 4C – OH H H H CH2OH
formation, C5 – OH of the fructose combines 1
|
with C2-keto group. As a result, C2 becomes H – 5C 4 3
chiral and thus has two possible arrangements | -D-Fructofuranose
6 OH OH
of CH2OH and OH group around it. Thus, CH2OH

D-fructose exists in two stereoisomeric forms, i.e., -D-fructopyranose and -D fructopyranose.
However in the combined state (such as sucrose), fructose exists in furanose form as shown
below:
Hydrolysis of Sucrose : (Invert Sugar or Invertose). Hydrolysis 6
of sucrose with hot dilute acid yields D-glucose and D-fructose. CH2OH

H
C12H22O11 + H2O 
 C6H12O6 + C6H12O6 5 O
Sucrose D-(+)-glucose D-(–)-fructose H H
[ ] D = +66.5° [ ]D = +53° [ ] D = –92° H
4 OH 1
Invert Sugar H
[ ]D = (+53°) – (–92°) = –39° HO 2
 -link
3
Sucrose is dextrorotatory, its specific rotation being +66.5%, D-
H OH O  Glycosidic
glucose is also dextrorotatory, []D = +53°, but D-fructose has a linkage
(Glucose unit)
large negative rotation,
[]D = -92°. Since D-fructose has a greater specific rotation than CH2OH O  -link
D-glucose, the resulting mixture is laevorotatory. Because
of this the hydrolysis of sucrose is known as the inversion of
sucrose, and the equimolecular mixture of glucose and fructose
is known as invert sugar or invertose. H H OH CH2OH

OH H
(Fructose unit) Sucrose
 Chemistry : Biomolecules and Polymers

1.14 POLYSACCHARIDES
Polysaccharides are the polymers of monosaccharides. The natural polysaccharides generally
contain about 100-3000 monosaccharide units. The three most abundant natural polysaccharides-
cellulose, starch and glycogen are derived from the same monomer, i.e., glucose.
Starch: It is a polymer of glucose. Its molecular formula is (C6H10 O5)n where the value of
n (200 – 1000) varies from source to source. It is the chief food reserve material or storage
polysaccharide of plants and is found mainly in seeds, roots, tubers, etc. Wheat, rice, potatoes,
corn, bananas etc., are rich sources of starch.
Starch is not a single compound but is a mixture of two components – a water soluble component
called amylose (20%) and a water insoluble component called amylopectin (80%). Both amylose
and amylopectin are polymers of -D-glucose.
Amylose is a linear polymer of -D-glucose. It contains about 200 glucose units which are linked
to one another through -linkage involving C1 of one glucose unit with C4 of the other as shown
below:
C1 – C4 – -linkage

(– Glucose – Glucose – Glucose – Glucose –)n

Linear Polymer

Amylopectin, on the other hand, is a highly branched polymer. It consists of a large number
(several branches) of short chains each containing 20-25 glucose units which are joined together
through -linkages involving C1 of one glucose unit with C4 of the other. The C1 of terminal
glucose unit in each chain is further linked to C6 of the other glucose unit in the next chain
through C1 – C6 -linkage. This gives amylopectin a highly branched structure as shown below:
C1  C4 -linkage
Glucose  Glucose  Glucose
 C1  C6 -linkage
Glucose  Glucose  Glucose
 C1  C6 -linkage
Glucose  Glucose  Glucose
Hydrolysis: Hydrolysis of starch with hot dilute acids or by enzymes gives dextrins of varying
complexity, maltose and finally D-glucose. Starch does not reduce Tollen’s reagent and Fehling’s
solution.
Uses: It is used as a food. It is encountered daily in the form of potatoes, bread, cakes, rice etc. It
is used in coating and sizing paper to improve the writing qualities. Starch is used to treat textile
fibres before they are woven into cloth so that they can be woven without breaking. It is used in
manufacture of dextrins, glucose and ethyl alcohol. Starch is also used in manufacture of starch
nitrate, which is used as an explosive.
Cellulose: Cellulose is the chief component of wood and plant fibers; cotton, for instance, is
nearly pure cellulose. It is insoluble in water and tasteless; it is a non-reducing carbohydrate.
These properties, in part at least, are due to extremely high molecular weight.
Chemistry : Biomolecules and Polymers

Cellulose has the formula (C6H10O5 )n. Complete hydrolysis by acid yields D-(+)-glucose as the
only monosacchardide. Like starch, cellulose is made up of chains of D-glucose units, each unit
joined by a glycoside linkage of C-4 of the next.
H H
OH H
H OH
HO
O
O O
HO HO O
HO H2O
O O
O
H OH
H OH
H
HO H
Cellulose

