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BASIC CHEMISTRY OF
BIOMOLECULES

Biomolecules:
Definition:
 Biomolecules are organic molecules that occur naturally in living
organisms. Biomolecules include macromolecules like proteins,
carbohydrates, lipids and nucleic acids.
 It also includes small molecules like primary and secondary
metabolites.

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1) Carbohydrates:
Carbohydrates are the most abundant organic molecules in nature. They are primarily
composed of the elements carbon, hydrogen and oxygen. The name carbohydrate
literally means ‘hydrates of carbon’ and comes from the observation that when you
heat sugars, you get carbon and water (hence, hydrate of carbon). It is also interesting
to note that some of the carbohydrates possess the empirical formula (C.H2O)n where
n ≥ 3, satisfying that these carbohydrates are in fact carbon hydrates. However, there
are several non-carbohydrate compounds (e.g. acetic acid, C2H4O2; lactic acid,
C3H6O3) which also appear as hydrates of carbon. Further, some of the genuine
carbohydrates (e.g. deoxyribose, C5H10O4) do not satisfy the general formula. Hence
carbohydrates cannot be always considered as hydrates of carbon.

Definitions:
 Carbohydrates are polyhydroxyaldehydes and polyhydroxyketones and their derivatives.
 Carbohydrates are defined chemically as aldehyde or ketone derivatives of the higher
polyhydric alcohols, or compounds which yield these derivatives on hydrolysis.
 Classification:
Carbohydrates are classified as:
 Monosaccharides
 Disaccharides
 Oligosaccharides
 Polysaccharides

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1. Monosaccharides:
Monosaccharides (also called “simple” sugars) are those which cannot be hydrolyzed
further into simpler units.
General formula: Cn(H2O)n

Sub-classification:
(a) Depending upon the number of carbon atoms they possess:
 Those containing 3 C-atoms are called Trioses,
 Those containing 4 C-atoms are termed as Tetroses
 Monosaccharides with 5 C-atoms are called Pentoses
 And those with 6 C-atoms are called Hexoses.
(b) Depending upon whether aldehyde (– CHO) or ketone (– C=O) groups are present:
 aldoses
 ketoses

2. Disaccharides:
Those sugars which yield two molecules of the same or different molecules of
monosaccharide on hydrolysis.
General formula: Cn(H2O)n-1
Examples:
• Maltose • Sucrose
• Isomaltose • Lactose

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3. Oligosaccharides:
 Those sugars which yield 3 to 10 monosaccharide units on hydrolysis are called
oligosaccharides.
 Examples: Maltotriose, Raffinose
4. Polysaccharides (Glycans):
 Those carbohydrates which yield more than ten molecules of monosaccharides on
hydrolysis are called polysaccharides.
General formula: (C6H10O5)n
Types:
a. Homopolysaccharides (homoglycans):
Examples—Starch, glycogen, cellulose, dextrins, inulin
b. Heteropolysaccharides (heteroglycans):
Example—Mucopolysaccharides, Gums, Heparin, Hyaluronic acid

General Properties of Monosaccharides

1. Isomerism in Monosaccharides:
All the monosaccharides except dihydroxyacetone contain at least one asymmetric carbon
atom. Presence of this asymmetric carbon imparts two important properties to the molecules,
i.e.
 Stereoisomerism and
 Optical activity
Asymmetric carbon:
A carbon atom to which four different atoms or groups of atoms are attached is said to
be asymmetric.
Van’t Hoff’s rule of ‘n’:
Van’t Hoff’s rule of ‘n’ states that the number of possible stereo-isomers for a compound
having n number of asymmetric carbon atoms is 2n. (where, n represents the number of
asymmetric carbon atoms in a compound).
Example: Glyceraldehyde that contain two and glucose containing four asymmetric carbon
atoms, have four and sixteen possible stereoisomers, respectively.

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Stereoisomerism:
It is the phenomena in which compounds have the same molecular formula and same
connectivity (order of attachment) of their atoms, but different 3D (3 dimensional)
orientations of their atoms in space.
Types of Stereoisomerism:
I. Conformational isomerism:
It is a type of stereoisomerism in which the isomers can be converted into one another
by rotation around a single bond.
Conformational isomers are different shapes of the same molecule resulting from
rotation around a single C-C bond.
II. Configurational isomerism:
A type of stereo-isomerism in which two isomers have different configuration (3 D
arrangement of atoms or groups in space).

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Types of configurational isomerism:

a) Optical isomerism:
It is a type of stereo-isomerism in which the two isomers
differ1 by the way they rotate the plane polarize light.
Types of optical-isomers:
i) Enantiomers:
Optical isomers that are non-
superimposable mirror images
of each other.
Example:
D-Glucose and L-glucose

ii) Diastereomers (Diastereo-isomers):

Diastereomers are stereoisomers that are neither mirror images and nor superimposable.
Example: D-Glucose and D-Mannose

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D and L series in Monosaccharides:

The orientation of H and OH groups around the Penultimate carbon atom leads to two
series of monosaccharides. When the –OH group on this carbon is on the right, the sugar
belongs to D-series, when the –OH group is on the left, it is a member of L-series.
Most of the monosaccharides occurring in mammals are D-sugars, and the enzymes
responsible for their metabolism are specific for this configuration.

2) Optical activity:
• It is the ability of the compounds to rotate plane polarized light to the right or to the left.
• If the compound rotates plane polarized light to the right, it is called dextrorotatory, d or
(+). If it rotates plane polarized light to the left, it is called levorotatory, l or (-).
• The direction in which the light is rotated (the optical rotation) is a specific property of the
molecule and is not at all related with the two D and L forms of a compound. Thus, D-
glucose is dextrorotatory & D-fructose is levorotatory.

