PHARMACEUTICAL CHEMISTRY-IIA (BIOCHEMISTRY) [Theory]

CARBOHYDRATES

Carbohydrates are the polyhydroxy aldehyde or ketone compounds. Carbohydrates are also
called “saccharides” and this word is derived from the Greek word “saccharo” which means
“sugar”. Another definition of carbohydrate is that they are polyhydroxylated compounds with
at least 3 Carbon atoms with potentially active carbonyl groups which may be either aldehyde
or ketone. Carbohydrates also include those substances that yield such compounds upon
hydrolysis. Some carbohydrates also contain N, P and S.

The name “carbohydrate” is derived from the fact that the first compounds of this group studied
had an empirical formula Cx(H2O)y (hydrates of carbon). Now it is known that many
carbohydrates do not fit into this formula e.g. deoxyribose which is C5H10O4. However, when
carbohydrates are heated then carbon and water are obtained.

Carbohydrates are the most abundant biomolecules on the earth. They form only 2% of human
body mass. They are the source of about 80% of human caloric intake. In plants, glucose is
synthesized from carbon dioxide and water by photosynthesis and stored as starch or used to
synthesize the cellulose of the plant cell walls. Animals can synthesize carbohydrates from
amino acids, but in most animal carbohydrates are derived ultimately from plant sources.
Mostly, dietary carbohydrate is absorbed into the bloodstream as glucose while other sugars that
are absorbed are converted to glucose in the liver.

Glucose is most important among all carbohydrates. Glucose is the precursor for synthesis of all
the other carbohydrates in the body including glycogen for storage; ribose and deoxyribose for
nucleic acids; galactose for lactose of milk, glycolipids and glycoproteins of the body. Diseases
associated with carbohydrate metabolism include diabetes mellitus, galactosemia, glycogen
storage diseases, and lactose intolerance.

Blood glucose is serving as direct food for the brain. Mammary glands take the glucose from
the blood and convert it into the galactose. Mammary glands combine this galactose with
glucose to form the lactose. Glucose is oxidized preferably by all tissues of the body to provide
energy. More than half of the oral energy of the body is provided by glucose. Excess of glucose
is readily converted into fats and stored in the fat depots.

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Classification
There is no single satisfactory classification of carbohydrates. Commonly used classification is
given below
1. Monosaccharides:

These are simple sugars which cannot be further hydrolyzed and have the empirical formula
(CH2O)n where n = 3 or greater. They may be classified as trioses, tetroses, pentoses, hexoses,
or heptoses, depending upon the number of carbon atoms. They are either aldoses (contain
aldehyde group) or ketoses (contain ketone group).

No. of Generic Name Examples

Carbons
Aldoses Ketoses
3 Trioses Glyceraldehyde Dihydroxyacetone
4 Tetroses Erythrose Erythrulose
5 Pentoses Ribose Ribulose
6 Hexoses Glucose Fructose
7 Heptoses Glucoheptose Seduheptulose

In nomenclature of carbohydrates, the type of carbonyl group (aldehyde or ketone) and the
generic name are combined to give the name to the monosaccharides. For example, glucose is
an aldose as well as a hexose; it is therefore, an aldohexose while fructose is a ketohexose.
Monosaccharides are white crystalline solids, freely soluble in water and most have a sweet
taste.

2. Disaccharides:

Disaccharides are the condensation product of two monosaccharide units linked together by a
covalent bond e.g., maltose (2 glucose molecules), sucrose (1 glucose + 1 fructose), lactose (1
glucose + 1 galactose). Monosaccharides are joined together by glycosidic linkage.

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Some important monosaccharides

3. Oligosaccharides:

The word oligosaccharide is derived from the Greek word “oligo” which means “few”. These are
the condensation products of 3 to 10 monosaccharide units. Sometimes disaccharides are also
included in this group. The monosaccharides are joined together through glycosidic linkages.
Examples include maltotriose (3 glucose molecules), α-dextrin (8 glucose molecules).

4. Polysaccharides:

Polysaccharides are the condensation product of more than ten monosaccharides units. They may
be in a straight chain or in branches (e.g. cellulose, glycogen, starch, and dextrin). There are two
types of polysaccharides.

a. Homopolysaccharides:
These are polysaccharides, formed from a combination of only one type of monosaccharide
units. They are also called homoglycans. Examples include starch, glycogen, cellulose and
dextrins. All of which yield glucose on hydrolysis.