Cellulose differs from starch, however, in the configuration of the glycoside linkage. Upon
treatment with acetic anhydride and sulfuric acid, cellulose yields octa-O-acetylcellobiose; there
is evidence that all glycoside linkages in cellulose, are beta linkages.
Physical methods give molecular weights for cellulose ranging from 250000 to 1000000 or more;
it seems likely that there are at least 1500 glucose units per molecule. End group analysis by both
methylation and periodic acid oxidation gives a chain length of 1000 glucose units or more. X-ray
analysis and electron microscopy indicate that these long chains lie side by side in bundles,
undoubtedly held together by hydrogen bonds between the numerous neighbouring –OH groups.
These bundles are twisted together to form rope-like structures, which themselves are grouped to
form the fibers we can see. In wood these cellulose “ropes” are embedded in lignin to give a
structure that has been likened to reinforced concrete.
Properties of Cellulose: We have seen that the glycoside linkages of cellulose are broken by the
action of acid, each cellulose molecule yielding many molecules of D-(+)-glucose. Now let us
look briefly at reactions of cellulose in which the chain remains essentially intact. Each glucose
unit in cellulose contains three free ––OH groups; these are the positions at which reaction occurs.
These reactions of cellulose, carried out to modify the properties of a cheap, available, ready-
made polymer, are of tremendous industrial importance.
Like any alcohol, cellulose forms esters. Treatment with a mixture of nitric and sulfuric acid
converts cellulose into cellulose nitrate. The properties and uses of the product depend upon the
extent of nitration. Guncotton, which is used in making smokeless powder, is very nearly
completely nitrated cellulose, and is often called cellulose trinitrate (three nitrate groups per
glucose unit). Pyroxylin is less highly nitrated material containing between two and three nitrate
groups per glucose unit. It is used in the manufacture of plastics like celluloid and collodion, in
photographic film, and in lacquers. It has the disadvantage of being flammable, and forms highly
toxic nitrogen oxides upon burning.
In the presence of acetic anhydride, acetic acid, and a little sulfuric acid, cellulose is converted
into the triacetate. Partial hydrolysis removes some of the acetate groups, degrades the chains to
smaller fragments (of 200-300 units each), and yields the vastly important commercial cellulose
acetate (roughly a diacetate). Cellulose acetate is less flammable than cellulose nitrate and has
replaced the nitrate in many of its applications, in safety-type photographic film, for example.
When a solution of cellulose acetate in acetone is forced through the fine holes of a spinnerette,
the solvent evaporates and leaves solid filaments. Threads from these filaments make up the
material known as acetate rayon.
When an alcohol is treated with carbondisulfide and aqueous sodium hydroxide, there is obtained
a compound called a xanthate. Treatment of the xanthate with aqueous acid regenerates the
starting materials.
 Chemistry : Biomolecules and Polymers

SNa

RONa + S C S 
 RO
S
A xanthate
H+
ROH  CS2

Cellulose undergoes an analogous reaction to form cellulose xanthate, which dissolves in the
alkali to form a viscous colloidal dispersion called viscose.
When viscose is forced through a spinnerette into an acid bath, cellulose is regenerated in the
form of fine filaments which yield threads of the material known as rayon. There are other
processes for making rayon, but the viscose process is still the principal one used in the United
States. If viscose is forced through a narrow slit, cellulose is regenerated as thin sheets which,
when softened by glycerol, are used for protective films (Cellophane).
Industrially, cellulose is alkylated to ethers by the action of alkyl chlorides (cheaper than sulfates)
in the presence of alkali. Considerable degradation of the long chains is unavoidable in these
reactions. Methyl, ethyl, and benzyl ethers of cellulose are important in the production of textiles,
films, and various plastic objects.

2. AMINO ACIDS
Amino acids are the compounds which contain both an amino group and a carboxy group in their
molecules. They constitute a particularly important class of difunctional compounds as they are
the building blocks of proteins.
While several hundred different amino acids are known to occur naturally, 20 of them deserve
special mention as they are present in proteins. These amino acids are listed in Table. As given in
this table, for amino acids trivial names are common. The convention to use a three letter code, as
an abbreviation, for each amino acid is also given in the table. These abbreviations are particularly
useful in designating the sequence of amino acids in peptides and proteins which you will study.

NH2
R
Name Abbreviation
O
HO
NH2
H
glycine Gly
O
HO
NH2
H3C
alanine Ala
O
HO
Chemistry : Biomolecules and Polymers

CH3

H3C

NH2 valine Val

HO

O
CH3 NH2

O
H3C leucine Leu

OH
NH2

O
H3C isoleucine Ile
CH3 OH

S
H3C OH methionine Met

NH2

NH

O proline Pro

HO

O
phenylalanine Phe
H2N OH
NH2

tryptophan Trp
O
N HO
H
O

HO OH serine Ser

NH2
OH O

H3C OH threonine Thr

NH2
 Chemistry : Biomolecules and Polymers

HS OH cysteine Cys

NH2

HO O
tyrosine Tyr
H2N OH
O NH2

O
H2N asparagines Asn
OH
O O

H2N OH glutamine Gln

NH2

O NH2

O
HO aspartic acid Asp

OH
O O

HO OH glutamic acid Glu

NH2
NH2

O
H2 N Lysine Lys
OH
NH NH2

O
H2N arginin Arg
OH

N
O
N histidine His
H
H2N OH

2.1 AMINO ACIDS AS DIPOLAR IONS

Amino acids contain both a basic group (—NH2) and an acidic group (—CO2H). In the dry solid
state, amino acids exist as dipolar ions, a form in which the carboxyl group is present as a
carboxylate ion, —CO2– , and the amino group is present as an aminium ion, — NH3 (Dipolar
ions are also called zwitterions.) In aqueous solution, an equilibrium exists between the dipolar
ion and the anionic and cationic forms of an amino acid.
Chemistry : Biomolecules and Polymers