Specific rotation of various carbohydrates at 20 oC

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Racemic mixture:
A 1:1 mixture of two enantiomers (i.e. d and l) is known as a racemate or racemic mixture.
Racemic mixture does not exhibit any optical activity, since the dextro- and levorotatory
activities cancel each other.
Resolution:
The separation of optically active isomers from a racemic mixture is called ‘resolution’.
Racemization:
The process of converting an optically active compound into the racemic form is called
racemization.
3) Epimers and epimerization:
Two sugars which differ from one another only in configuration around a single
specific carbon atom other than carbonyl carbon are termed Epimers.
• For Example:
For instance, glucose and galactose are epimers with regard to carbon 4 (C4-epimers).
That is, they differ in the arrangement of OH group at C4. Glucose and mannose are
epimers with regard to carbon 2 (C2-epimers).

Note: Epimers are a type

of diastereomers.

Epimerization:
The interconversion of epimers (e.g. glucose to galactose and vice versa) is known as
epimerization and is catalyzed by a group of enzymes called epimerases,
e.g. conversion of galactose to glucose in liver.

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4) Aldose-Ketose (functional) isomerism:

It is the phenomena in which two sugars
have the same molecular formula but
different functional groups (i.e. one is
aldose & the other is ketose).
E.g. Glucose and fructose.
5) Cyclization of Monosaccharides
(Ring structures)
Before discussing cyclic structures of
monosaccharides let’s consider the open chain structure of monosaccharides first.
 As you can see two types of chemically reactive groups in the structure of mono-
saccharides. One reactive group is the carbonyl group (aldehydic/ ketonic) and the
others are alcoholic groups.
 These two types of groups have a tendency to react and form hemiacetal in case of
aldo sugars and hemi ketals, in case of keto sugars as shown.

 In fact, due to the angles of the tetrahedral carbon atoms in monosaccharide skeleton,
the molecules tends to bend forming a ring like bent structure. Due to this bent
structure, the aldehyde/ketone group & the alcohol group of carbon 5 or carbon 4
readily approach each other forming intramolecular hemiacetals or hemiketals. This
results in cyclization of the linear forms to stable ring structures. The cyclization is a
spontaneous process in solutions.
 In solution, monosaccharides with 5 or > carbons exist in less than 1 % in the open-
chain (acyclic) form.

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Pyranose and furanose ring structures:

If the ring structure formed by cyclization of monosaccharide is six membered (made
of 5 carbons and 1 oxygen), it is called a pyranose ring (similar to pyran); if it is five-
membered (made of four carbons and one oxygen), it is called a furanose ring (similar
to furan).
Fructose, a ketohexose, is usually found in the Furanose form, called fructofuranose,
whereas, glucose is most stable in the pyranose form. More than 99.7% of the total
glucose molecules in solution exist in pyranose form, and termed glucopyranose.

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6) Anomers and anomeric carbon:

Anomers are stereoisomers of cyclic monosaccharides that differ in the position of the OH
group at the hemiacetal/hemiketal carbon (carbonyl carbon).
Remember that epimers are stereoisomers that differ in configuration at any single
stereogenic center, whereas anomers are cyclic monosaccharides that differs in
configuration, specifically at the hemiacetal carbon, also called the anomeric carbon.
Anomeric carbon:
The hemiacetal (or carbonyl) carbon atom of cyclic
monosaccharide is called the anomeric carbon.
 Anomerization is the process of conversion of
one anomer to the other.
 Unlike enantiomers and epimers, which are not
interchangeable, anomers in an aqueous
solution freely interconvert between the α and β
forms, unless the hydroxyl group attached to the
anomeric carbon is linked to another molecule.

7) Mutarotation:
Mutarotation refers to the change in optical rotation when an aqueous sugar solution is
allowed to stand. OR
 Mutarotation is the change in specific rotation of a chiral compound due to
anomerization.
When D-glucose is first dissolved in water and the solution is put in optical path so that
plane polarized light is passed, the initial optical rotation shown by the sugar gradually
changes until a constant fixed optical rotation is reached (12-18 hrs). This phenomenon
of change of rotation is called as mutarotation.

Explanation:
Ordinary crystalline glucose happens to be in the α-form. The above change in optical
rotation represents a conversion from α-Glucose to an equilibrium mixture of α and β-
forms involving opening of the hemiacetal ring to form traces of the aldehyde form
(acyclic form), and then re-condensation to the cyclic forms.

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The equilibrium mixture contains

63% β-anomer and 36% α-anomer
of glucose with less than 1% open
chain form.
8) Reducing & non-reducing sugar:
Any sugar that has a potential
aldehyde or ketone functional
group and thus reacts as a reducing
agent is called a reducing sugar.
Monosaccharides by virtue of free
aldehydic or ketonic group in their
structure, i.e. presence of free anomeric carbon atom, reduces certain heavy metallic cation,
such as ferric (Fe3+) or cupric (Cu2+) ion in alkaline solution at high temperature and are
hence called as reducing sugars. During this reaction, the carbonyl carbon is oxidized to a
carboxyl group.