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b. Heteropolysaccharides:
These are the polysaccharides, formed from a combination of two or more types of
monosaccharides units. They are also called heteroglycans. These are divided into the following
three groups.
I. Mucopolysaccharides:
They are also called glucos-amino-glycans(GAGs). These polysaccharides, in addition to
containing carbohydrate groups, also contain acid groups e.g. hyaluronic acid, heparin, blood
groups polysaccharides, serum mucoids.
II. Mucilages:
These polysaccharides occur in plants e.g. agar, vegetable gums and pectin
III. Hemicellulose:
These polysaccharides occur in plants e.g. hemicellulose.
IV. Glycoconjugates:
These include glycolipids, glycoproteins, proteoglycans.

5. Derived Carbohydrates
These carbohydrates are derived from carbohydrates by various chemical reactions. These may
be
A. Oxidation products:
These sugar acids are derived from glucose on its oxidation e.g., gluconic acid, glucuronic acid,
glucaric acid, Ascorbic acid (vitamin C).
B. Reduction products:
These are the reduced products of carbohydrates. These are polyhydroxy alcohols e.g., glycerol
(derived from glyceraldehydes), ribitol (derived from ribose).
C. Amino sugars:
Sugars containing an –NH2 group in their structure are called amino sugars. These have –NH2
group at carbon No.2 e.g., glucosamine, galactosamine, and mannosamine.
D. Deoxy sugars:
Deoxy sugars represent sugars in which the oxygen of a –OH gr. has been removed, leaving the
hydrogen. These have less number of oxygen atoms than other sugars e.g., deoxyribose (present
in DNA and is one oxygen atom lesser than ribose).

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Isomerism in carbohydrates
Stereoisomerism
The word isomer is derived from the Greek words “isos” meaning "equal" and “meros” meaning
"part". Isomers are compounds with the same molecular formula but different structural formula
e.g. glucose, fructose, mannose and galactose has same molecular formulas i.e. C6H12O6 but
different structural formulas. The isomerism which is based on the difference in the arrangement
of the atoms in the space is called stereoisomerism.

Epimers

The stereoisomers that differ in configuration around one specific carbon atom (optically active
carbon atom) other than carbonyl carbon are called epimers e.g. glucose and galactose differ
from each other only in the position of –OH at Carbon No. 4. Similarly, glucose and mannose
are different from each other only in the position of –OH at Carbon No 2. So, both are epimers
of each other.

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Anomers
The stereoisomers that differ from each other in configuration around carbonyl carbon only are
called anomers. When a monosaccharides cyclizes, its anomeric carbon also becomes
asymmetric with two possible forms of their configurations i.e. α and β forms. Such
stereoisomers that differ in configuration at the anomeric carbon atom i.e. carbon no 1 in aldoses
(e.g. glucopyranose) or carbon no 2 in ketoses (e.g. fructofuranose) are called anomers. e.g.
α-D-glucopyranose and β-D-Glucopyranose. Both anomers have different physical and chemical
properties. Both α and β anomers are interconvertible in aqueous solution. The process of
inter-conversion of as α and β anomers is called mutarotation. Phenomenon of mutarotation
increases with increase in the number of OH groups. Other examples are α-D-fructofuranose and
β-D-fructofuranose.

C1 after cyclisation becomes asymmetric—it is called “anomeric” carbon and α-D-glucose and
β-D-glucose are “anomers”

Enantiomers

Enantiomers are the compounds that are the mirror images of each other with reference to
asymmetric carbon atoms in their molecules are called enantiomers. Both can rotate the plane
polarized light and the degree of optical rotation in each compound is exactly the same but

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opposite in directions e.g. L- glucose and D- glucose are the enantiomers of each other. Every
sugar in L and D form is a mirror image of each other except dihydroxyacetone.

The name D and L depends upon the position of the –OH group on the last asymmetric carbon
atom of the monosaccharides. The enantiomers possess similar physicochemical properties. It
is even difficult to separate them. If they need to separate out they should convert to the
diastereomers.

Diastereoisomers

Diastereoisomers (that have one or more chiral centers) are the compounds that are not mirror
images of each other and different only with respect to configuration around the asymmetric
carbon atoms and rotate the plane-polarized lights in same direction but with different speed
are called diastereoisomers. The phenomenon is called diastereoisomers. e.g. α-D-glucose and
β-D-glucose are the diastereoisomers. Anomers are diastereomers.

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Optical activity of carbohydrates

Carbohydrates solutions have the property to rotate the plane-polarized light to the right or left.
This property is called optical activity of the carbohydrates. This property is due to the presence
of the asymmetric carbon atoms in their structures. The sugars rotating the plane- polarized
light to left are termed as levorotatory while those which rotate the plane-polarized light to
right are termed as dextrorotatory. The levorotation is represented by l or (–) sign while the
dextrorotation is represented by d or (+) sign. There is no relation of “D and L” and “(–) and
(+)” signs. A sugar may be a D sugar and levorotatory e.g. D-fructose. In the solution, glucose
is dextrorotatory and sometimes glucose is called dextrose. Trend of use of “l” and “d” has
become deleted. Nowadays (–) and (+) signs are used for optical activity.