 
OH – OH 
H3 N CHCO2 H H3 O
H 3 N CHCO 2– H 3 O
H 2 NCHCO 2

R R R
Cationic form (predominant in strongly Dipolar ion Anionic form (predominant in strongly
acidic solutions, e.g., at pH 0) basic solution, e.g., at pH 14)

The predominant form of the amino acid present in a solution depends on the pH of the solution
and on the nature of the amino acid. In strongly acidic solutions all amino acids are present
primarily as cations; in stronglybasic solutions they are present as anions. At some intermediate
pH, called the isoelectric point (pI), the concentration of the dipolar ion is at its maximum and the
concentrations of the anions and cations are equal. Each amino acid has a particular isoelectric
point. Proteins have isolectric points as well. As we shall see later this property of proteins is
important for their separation and identification.
Let us consider first an amino acid with a side chain that contains neither acidic nor basic groups
— an amino acid, for example, such as alanine.
If alanine is dissolved in a strongly acidic solution (e.g., pH 0), it is present in mainly a cationic
form. In this state the amine group is protonated (bears a formal + 1 charge) and the carboxylic
acid group is neutral (has no formal charge). As is typical of -amino acids, the pKa for the
carboxylic acid hydrogen of alanine is considerably lower (2.3) than the pKa of an ordinary
carboxylic acid (e.g., propanoic acid, pKa 4.89):
CH 3CHCO 2 H CH 3CH 2 CO 2 H
Propanoic acid
N H3
 pK a  4.89
Cationic formof alanine
pK a1  2.3
The reason for this enhanced acidity of the carboxyl group in an -amino acid is the inductive
effect of the neighboring aminium cation, which helps to stabilize the carboxylate anion formed
when it loses a proton. Loss of a proton from the carboxyl group in a cationic -amino acid leaves
the molecule electrically neutral (in the form of a dipolar ion). This equilibrium is shown in
equation below.
The protonated amine group of an -amino acid is also acidic, but less so that the carboxylic acid
group. The pKa of the aminium group in alanine is 9.7. The equilibrium for loss of an aminium
proton is shown in the blue-shaded portion of the equation below. The carboxylic acid proton is
always lost before a proton from the aminium group in an -amino acid.
OH – OH –
CH 3CHCO 2 H H 3O 
CH 3CHCO 2– H 3O 
CH 3CHCO 2–

N H3 N H3 NH 2
 

Cationic form Dipolar ion Anionic form

pK a1  2.3 pK a 2  9.7
The state of an -amino acid at any given pH is governed by a combination of two equilibria, as
shown in the above equation for alanine. The isoelectric point (pI) of an amino acid such as
alanine is the average of pK a1 and pK a 2 :
1
pI  (2.3  9.7)  6.0 (isolelectric point of alanine)
2
 Chemistry : Biomolecules and Polymers

When a base is added to a solution of the net cationic form of alanine (initially at pH 0, for
example), the first proton removed is the carboxylic acid proton, as we have said. In the case of
alanine, when a pH of 2.3 is reached, the acid proton will have been removed from half of the
molecules. This pH represents the pKa of the alanine carboxylic acid proton, as can be
demonstrated using the Henderson-Hasselbalch equation. The Henderson – Hasselbalch equation
shows that for an acid (HA) and its conjugate base (A – ) ,
[HA]
pK a  pH log
[A – ]
When the acid is half neutralized,
[HA]
[HA]  [A – ] and log 0
[A – ]
thus pH = pKa
As more base is added to this solution, alanine reaches its isoelectric point (pI), the pH at which
all of alanine’s carboxylic acid protons have been removed but not its aminium protons. The
molecules are therefore electrically neutral (in their dipolar ion or zwitterions form) because the
carboxylate group carries a –1 charge and the aminium group a +1 charge. The pI for alanine is
6.0.
Now, as we continue to add the base, protons from the aminium ions will begin to be
removed,until at pH 9.7 half of the aminium groups will have lost a proton. This pH represents the
pKa of the aminium group. Finally, as more base is added, the remaining aminium protons will be
lost until all of the alanine molecules have lost their aminium protons. At this point (e.g., pH 14)
the molecules carry a net anionic charge from their carboxylate group. The amine groups are now
electrically neutral.
A titration curve for these equilibria. The graph represents the change in pH as a function of the
number of molar equivalents of base. Because alanine has two protons to lose in its net cationic
form, when one molar equivalent of base has been added, the molecules will have each lost one
proton and they will be electrically neutral (the dipolar ion or zwitterion form).
If an amino acid contains a side chain that has an acidic or basic group, the equilibria become
more complex. Consider lysine, for example, an amino acid that has an additional –NH2 group on
its  carbon. In strongly acidic solution, lysine is present as a
dication because both amino groups are protonated. The first proton to be lost as the pH is raised
is a proton of the carboxyl group (Pka = 2.2), the next is from the -aminium group (pKa = 9.0),
and the last is from the -aminium group.
  