 All monosaccharides are reducing sugars; they all have a free reactive carbonyl group.
 Although ketones, in contrast to aldehydes, show no reductive ability, in an alkaline
environment the ketoses undergo isomerization to aldoses- e.g. fructose (ketose)
isomerize to glucose (aldose) - therefore the ketoses are also reducing sugars.
 Some disaccharides like maltose, lactose, Isomaltose etc, have exposed carbonyl groups
and are also reducing sugars, While other disaccharides such as sucrose are non-reducing
sugars and will not react with Benedict's solution. This is because both the anomeric
carbon atoms are involved in glycosidic linkage.

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 Polysaccharides such as starch etc, are non reducing sugars, since the concentration of
hemiacetal groups is very low.

 In describing disaccharides or polysaccharides, the end of a chain with a free anomeric

carbon (one not involved in a glycosidic bond) is commonly called the reducing end and
the other as non reducing end.

Important Reactions of Monosaccharides (with special reference to Glucose)

1. Reduction reactions:
 Mild reduction of D-glucose with sodium borohydride/ Na-amalgam yields a hexa-
hydroxy alcohol called D-sorbitol.
 Fructose gives 2 isomeric products sorbitol and Mannitol
 Since names for the polyhydroxy alcohols may be derived from the names of the
corresponding sugars by changing the suffix -ose to -itol, another name for sorbitol is D-
glucitol.

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• D-Mannose yields D-Mannitol.

• D-Galactose yields D-Dulcitol (galactitol).
• D-Ribose yields D-Ribitol

 Drastic reduction of glucose with hydro-iodic acid yields n-hexane.

2. Oxidation:
Aldoses contain 1° and 2° alcohols groups and an aldehyde group, all of which are
oxidizable functional groups. Three different types of oxidation reactions are seen:
A) Oxidation of the aldehyde to a carboxylic acid (an aldonic acid)
Mild oxidation of D-glucose with bromine water or hypobromous acid (HOBr)
gives a monocarboxylic acid called D-gluconic acid (aldonic acid).
 Galactose yield galactonic acid
 Mannose yield mannonic acid
Fructose does not react with mild
oxidizing agents such as bromine
water.

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B) Oxidation of both the aldehyde and 1° alcohol to a diacid:

Both the aldehyde and 1° alcohol of an aldose are oxidized to carboxy groups by
treatment with warm nitric acid, forming aldaric acid. Under these conditions, D-
glucose is converted to D-glucaric acid.
 D-Mannose yield mannaric acid
 D-Galactose yield Mucic acid
 Oxidation of fructose with
concentrated nitric acid yields a
mixture of glycolic acid (2-C) and
tartaric acid (4-C).

C) Oxidation of the 1° alcohol group to a carboxylic acid (Uronic acids):

When an aldose is oxidized in such a way that the primary alcohol group is converted
to – COOH group, without oxidation of aldehyde group, a uronic acid is formed.
They exert reducing action due to presence of free –CHO group.
Glucose on oxidation with dil HNO3 or H2O2 yield glucuronic acid.
 Mannose yield manno-uronic acid
 D-Galactose yield D-Galacto-uronic acid

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3. Ester formation:
 The alcoholic groups of monosaccharides may be esterified non-enzymatically or
enzymatically
 In fact, the metabolism of sugars inside the body starts with esterification of carbohydrates
with phosphoric acid.
 Glucose 6-phosphate and glucose 1-phosphate are good examples where ATP donates the
phosphate moiety
 Invitro, D-Glucose reacts with acetic anhydride in pyridine solution at 0 ºC to form penta-
acetate.

4. Osazone formation:
Osazones are yellow crystalline substances which are obtained by treating
monosaccharides with Phenyl hydrazine. Osazones have characteristic:
• Melting points
• Crystal structures, and
• Precipitation time and thus are valuable in identification of sugars.
Basis of reaction:
The reaction involves only the carbonyl carbon (i.e. aldehyde or ketone group) and the
next adjacent carbon. First Phenyl hydrazone is formed and then the hydrazone reacts
with two additional molecules of Phenyl hydrazine to form the osazones. The reaction
with a ketose or aldose is similar.
Note: This test is given by reducing sugars only.

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Types of Crystals
• Glucosazone crystals:
These are fine, yellow needles like crystals also called Bundle of Hay.
Note: Glucose, mannose and fructose due to similarities of structures form the same
osazones. [since these only differ in regards to C-1 and C-2 which after reacting with
phenylhydrazine also come to have the same configuration as is present in osazone
derived from glucose itself] But since the structure of galactose differs on C-4, that part of
the molecule is unaffected in osazone formation, it would form a different osazone.

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However, still we can use this test for identification due to the fact that the time of formation
of crystals varies depending on the sugar. Furthermore, some Osazones are precipitated only
from hot solution , others only upon cooling.
• Lactosazone crystals:
These are Powder puff/cotton ball shaped.
• Maltosazone:
These are star-shaped and compared to Sunflower petals.

Osazones Minimum time Appearance of crystals

for formation of crystals

Glucosazone 5 minutes Needle shaped/bundle of hay

Fructosazone 2 minutes Needle shaped/bundle of hay

Mannose 30 seconds Needle shaped/bundle of hay

Galactosazone 15-19 minutes Thorny ball shape

Lactosazone 30 minutes Powder puff shaped/cotton ball

shaped

Maltosazone 30-40 minutes Sunflower shaped/star

shaped crystals

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5. Reaction with Hydroxyl amine:

Glucose and fructose condense with hydroxyl amine to produce oximes.

6. Action of acids:
When treated with concentrated sulfuric acid/HCl, monosaccharides undergo dehydration
with an elimination of 3 water molecules. Thus hexoses give hydroxymethyl furfural while
pentoses give furfural on dehydration. These furfurals can condense with phenolic
compounds (α-naphthol) to form colored products. This is the chemical basis of the
popular Molisch’s test, Anthrone test and Seliwanoff’s test.
In case of oligo- and polysaccharides, they are first hydrolyzed to monosaccharides by
acid, and this is followed by dehydration.

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7. Action of Alkalis:
In mild alkaline solutions, carbohydrates containing a free anomeric carbon tautomerise to
form enediols, where two hydroxyl groups are attached to the double-bonded carbon atoms.

For example, Glucose, in mild alkaline

conditions, is converted into fructose and
mannose via a common endiol intermediate.
This reaction is known as the Lobry de
Bruyn-von Ekenstein transformation.

Whereas, sugars on boiling with strong

alkalis are caramelized to give yellow to
brown resinous product1.

8. Action as a Reducing Agent.

Monosaccharides by virtue of free aldehydic or ketonic group in their structure, i.e.
presence of free anomeric carbon atom, tautomerise to form enediols when placed in
alkaline solution. The enediol forms of the sugars are highly reactive and easily reduce
ions such as Fe3+, Ag+, Cu++ etc.

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9. Glycosides formation:
Glycosides are formed when the hemiacetal or hemiketal hydroxyl group (at anomeric
carbon) of a carbohydrate reacts with a hydroxyl group of another carbohydrate or a non
carbohydrate (e.g. methyl alcohol, phenol, glycerol). The bond so formed is known as
glycosidic bond and the non-carbohydrate moiety (when present) is referred to as
aglycone.
The monosaccharides are held together by glycosidic bonds to result in di-, oligo- or
polysaccharides.

10. Formation of amino sugars:

A hydroxyl group of monosaccharides can be replaced by amino group to form an amino
sugar. For example D-glucosamine, D-Galactosamine, D-Mannosamine. In all of these
hexosamines, the amino group is attached to C-2.

Several antibiotics (eg, erythromycin) contain amino sugars believed to be important for
their antibiotic activity.

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(11) Fermentation:
Fermentation is the process of breakdown of complex organic substances into smaller
substances with the help of enzymes. For example;
Monosaccharides such as glucose, fructose and mannose are readily fermented by
zymase from yeast. The process of yeast fermentation is very complex. Ordinarily, this
process results in the formation of alcohol and carbon dioxide.

Sugars can also be classified as:

Fermentable sugar (can be fermented by yeast)
eg Glucose, fructose and mannose, sucrose and maltose
Non- fermentable sugar (can not be fermented by yeast).
eg lactose, galactose, all pentoses and polysaccharides

MONOSACCHARIDES OF BIOLOGICAL IMPORTANCE

(a) Trioses:
Both D-glyceraldehyde and dihydroxyacetone occur in the form of phosphate esters, as
intermediates in glycolysis. They are also the precursors of glycerol, which the organism
synthesizes and incorporates into various types of lipids.
(b) Tetroses:
Erythrose-4-P occurs as an intermediate in hexose monophosphate shunt which is an
alternative pathway for glucose oxidation.

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(c) Pentoses
 widely distributed in nature both in plants & in animals (hemicellulose & nucleic acids).
 Ribose is a constituent of the Ribonucleic acid (RNA) of the cell and of many important
substances found in cell such as ATP, GTP, CTP, UTP, NAD+, NADP+, FMN, FAD and
coenzyme A.
Pentoses have the following properties:
1. May be aldose or ketose
2. Possess strong reducing properties
3. Form osazone crystals with phenyl hydrazine
4. With acids they are converted to furfural
5. Are not fermented by yeast

6. Several pentose have important physiological roles as given below.

a. Ribose and ribulose as phosphates are intermediates in pentose phosphate pathway.
b. L-xylulose is an intermediate in uronic acid pathway of glucose metabolism.
c. D-Lyxose is found in heart muscle as a component of lyxoflavin.
d. D-arabinose and D-xylose is found in glycoproteins.

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d) Deoxy sugars:
 Sugars in which the oxygen of a -OH group has been removed, leaving behind the H are
called deoxy sugars.
 Most important is the 2-deoxyribose, which is a constituent of DNA.
 It gives most of the reactions of sugars but does not form osazones.
 Deoxyhexoses also occurs in nature e.g L-fucose (6-deoxy-L-Galactose) in milk and
blood group substances and rhamnose (6-deoxy-L-Mannose) in strophanthin.

e) Hexoses:
D-Glucose:
 It is also called Grape sugar and Dextrose and is 74% as sweet as sucrose.
 It is widely distributed in nature and is the chief physiological sugar present in
normal blood (70-110 mg/dl).
 All tissues utilize glucose for energy. Erythrocytes and Brain cells utilize glucose
solely for energy purposes.
 In combination with other monosaccharides, glucose functions as a constituent of
disaccharides and polysaccharides.
 It is stored as glycogen in liver and muscles mainly.
 Shows mutarotation.
 on reduction, it forms sorbitol
 oxidation results in three types of acids i.e
gluconic acid, glucoronic acid and glucaric
acids.
 Pyranose form is predominant.

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2. Fructose:
 It is a keto-hexose and commonly called “fruit sugar” as it occurs free in fruits.
 It is very sweet sugar, much sweeter than sucrose (173% of sucrose) and more
reactive than glucose.
 It occurs as a constituent of sucrose and also of the polysaccharide inulin. It also
occurs in honey
 It is also found in seminal fluid and sperms utilize fructose for energy
 It is levorotatory and hence is called “laevulose”.
 It exhibits mutarotation
 When fructose is free, pyranose form is predominant. However, in sucrose it occurs
in furanose form.