OH – OH –
H 3 N(CH 2 )CHCO 2 H H 3O –
H3 N(CH 2 ) 4 CHCO2– H 3O –
H 3 N(CH 2 ) 4 CHCO2–

N H3 N H3 NH 2
 

Dicationic form of lysine Monocationic form Dipolar ion

pK a1  2.2 pK a 2  9.0 pK a3  10.5

OH –
H 3O –
H 2 N(CH 2 ) 4 CHCO 2–

NH 2
Anionic form
Chemistry : Biomolecules and Polymers

The isoelectric point of lysine is the average of pK a 2 (the monocation) and pK a3 (the dipolar
ion).
1
pI  (9.0  10.5)  9.8 (isoelectric oint of lysine)
2

3. PEPTIDES AND PROTEINS

In the last section, you studied the polymers of monosaccharides which act as structural
components in plants and serve as energy storage in animals. In this section, you will study
another kind of natural polymers called peptides and proteins.
Peptides are biologically important polymers in which 2-amino acids are joined by the amide
linkages, formed by the reaction of the carboxy group of one amino acid with the amino group of
another amino acid. These amide linkages are also called peptide bonds. The general structure of
a peptide is shown below:
O R 153 pm O
12 2
1° 5°
NH 12
114° C CH 2p
m NH C
13
123° CH NH

124 pm
123°

R O R
1 3
Peptide bonds
General Peptide Structure

Peptides can be classified as dipeptides, tripeptides and tetrapeptides, depending on whether the
number of amino acids, two, three or four, respectively. Peptides containing upto 50 amino acids
are called polypeptides. Bradykinin is an important naturally occurring nonapeptide which is
present in blood plasma and is involved in the regulation of blood pressure.
Arg  Pr o  Pr o  Gly  Phe  Ser  Pr o  Phe  Arg
bradykinin

Proteins are large polypeptides containing from about 50 to more than 8,000 amino acids per
molecule. Proteins have diverse biological functions. As enzymes and hormones, proteins catalyse
and regulate various reactions occurring in our body. As skin and hair, they give outer covering to
our body and as muscles they provide movement. In the form of antibodies, they protect us from
diseases. The oxygen present in the air we breath, is transported by the proteins haemoglobin.
The nucleoproteins in the genes supply and transmit the genetic information in cell division. In
addition, proteins also provide structural support in combination with other substances.
After having an idea about the importance of proteins, you must be curious to known about the
structure of peptides and proteins.

4. POLYMERS
5.1 INTRODUCTION
1. Polymers are giant and complex molecules.
2. Polymers have very high molecular weight usually of the order 103 to 106.
3. Arrangement of atoms in polymer is not entirely random.
4. Building blocks of polymers are called ‘mers’ or monomers.
5. a) Simplest type of polymers are homopolymers. They are made up of single type of
monomer.
 Chemistry : Biomolecules and Polymers

CH2 CH2 CH2 CH2 CH2

CH2 CH2 CH2 CH2
Polymethylene

b) Co-polymers are another type of polymer. These contains more than one sub-unit (or
monomer).
Example
O O O
Ph
C C
Ph
HC CH2 CH CH
CH2 HC CH2
CH CH HC
CH CH
C C
O Ph
O O C C
O O O
In the above example styrene and maleic anhydride monomers alternate. Co-polymer can
be a block co-polymer.
Example
CH2 CH2 CH2 CH2 CH2 CH CH2 CH CH2 CH
CH CH CH CH C CH2 C CH2 C CH2

Ph Ph Ph Ph CH3 CH3 CH3

Styrene units Isoprene units

Co-polymers can be random as well.

–– B – A – A – B – A – B – B – A – B – A – B – B – A ––
A and B are monomers.
6. There are many polymers in nature.
Example: Cellulose, starch, pepsin, insulin, egg alubumin, rubber, DNA (Deoxyribonucleic
aid), etc. These are called Biopolymers.
Man made polymers are, Nylon, Terylene, Polythene, Polystyrene, PVC (Polyvinyl chloride),
Bakelite, Perspex, Polysiloxane etc.
7. The properties of a polymer solution are strikingly different from those of a true solution. For
example, when polyvinyl alcohol is added to water, it swells.
a) Its shape gets distorted and after a long time it dissolves.
b) When more of polymer is added to a given solvent, saturation point is not reached. The
mixture of polymer and solvent assumes a soft dough-like consistency.
8. Addition polymers and condensation polymers are two important types of polymers.
9. Polymer can be described as linear, branched and network.