3. D-Galactose
 It is seldom found free in nature.
 In combination, it is widely distributed in plant gums, seed coats of legumes and
pectins, and is a component of the disaccharide lactose. It is also a constituent of
glycolipid & glycoproteins
 It differs from glucose only in the spatial orientation of the —OH group at C-4 (Epimer).
 In the body, galactose is converted to glucose to provide energy and is synthesized from
glucose as needed.
 It is less sweet than glucose
and less soluble in water.
 D-Galactose is dextrorotatory
& show mutarotation.
 On oxidation with hot HNO3,
it yields mucic acid.

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4. D-Mannose:
 It does not occur free in nature but widely distributed in combination as the
polysaccharide mannan, e.g. in ivory nut.

 In the human body, it is found as a constituent of glycoproteins.

 It is epimer glucose with respect to Carbon # 2.

 Its reduction product, mannitol is important clinically in cerebral edema

 It gives all the reactions of glucose, however, it
cannot be differentiated from glucose through
osazone formation??.

DISACCHARIDES
 Those sugars which yield two molecules of the same or different monosaccharides on
hydrolysis are called disaccharides
 In disaccharides, two monosaccharides are covalently bonded together by glycosidic
linkages.
Glycosidic linkage:
 Glycosidic bond is a bond that is formed by
condensation reaction of the hydroxyl group at
anomeric C of one monosaccharide with the
hydroxyl group of another monosaccharide or
another molecule.
 Types:
 O-glycosidic linkages
• In these, the carbohydrate residue is bonded
with another carbohydrate or non carbohydrate
residue through oxygen atom.
• All sugar-sugar glycosidic bonds are O-type
linkages

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 N-glycosidic linkages
• In these, the carbohydrate residue is bonded with another carbohydrates or non
carbohydrate residue through N- atom.
• In nucleotides, the purine and pyrimidine bases are linked through N-glycosidic linkages
with ribose.
• Other Types:
 α-glycosidic linkages
 β-glycosidic linkages

Naming glycosidic bonds

A glycosidic linkage is named by considering the:
 numbers associated with the carbon atoms joined together by the linkage.
 Configuration of the anomeric hydroxyl group of the sugar involved in the bond.
 If this anomeric hydroxyl group is in the α configuration, the linkage is an α-bond.
 If it is in the β configuration, the linkage is a β-bond.

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 When only one anomeric carbon is involved in glycosidic bond formation, reducing
disaccharides are formed. If both anomeric carbon atoms of monosaccharides are
involved in glycosidic bond formation, it results in the formation of a non-reducing
disaccharides such as sucrose.
 In the case of reducing disaccharides, one end of the molecule having free anomeric
carbon is called reducing end and the other end, where the anomeric carbon is involved
in glycosidic bond, is called as non-reducing end.
Homodisaccharides vs Heterodisaccharides
Homodisaccharides:
In these both the monosaccharide units are the same.
Example: Maltose, Isomaltose and Cellobiose
Heterodisaccharides:
In these the monosaccharide units are different.
Example – Sucrose and lactose.
 Three most common disaccharides of biological importance are:
 Maltose, Lactose and Sucrose.

Maltose:
 It is also called Malt sugar
 Maltose consists of 2 α-D-glucose units linked
by α-(1→4) glycosidic linkage.

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 It is found naturally in germinating seeds and barley and produced commercially by

hydrolysis of starch.
 In-vivo formed during the digestion of starch to glucose by amylase.
 Maltose, when hydrolyzed forms two molecules of D-glucose.
 It possess free anomeric C, which means maltose is a reducing sugar.
 It displays mutarotation and forms osazones
 It is Dextrorotatory (+130.5°)
 Maltose is 32 % as sweet as sucrose
 It is frequently found in baby foods b/c its easy to
digest.
 Isomaltose consists of 2 units of α-D-glucose units
linked by α-(1→6) glycosidic linkage

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Sucrose
 It is commonly known as Table sugar, Cane sugar, Beet sugar.
 It is formed by linking α-D-glucose (Pyranose) with β-D-fructose (Furanose form) to give a
α1-β2-glycosidic linkage.
 Sucrose is formed only in plants. No animals are known to produce sucrose.
 It is hydrolyzed by the enzyme Invertase /Sucrase into glucose and fructose.
 Sucrose is not a reducing sugar, does not reduce
Benedict’s reagent, and it will not form osazone.
This is because the linkage involves first carbon of
glucose and second carbon of fructose, and free
reducing groups are not available.
 Sucrose is dextrorotatory (+62.5°)
 It shows none of the typical reactions of carbonyl
compounds
 It does not exhibit mutarotation

Invert sugars and ‘inversion’:

Sucrose, as such is dextrorotatory (+66.5°). But, when hydrolyzed, sucrose becomes
levorotatory (–28.2°). The process of change in optical rotation from dextrorotatory (+) to
levorotatory (–) is referred to as inversion.
The hydrolyzed mixture of sucrose, containing glucose and fructose, is known as invert
sugar. Invert sugar is sweeter than sucrose.
Honey is largely “Invert sugar” and the presence of fructose accounts for the greater
sweetness of honey. Invert sugar has specific rotation of -28.2°

Polysaccharides (glycans)
Polysaccharides consist of more than 10 monosaccharide units and /or their derivatives.
 Classification According to structure:
1‐ Homo polysaccharides (Homo glycans):
 contain only one type of monosaccharide units. For example; starch, glycogen

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dextrin, cellulose and chitin

2‐ Hetero polysaccharides:
 contain more than one type of monosaccharides.
E.g. Glycosaminoglycan, glycoprotein, gums.