4.1 POLYMERS AND POLYMERIZATION

Macromolecules, both natural and man-made, owe their great size to the fact that they are
polymers (Greek: many parts); that is, each one is made up of a great many simpler units —
identical to each other or at least chemically similar — joined together in a regular way. They are
formed by a process we touched on earlier: polymerization, the joining together of many small
molecules to form very large molecules. The simple compounds from which polymers are made
are called monomers.
Polymers are formed in two general ways.
a) In chain-reaction polymerization, there is a series of reactions each of which consumes a
reactive particle and produces another, similar particle; each individual reaction thus depends
Chemistry : Biomolecules and Polymers

upon the previous one. The reactive particles can be free radicals, cations, or anions. A typical
example is the polymerization of ethylene. Here the chain-carrying particles are free radicals,
each of which adds to a monomer molecule to form a new, bigger free radical.
CH 2  CH 2
Rad  + CH2 = CH2  RadCH2CH2  
RadCH2CH2CH2CH2  etc.
b) In step reaction polymerization, there is a series of reactions each of which is essentially
independent of the preceding one; a polymer is formed simply because the monomer happens
to undergo reaction at more than one functional group. A diol, for example, reacts with a
dicarboxylic acid to form an ester; but each moiety of the simple ester still contains a group
that can react to generate another ester linkage and hence a larger molecule, which itself can
react further, and so on.
O O
HO

OH HO OH
ethylene glycol terephthalic acid

OH

O O

O OH

HOCH2CH2OH

OH

OH
O O

O O
OH
p-C6H4(COOH)2
O O

O O
HO O

O O

4.2 FREE-RADICAL VINYL POLYMERIZATION

We discussed briefly the polymerization of ethylene and substituted ethylenes under conditions
where free radicals are generated –– typically in the presence of small amounts of an initiator,
such as a peroxide. Reaction occurs
 Chemistry : Biomolecules and Polymers

CH2 CH2 CH2 CH2

nCH2 initiator
  CH CH CH CH
G
G G G G
vinyl monomer

or CH2 CH

G n
polymer

at the doubly bonded carbons –– the vinyl groups –– and is called vinyl polymerization. A wide
variety of unsaturated monomers may be used, to yield polymers with different pendant groups
(G) attached to the polymer backbone. For example:
CH2 CH2 CH2
H2C

 CH CH CH
Cl
Cl Cl Cl
vinyl chloride
Poly (vinyl chloride) (PVC)
CH2 CH2 CH2
H2C

 CH CH CH
CN
acrylonitrile CN CN CN
Polyacrylonitrile (Orlon)
CH2 CH2 CH2
H2C CH

 CH CH CH
Styrene C 6H5
C 6 H5 C 6 H5 C 6 H5
Polystyrene
CH3
CH3 CH3 CH3
H2C CH2 CH2 CH2

 C C C
O
COOCH3 COOCH3 COOCH3
O
Poly(methyl methacrylate)
CH3 (Plexiglas, Lucite)
Methyl methacrylate

Polymerzation involves addition of free radicals to the double bond of the monomer: addition,
first, of the free radicals generated from the initiator, and then of the growing polymer molecule.
This is, of course, an example of chain-reaction polymerization.
1. Peroxide  Rad  Chain – initiating steps
Rad. + H2 C CH
 Rad CH2
 CH
Chain – initiating steps
G G
G
2.
CH2 CH
Rad CH2 CH  H2C CH 
 Rad CH 2 HC Chain propagating steps
G G G
then steps like (3) repeated, until finally;
Chemistry : Biomolecules and Polymers

3. 2Rad(CH 2 CH) n CH 2 CH

G G
combination

Rad(CH 2 CH) n CH 2CH  CHCH 2 (CHCH 2 ) n Rad

G G G G
or Chain terminating steps
4. 2Rad(CH 2CH) n CH 2CH

G G
disproportionation
Rad(CH 2 CH) n CH 2CH 2  Rad(CH 2 CH) n CH  CH

G G G G

In each step the consumption of a free radical is accompanied by the formation of a new, bigger
free radical. Eventually, the reaction chain is terminated by steps that consume but do not form
free radicals; combination or disproportionation of two free radicals.
Copolymerization: Polymerization of a single monomeric compound to form a homopolymer is
known as homopolymerization. Evidently such a polymer is made up of identical units. In
contrast, a copolymer results when two different kinds of monomers are polymerized together to
give a product containing both the monomers. Such as process, known as copolymerization, is of
great industrial importance as it enables us to get a polymer possessing desired properties. To a
certain extent we can control the composition of a copolymer by varying the proportions of the
monomer in the polymerizing mixture. However, the composition of the polymer depends not
only on the relative concentrations of the two monomers, but also on the relative reactivities of
the monomers toward free radical addition. In other words, a more reactive monomer has greater
chance of being incorporated into a copolymer. As the reactivity of a carbon-carbon double bond
toward free radical addition is affected by the stability of the new free radical being formed, the
more stable free radicals will preferentially be produced.
Copolymerization of styrene with methyl methacrylate to produce polystyrene (co-methyl
methacrylate) (A) is an industrially important process.
CH3
CH3 CH2 CH2
CH C
H2C CH  H2C C 

C6 H5
C6 H5 C O O O
H3C O
CH3
n
(A)
Saran Wrap (B) is another copolymer formed by the copolymerization of vinylidene and vinyl
chlorides.

Cl Cl

H2C C  H2C CH 
 CH2 C CH2

Cl Cl Cl CH
n
Cl
(B)
 Chemistry : Biomolecules and Polymers

4.3 IONIC POLYMERIZATION: LIVING POLYMERS

Chain-reaction polymerization can proceed with ions instead of free radicals as the chain-carrying
particles: either cations or anions, depending on the kind of initiator that is used.

Cationic Polymerization

Y H2C CH  Y H2 C
 CH
An acid
G A carbocation G
G

CH2 CH

Y H2 C CH H2C CH  Y H2 C HC
 
 etc.
A carbocation G G G

Anionic Polymerization

Z H2C CH  Z H3C
 CH

A base G G
A carbanion

CH2 CH

Z H2 C CH H2C CH  Z H2C HC
 
 etc.
G G G
A carbanion

Cationic Polymerization is initiated by acids. Isobutylene, for example, undergoes cationic

polymerization to a tacky material used in adhesives. Copolymerization with a little isoprene
gives butyl rubber, used to make automobile inner tubes and tire liners. A variety of acids can be
used: sulfuric acid; AlCl3 or BF3 plus a trace of water.
CH3 CH3 CH3 CH3 CH3

H H2C H2C H2 C 
 H3C C CH2 C CH2

CH3 CH3 CH3 CH3 CH3

Anionic polymerization, as we might expect, is initiated by bases: Li , NH 2 , for example, or +

organometallic compounds like n-butyllithium. For example:

CH2 CH2
NH 2 K  + H2C CH  H2N
 CH 2  CHPh
  H2N CH CH K
- +

 etc.
Ph
+ - Ph Ph
Styrene K HC
Ph
Chemistry : Biomolecules and Polymers

H3C
CH3 - +
O C Li
n  BuLi + H2C 
 H3C 
 etc.
O O n-Bu
O

CH3
methyl methacrylate

Active metals like Na or Li can be used; here the initiation becomes a little more complicated, as
in the polymerization of styrene by the action of sodium metal and naphthalene. A sodium atom
transfers an electron (1) to naphthalene to form a radical-anion:
1. 
Na  naphthalene  Na  naphthalene

Naphthalene radical-anion

2. naphthalene   HC CH2 
 naphthalene  CH CH2

Ph Ph
Styrene radical-anion Formed by
one-electron transfer

3.
CH CH2 Ph
2 HC CH2 
 Ph CH2 CH
A dianion
Ph
The radical-anion then donates the electron to styrene (2) to form the styrene radical-anion. Like
many other free radicals, these dimerize (3). The resulting dianion is the true initiator, and begins
to grow at both ends:
CH CH2 Ph
Ph CH2 CH

CH 2 CHPh

Ph Ph

CH CH CH CH2 CH2 CH2 Ph

Ph CH2 CH2 CH2 CH CH CH

Ph Ph
Anionic polymerization is not limited to the vinyl kind, involving addition to carbon-carbon
double bonds. Ethylene oxide, for example, is converted by a small amount of base into a high
molecular weight polyether.
O
CH 3O    H3C
 O
O
O O O
H3C O  
 H3C O
O

4.4 SOME IMPORTANT POLYMERS

Natural Rubber : Natural rubber is isolated from a white fluid, called latex, that exudes from
cuts in the bark of Hevea brasiliensis, the South American rubber tree. Many other plants secrete
this polymer, as well. The name rubber was first used by Joseph Priestly, who used the crude
 Chemistry : Biomolecules and Polymers

material to “rub out” errors in his pencil writing. Natural rubber is soft and sticky. An enterprising
Scotsman named Charles Macintosh found that rubber makes a good waterproof coating for
raincoats. Natural rubber is not strong or elastic, however, so its uses were limited to
waterproofing cloth and other strong materials.
Structure of Natural Rubber : Like many other plant products, natural rubber is a terpene
composed of isoprene units. If we imagine lining up many molecules of isoprene in the s-cis
conformation, and moving pairs of electrons as shown below, we would produce a structure
similar to natural rubber. This polymer results from 1,4-addition to each isoprene molecule, with
all the double bonds in the cis configuration. Another name for natural rubber is cis,1-4-
polyisoprene.
Imaginary polymerization of isoprene units.