 Classification According to function:

Storage polysaccharides:
They are those polysaccharides which serve as reserve food. At the time of need,
storage polysaccharides are hydrolysed. Sugars thus released become available to the
living cells for production of energy.
 contain only α-glucose units. Three important ones are starch, glycogen, and
amylopectin.
Structural polysaccharides
Structural polysaccharides are polysaccharides that take part in forming the structural
frame work of the cell walls in plants and skeleton of animals.
 contain only β-glucose units. Two important ones are cellulose and chitin.

Homopolysaccharides:
1. Starch
Starch is a polymer composed of repeating glucose units
joined in α-glycosidic linkages and is the main carbohydrate
found in the seeds and roots of plants. Corn, rice, wheat, and
potatoes are common foods that contain a great deal of starch.
Starch is not a pure compound. It is a mixture of two
polysaccharide units, amylose and amylopectin, which can be
separated from one another.
Amylose
 about 20% of starch is in amylose form, with
200–1,000 glucose units & has an unbranched
skeleton of glucose molecules with α 1-4-
glycoside bonds.
 Because of this linkage, an amylose chain adopts
a helical arrangement, giving it a very different
three-dimensional shape from the linear chains of
cellulose.
 It has 6 glucose units per turn

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Amylopectin
 comprises about 80 % of starch molecules with several
thousand glucose units
 It has a backbone of glucose units joined in α-1-4-
glycosidic bonds, but it also contains considerable
branching along the chain with α-1-6-glycosidic linkages.
 Like amylose, the glucose chains in amylopectin also has
a helical structure. However, the helical structure of
amylopectin is disrupted by the branching of the chain,
which repeat about every 20 to 30 (1-4) linkages.

Properties of Starch
Action of amylases on starch:
Both type of starch molecules can be digested by humans using the enzyme amylase.
Types of amylases:
Two broad classes of amylases exist as:
– α-amylase is present in saliva and pancreatic juice
– β-amylase is present in sprouted grains and malts (plant sources).
 Both of them hydrolyze only α-1,4 glycosidic linkage and can neither hydrolyze α-1,6
linkages nor β glycosidic linkages.
 α-amylase produces a random cleavage of glycosidic bonds well inside the starch
molecule yielding a mixture of maltose and some fragments larger than maltose (starch
dextrins)
 β-amylase splits off maltose moieties liberating successive maltose units commencing at
the non-reducing end of the starch molecule.

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Action of acids on starch (Hydrolysis): Course of Hydrolysis Reaction with Iodine

 It yield succession of polysaccharides of Starch Blue
gradually decreasing molecular size with the end ↓
product glucose. Both 1-4 and 1-6 linkages are Soluble starch Blue
cleaved by acids.1 ↓
Solubility in water: Amylodextrin Purple
↓
 When starch granules are heated in water,
Erythrodextrin Red
swelling occurs to several hundred times of their
↓
original volume, viscosity increases and starch
Achroodextrin Colorless
“gels” or “pastes” are formed.
↓
Reaction with I2: Maltose Colorless
Starch solutions react with Iodine to give a blue ↓
color. This is chiefly due to amylose, which forms Glucose Colorless
a deep-blue complex, which dissociates on heating. Amylopectin
solutions are colored blue-violet or purple.
Ester Formation:
Starches are capable of forming esters with either organic or inorganic
acids.

 Starch is a non reducing polysaccharide,

 Don’t form osazone
DEXTRINS:
 They are the partial hydrolytic products of starch by α-amylase, β-amylase and acids.
 It is very complex mixture of molecules of different sizes and structures.
 Dextrins formed from amyloses have unbranched chains (possess α-1-4 linkages only) and
while those formed from amylopectin are branched (possess α-1-6 linkages)
 All dextrins have free sugar group & accordingly reduce alkaline copper sulphate solution.
 It is found in the leaves of all starch producing plants representing intermediates either in the
synthesis of starch from glucose or in the breakdown of starch.
 Dextrin has a sweet taste and has typically less than 100 D-glucose units and even as few as 6
D-glucose units per molecule.
 DEXTRANS
 These are highly branched polymers of glucose units with α 1-6, 1-4 and 1-3 linkages.
 It is synthesized by the action of Leuconostoc mesenteroides, a nonpathogenic gram positive
bacteria in a sucrose medium.

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Medical importance
1. They are used for intravenous infusion as plasma volume expander for treatment of hypo-
volemic shock.
2. Dental plaque is due to dextran synthesized from sucrose by oral bacteria.
CELLULOSE
 Cellulose is a linear polymer of β-D-glucose units joined together by β–(1,4) glycosidic
linkages.
 In cellulose about 15000 units are linked to form long, straight chains strengthened by
cross‐linked hydrogen bonds. This results in a very rigid structure and a different overall
shape from amylose.
 It is insoluble in water.

 Non reducing and gives no color with iodine.

 On partial hydrolysis, cellulose yields β-1,4 disaccharide cellobiose instead of maltose.

Cellulose cannot be digested by

mammals because of the absence of an
enzyme (cellulase) that hydrolyzes the
β linkage. Still, it is an important
source of “bulk” in the diet. So
prevent constipation.

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Glycogen
 It is also called animal starch.
 It is a polymer of α-D-glucose units.
 Glycogen is a highly branched-chain molecule in which
glucose unit, in addition to linear α-(1,4) linkages are
also linked by α-(1,6) at the branched point.
 Glycogen has many more branches & branching occurs
after every 12-18 glucose units
 It contains up to 25000 glucose units per molecule.
 It is used by animals to store glucose, especially in the
liver and muscles.
 Glycogen is water insoluble and has no reducing
property.
 It gives red color with iodine.