Natural rubber

The cis double bonds in natural rubber force it to assume a kinky conformation that maybe
stretched and still return to its shorter, kinked structure when released. Unfortunately, when we
pull on a mass of natural rubber, the chains slide by each other and the material pulls apart. This is
why natural rubber is not suitable for uses requiring strength or durability.
Vulcanization : Cross-Linking of Rubber: In 1839, Charles Goodyear accidentally dropped a
mixture of natural rubber and sulfur onto a hot stove. He was surprised to find that the rubber had
become strong and elastic. This discovery led to the process that Goodyear called vulcanization,
after the Roman god of fire and the volcano. Vulcanized rubber has much greater toughness and
elasticity than natural rubber. It withstands relatively high temperatures without softening, and it
remains elastic and flexible when cold.
Vulcanization also allows the casting of complicated shapes such as rubber tires. Natural rubber is
putty-like, and it is easily mixed with sulfur, formed around the tire cord, and placed into a mold.
The mold is closed and heated, and the gooey mass of string and rubber is vulcanized into a
strong, elastic tire carcass.
On a molecular level, vulcanization causes cross-linking of the cis-1,4-polyisoprene chains
through disulfide (–– S –– S ––) bonds, similar to the crysteine bridges that link peptides. In
vulcanized rubber, the polymer chains are linked together, so they can no longer slip past each
other. When the material is stressed, the chains stretch, but cross-linking prevents tearing. When
the stress is released, the chains return to their shortened, kinky conformations as the rubber snaps
back. Figure given below shows the structure of rubber before and after vulcanization.
Rubber can be prepared with a wide range of physical properties by controlling the amount of
sulfur used in vulcanization. Low-sulfur rubber, made with about 1 to 3% sulfur, is soft and
stretchy. It is good for rubber bands and inner tubes. Medium-sulfur rubber (about 3 to 10%
sulfur) is somewhat harder, but still flexible, making good tires. High-sulfur rubber (20 to 30%
sulfur) is called hard rubber and was once used as a hard synthetic plastic.
Chemistry : Biomolecules and Polymers

S S S S

S S S

S

heat S S

S S
S S

Figure: Vulcanization of rubber introduces disulfide cross-links between the polyisoprene chains. Cross-linking forms a stronger,
elastic material that does not pull apart when it is stretched.
Synthetic Rubber : There are many different formulations for synthetic rubbers, but the
simplest is a polymer of 1,3-butadiene. Specialized Ziegler – Natta catalysts can produce 1,3-
butadiene polymers where 1,4-addition has occurred on each butadiene unit, and the remaining
double bonds are all cis. This polymer has properties similar to those of natural rubber, and it can
be vulcanized in the same way.

1,4-polymerization of 1,3-butadiene

cis-1,4-polybutadiene

Buna Rubbers: Butadiene polymerises in the presence of sodium to give a rubber substitute viz.
BuNa. It is of two types
i) Buna - N or GRA: it is synthetic rubber obtained by copolymerisation of one part of acryl
nitrile and two parts of butadiene.

CH2  nCH 2 CN 

nCH 2 n
Buna-S
CN
It is more rigid responds less to heat and very resistant to swelling action of petrol, oils and
other organic solvents.
ii) Buna -S or GRS (General purpose Styrene rubber): It is a copolymer of three moles of
butadiene and one mole of styrene\ and is an elastomer. It is obtained as a result of free
radical copolymerisation of its monomers.
C6 H5

CH2
nC 6 H5 CH2  nCH 2 

n
Buna-S

It is generally compounded with carbon black and vulcanised with sulphur. It is extremely
resistant to wear and tear and finds use in manufacture of tyres and other mechanical rubber
goods.
 Chemistry : Biomolecules and Polymers

Polyvinyl Chloride (PVC)

1. Structure
CH2
CH

Cl

2. PVC is the most important plastic currently used in industry. It is used for cable insulation,
chemical plant, leather cloth, packaging and toys.
3. Acetylene is manufactured by one of two processes.
3000  C
i) CaO  3C 
electric furnace
 CaC 2  CO
coke

2H 2O

C 2 H 2  Ca(OH) 2
or
Cracking
ii) 2CH 4 
High Temperature
 C2 H 2  3H 2
Acetylene is then treated with HCl
Vapour Phase
CH  CH  HCl 
MgCl2 (catalyst )
 CH 2  CHCl heat
( Vinyl chloride)

The reaction mixture is cooled to 100-130°C. Unreacted HCl is removed by adding NaOH. The
product is liquefied at –40°C. Pure vinyl chloride is obtained on distillation. Vinyl chloride is a
colourless gas with sweet odour.
Vinyl chloride can also be prepared from ethylene.
FeCl3 500 C
CH 2  CH 2  Cl 2 
50 C
 CH 2Cl  CH 2 Cl 
3atm Kaolin catalyst
 CH 2  CHCl  HCl
Suspension polymerization method of obtaining PVC follows the formulation:
Vinyl chloride, water, polyvinyl alcohol, trichloroethylene and lauroyl peroxide (initiator) are
mixed and heated to 50°C. Polyvinyl chloride in the form of granules are obtained. It is used in
pastes as filler polymer.
Emulsion polymerization method uses vinyl chloride, water, ammonium stearate and ammonium
persulphate at 50°C for 2 hours. The polymer obtained is smooth spherical particles.
Head to tail structure for PVC has been proved by physical methods.
CH2 CH2 CH2 CH2 CH2
CH CH CH CH

Cl Cl Cl Cl

Commercial PVC is slightly branched. Branching occurs during polymerization by transfer of

hydrogen from within the polymer to growing radicals.
CH2 CH2 CH2 CH2

CH CH 

CH
 CH2

Cl Cl Cl Cl
Chemistry : Biomolecules and Polymers

Cl
Cl
CH CH2
CH2  nCH2 
 C
CH
CH
Cl
CH

Cl n
Unsaturated terminal groups containing allylic chloride are also thought to contribute to the
instability of polyvinyl chloride.
Cl

CH CH
Cl CH CH2
Detection of HCHO after ozonolyis of PVC is evidence of unsaturated terminal.
4. Commercial polyvinyl chloride has an average molecular weight in the range of 40,000 –
80,000.
Commercial polyvinyl chloride is atactic.
Cl H Cl H H Cl Cl H H Cl H Cl

H H H H H H H H H H
5. PVC is a colourless rigid material. PVC has limited solubility. It is soluble in ethers such a
tetrahydrofuran or ketones such as cyclohexanone, and nitro compounds such as nitro
benzene
Rigid PVC is extensively used in chemical plant because it is corrosion resistant. PVC is
unaffected by acids, alkalis and strong oxidizing agents (CrO3 or HNO3). Exposure of PVC to
UV light has adverse effect. High temperature (above 70°C) would change the colour of PVC
to yellow, orange, brown and finally black. Lead compounds such as lead carbonate and di-
basic lead phthalate stabilize PVC.
6. Degradation of PVC involves liberation of hydrogen chloride.
H Cl H Cl H Cl H Cl H
CH CH2 CH CH
CH CH CH CH CH CH CH CH CH CH CH CH CH

Cl
Teflon or PTFE (Polytetrafluoro ethylene): It is an addition polymer of tetrafluoroethylene
Pt, 700°C
nCF  CF 
2 2 
and high pressure
 (F2C  CF2 )n
Tetrafluoro ethylene Teflon
Commercial polymerizatioin of tetrafluoroethylene is essentially aqueous polymerization
accomplished by using free radical initiators (persulphate of hydrogen peroxide).
Teflon is a linear polymer with a high density and is resistant towards heat, action of chemicals
such as acids and bases. It’s electrical insulation property; weather resistant and chemical resistant
are excellent.
Uses: Major applications of PTFE are as seals films, gaskets, laboratory equipments or
components thereof, packings in pumps and valves, stopcocks, machine components,
kitchenwares (non-stick PTFE coated pans) etc., and in electrical insulation and electronics. Its
high volume cost is a constraint for its use for making large objects. Outstanding weather resistant
and chemical resistant polymers are also obtained from polymerization and copolymerization of
chlorotrifluoroethylene, vinyl fluoride, vinylidine fluoride and hexafluoropropylene.
 Chemistry : Biomolecules and Polymers

Nylon-66: Polymer which has polyamide linkage (–CO – NH –). Therefore these polymers are
known as nylons. A nylon-66 has hexamethylenediamine and adipic acid as its monomer unit.
nNH 2  (CH 2 ) 6  NH 2  nHOOC  (CH 2 ) 4  COOH
Hexamethylenediamine adipic acid

( CO  NH  (CH 2 ) 6  NH  CO  (CH 2 ) 4  CO ) n

Nylon  66

It is used for making bristles for brushes, in textiles in making sheets. It is blended with wool to
make socks and sweaters, cords and climbing ropes.
a) Nylon-6: Another polymer of this class is nylon-6. It is a monomer of caprolactum which is
obtained from cyclohexane.
OH
O N
H
N O
H 2SO4
oxidation
 
NH 2 OH
 
Beckmann rearrangement
 H 2O

cyclohexane cyclohexanone oxime caprolactum

O
H2O / 

NH CH2 CH2 C CH2 CH2 CH2 O

 H2N CH2 CH2 C
CH2 CH2 CH2 
 H2O

n
Nylon-6 OH
Amino caproic acid

It used for making tyre cords, fabrics and ropes.

b) Nylon-6, 10: A polymer of hexamethylene diamine (six carbon atoms) and sebacic acid (ten
carbon atoms).
2n H 2 O
nNH 2  (CH 2 ) 6  NH 2  nCOOH  (CH 2 )8  COOH  
hexamethylene diamine sebacic acid

( CO  (CH 2 )8  CO  NH  (CH 2 ) 6  NH  CO  (CH 2 )8  CO) n

Nylon  6,10

These polymers are formed by the condensation of two or more monomers with the
elimination of simple molecules like H2O, NH3 , ROH etc.