Chitin
 It is the structural polysaccharide present in the
exoskeleton of insects and also in mushrooms.
 It consists of N‐acetyl‐D‐glucosamine units
joined by β (1→4)‐glycosidic linkages.
 It is structurally strong and serves as a
protection from water in insects.
 Chitin is used as surgical thread that
biodegrades as a wound heals.
 Chitin is also used to waterproof paper, and in
cosmetics and lotions to retain moisture.

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Inulin
 It is a polysaccharide of FRUCTOSE
(fructosan) found in plants with β
(2,1) linkages.
 Inulin has a molecular weight of about
5,000 and consists of about 30–35
fructose units per molecule.
 It is readily soluble in water.
 Inulin is used to determine the glomerular
filtration rate.

Heteropolysaccharides:
Types:
 Glycosaminoglycans (GAGs)
 Glycoconjugates
 Mucilages
Glycosaminoglycans (GAGs)/Mucopolysaccharides
 They owe the name mucopolysaccharides to their slime-like
consistency (Latin mucus, slime).
 These polysaccharides are highly hydrated, gel-like sticky materials
bearing a distinct negative charge.
 Chemically, glycosaminoglycans are unbranched polysaccharides consisting of repeating
disaccharide units comprising a sugar acid (uronic acid) linked to amino sugar (either N-
acetylglucosamine or N-acetylgalactosamine).

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 The amino sugar also possess sulphate group/s attached to one or more of its -OH groups
 Because of the presence of these charged groups, they attract water molecules and so they
produce viscous solutions.
 They all are found in the extracellular material, not in a free state but rather bound with
proteins. Such GAG and protein conjugates are referred to as proteoglycans (since the
basic properties of these macromolecules are mainly due to the carbohydrate, rather than
the protein, moiety).
Importance:
 The mucopolysaccharides/GAGs are found in mucous secretions.
 The mucopolysaccharides combines with proteins like collagen and elastin and forms
extracellular medium or ground substance of connective tissue
 Mucopolysaccharides/GAGs also function as lubricants and shock absorbers.

Some important mucopolysaccharides or glycosaminoglycans (GAGs) are:

1. HYALURONIC ACID
 A gel like aminoglycan that is found in the tissue space, the synovial fluid of joints, the
vitreous humor of the eyes and around the ova and acts as a binding, lubricating, and
protective agent.
 Hyaluronic acid is unique among the GAGs b/c it doesn't contain any sulfate (non-
sulphated) and is not found covalently attached to proteins. It forms non-covalently linked
complexes with proteoglycans in the ECM.
Structure:
It is a straight-chain polymer
consisting of D-glucuronic acid &
N-acetyl glucosamine. Where, N acetyl glucosamine and glucuronic acid are alternately
linked through β1-4 and β1-3-glycosidic bonds with up to 50000 repeating disaccharide
units per molecule of HA.
Hyaluranidase:
Hyaluronidase is an enzyme produced by many bacteria and present in the stings of bees

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& in snake venom, also found in humans in synovial fluid, spleen, testes, seminal fluids etc.
Biomedical importance
 The invasive power of some pathogenic organisms may be increased because they secrete
Hyaluronidase that tends to destroy the intercellular HA barrier and permits the invading
agent to penetrate the tissues, hence called spreading factor.
 In the testicular secretions, it may dissolve the viscid substances surrounding the ova to
permit penetration of spermatozoa.
 Clinically Hyaluronidase is used to increase the absorption of fluids administered Sc.
2. CHONDROITIN SULFATES (Greek: chondros cartilage)
 It is the most abundant GAG in the body.
 It is present in ground substance of tissues esp. Cartilages, Tendons, Ligaments & Aorta
and occurs combined with proteins.
 In the cartilage, it binds to the collagen to hold its fibers in a tough, strong network.

Structure:
 Chondrotin sulfates consists of repeating disaccharides units composed of D-Glucoronic
acid & N- acetyl Galactosamine-sulfate.
 A chondroitin chain can have over 100 of the disaccharide units, each of which can be
sulfated in variable positions and quantities.

Chondroitin sulphate B, a type of chondroitin sulphate, has weak anticoagulant activity, hence
sometimes it is called as β-Heparin.
Importance:
 Chondroitin is in dietary supplements used as an alternative medicine to treat osteo-
arthritis. It is commonly sold together with glucosamine.

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3. HEPARIN
 It is a naturally occurring anticoagulant present in mast cells of liver, Lungs, Thymus,
Spleen, walls of large arteries, skin and in small quantities in blood.
 When released into the blood it acts as anticoagulant by its antithrombin activity by
inhibiting the conversion of prothrombin to thrombin.
Structure of Heparin
 Repeated disaccharide units of heparin contains;
 Glucuronic acid or Iduronic acid with sulfate on C-2. Mostly iduronic acids is present.
 Sulfated Glucosamine.

4. DERMATAN SULPHATE
 Dermatan sulfate is mostly found in skin, cornea and bones and is structurally related to
chondroitin 4 sulfate.
 It plays a role in corneal transparency maintenance.

Structure
The repeating disaccharide unit of dermatan sulphate consist of Iduronic acid and N-
acetyl galactosamine sulfate.

5. KERATAN SULPHATE (Greek keras, “horn”)

They are present in cornea, cartilage, bone, and a variety of horny structures formed of
dead cells: horn, hair, hoofs, nails, and claws. It is a heterogeneous GAG with a variable
sulfate content.
Structure
The repeating disaccharide units consist of galactose and N-acetyl glucosamine sulfate.

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Glycoconjugates:
These include:
 Proteoglycans
 Glycoproteins and
 Glycolipids
ProteoGlycans:
 Proteoglycans are conjugated proteins in
which “core” proteins are covalently linked
to glycosaminoglycans (GAGs).
 Proteoglycans consist of long linear chains
of glycosaminoglycans attached to a core
protein.
 Any of the GAGs i.e. hyaluronic acid (HA); keratan sulphates, chondroitin sulphates,
heparin and heparan sulphate can take part in its formation.
 The amount of carbohydrates in proteoglycans is much greater as compared to
glycoproteins.

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 Many proteoglycan monomers can associate with one molecule of hyaluronic acid to form
proteoglycan aggregates. The association is not covalent and occurs primarily through
ionic interactions between the core protein and the hyaluronic acid. The association is
stabilized by additional small proteins called link proteins.

Glycoproteins:
 Glycoproteins are proteins to which oligosaccharides are covalently
attached.
 The oligosaccharide chains are attached to proteins by O-glycosidic
& N-glycosidic bonds.
 Glycoproteins are very widely distributed in the cells and perform
variety of functions. These include their role as:
 Enzymesa, hormones1, transport proteins3, structural2 proteins
and receptors.
 Oligosaccharide present on the surface of erythrocytes are
responsible for the classification of blood groups. They determine
blood group and hence they are called as blood group substances.
 Cell-cell recognition depends on oligosaccharide chains of
glycoproteins.
 The carbohydrates found in glycoproteins include mannose,
galactose, N-acetyl glucosamine, N-acetyl galactosamine, xylose, L-
fucose and N-acetyl neuraminic acid (NANA).

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Glycolipids:
Certain oligosachharides can bind covalently with lipids that form the outer surface of the
plasma membrane to form glycolipids. An example is the ganglioside which bind to a
complex oligosaccharide containing sialic acid and other monosachharides.
Functions:
 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.
 Also has role in determining blood group types (A, B,
AB, O).

Mucilages:
These are complex colloidal materials present in plants and possess the property of forming
gels or have adhesive properties. These include;
 agar
 vegetable gums and
 pectins
Agar:
It is a vegetable mucilage obtained from sea weeds. It is a complex polymer of galactose
sulfate and glucose.
Agar is non digestible and if ingested stimulates intestinal peristalsis. For this reason, it is
used as a laxative.
It is also used in making media to grow bacteria.
Vegetable gums:
These are carbohydrate materials containing hexoses or pentoses or both in glycosidic
union and a carbohydrate acid (D-glucuronic acid).

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 Gum Arabic upon hydrolysis, yields galactose, arabinose, rhamnose and glucuronic acid.
 It is used in the preparation of pharmaceuticals, in confectioneries and as adhesive.
Pectins:
 Pectin occurs widespread in nature especially in the pulp of citrus fruits, apples, beets
and carrots.
 It is non digestible and is useful as dietary fiber.
 On hydrolysis pectins yield galacto-uronic acid, arabinose, galactose, acetic acid and
methyl alcohol (10-12%).
Biological and pharmaceutical importance of carbohydrates
1. Carbohydrates are the most abundant dietary source of energy (4 Cal/g) for all
organisms.
2. They also serve as the storage form of energy (glycogen) to meet the immediate energy
demands of the body.
3. Carbohydrates are precursors for many organic compounds (fats, amino acids).
4. They are structural components of many organisms. These include cellulose in plant
cell walls, exoskeleton of insects.

5. Carbohydrates (as glycoproteins and glycolipids) participate in the structure of cell

membrane and cellular functions such as cell growth, adhesion and fertilization.
6. Act as structural basis for DNA and RNA (Ribose/Deoxyribose).
7. Act as structural basis for nucleosides and nucleotides.
8. Important agents like antibodies, blood clotting factors, lactalbumin, pancreatic RNAase,
and certain hormones like FSH, LH, and TSH are glycoproteins in nature.
8. Heparan sulfate molecules in proteoglycans act as receptors on cell membranes.
9. Glycolipids and Glycoproteins on erythrocyte surfaces gives rise to ABO blood group
system antigens.
10. Heparin, an endogenously produced anticoagulant, is basically carbohydrate
(Heteropolysaccharide) in nature.
11. Inherited deficiency of certain enzymes in metabolic pathways of different
carbohydrates can cause diseases, e.g. galactosemia, glycogen storage diseases (GSDs),
lysosomal storage disease, lactose intolerance, etc.
12. Imbalance of glucose metabolism results in diabetes mellitus.

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13. Lactose is used as diluent in tablet and capsule manufacture.

14. Gums (heteropolysaccharides) and cellulose derivatives are used as viscosity builders in
Pharmaceutical liquid preparations. Eg Acacia, CMC.
15. Synthetic cellulose derivatives are used as tablet coating agents. Cellulose acetate
phthalate, Ethyl cellulose
16. Sorbitol is used as sweetening agent and as co-solvent.
17. Mannitol is used as an excipient in chewable tablets b/c of its sweetness.
18. Liquid glucose is used as a base in oral solutions and syrups.
19. Sucrose is used as sweetening agent in the preparation of liquid oral dosage forms.
20. Dextrose is used in the preparation of sterile IV fluids.
21. Inulin is used for assessment of kidney function.

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