There are some conditions in which the plane-polarized light will neither be rotated to right nor
to left. Those are

1. If the compound does not possess an asymmetric carbon atom in its structure.

2. If equal quantities of the dextrorotatory and levorotatory isomers are present. Such
mixtures are termed as racemic mixtures.
Resolution: The separation of optically active isomers from a racemic mixture is called
resolution.

3. If a compound is a meso compound. Such compounds contain asymmetric carbon atoms

but do not rotate the light. This is due to the fact that such compounds have two halves,
one rotating the light to the right and the other to the left. This phenomenon is called
internal compensation e.g. meso tartaric acid.

Asymmetric (Chiral) Carbon atom and D- and L-Monosaccharides

Asymmetric carbon: A carbon atom to which four different atoms or groups of atoms are
attached is said to be asymmetric.

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All the monosaccharides except dihydroxyacetone contain one or more asymmetric (chiral)
carbon atoms. That is why they are optically active. The simplest aldose, glyceraldehyde,
contains one chiral center (the middle carbon atom) and therefore has two different optical
isomers, or enantiomers. One of these two forms is designated the D isomer and the other is L
isomer depending on the sides on which H and OH are attached.

❖ In structure No. (1), -OH group attached to the asymmetric carbon atom, i.e. carbon No.2
is on the right and this structure is called D-glycerose; in structure No.2, -OH group
attached to carbon No.2 is on the left and this structure is called L-glycerose.
❖ All monosaccharides having more than three carbon atoms have two or more asymmetric
carbon atoms. In these cases, the designation D or L is given by seeing the configuration
of H and OH around the penultimate carbon atom, ie, the asymmetric carbon atom
situated farthest from the potential aldehyde or ketone, ie. carbonyl group.
❖ If the penultimate carbon atom has the same configuration of H and OH around it as the
asymmetric carbon atom of D-glycerose, the monosaccharide is of D type. On the other
hand, a monosaccharide whose penultimate carbon atom has the same configuration as
the asymmetric carbon atom of L-glycerose is called L-monosaccharide.
❖ Because all monosaccharides are compared with D- and L-glycerose for this purpose,
glycerose is called the reference sugar.

Structural representation of sugars

1. Fischer projection: straight chain representation

2. Haworth projection: simple ring
representation
3. Conformational representation: chair and boat
configurations

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A: Fischer Projection Formulas

D-glucose is an aldohexose. The open chain structure of glucose was first suggested by Fischer (Fischer’s
projection formula) in 1891.
❖ In the Fischer projection formula of glucose, the carbon chain is written vertically with
carbon No. 1 at the top and the –H and –OH are written to the left or right.
❖ Carbon No.2 in both the cases is an asymmetric carbon atom (the carbon atom to which
four different atoms or groups are attached). All carbohydrates having more than 3
carbon atoms have two or more asymmetric carbon atoms.
❖ In such compounds, the most distant asymmetric carbon atoms from the carbonyl group
having the same configuration as that of the asymmetric carbon atom of the
D-glyceraldehyde are called D sugars.
❖ On the other hand, all sugars whose farthest asymmetric carbon atoms from the carbonyl
group have the same configuration as that of the asymmetric carbon atom of the
L-glyceraldehyde are called L sugars.
❖ The D and L forms of a sugar are stereoisomers and mirror images of each other and are
termed as enantiomers. All sugars are compared with D- and L-glyceraldehydes and thus
glyceraldehyde is called the reference sugar.
❖ n D sugars are most abundantly available in nature than the L sugars. L isomers of
monosaccharide are also found in the human body e.g. L-xylulose.

Open chained form of D-glucose (Fischer projection)

B: Haworth Projection Formulas

❖ Monosaccharides normally adopt a ring configuration.
❖ When a D-glucose adopts a six membered ring structure, a hemiacetal bond is formed
between the aldehydic carbonyl group of carbon No 1 and hydroxyl group on carbon No

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5 (aldehydes react readily with Alcohols to form hemiacetal). Cyclization of glucose

thus results in the formation of ring structure, which is analogous to the structure of
pyran, a six membered ring containing five carbon and one oxygen atom. Sugars with a
six membered pyran ring are designated as pyranose. Cyclization of D-glucose thus
yields a cyclic hemiacetal, i.e. glucopyranose.
❖ Fructose, on the other hand, forms a five membered furan ring with four carbon and one
oxygen atom. The linear form of D-fructose thus cyclize between carbonyl carbon of
second carbon (C2) and alcoholic group of the fifth carbon (C5), and yield the
hemiketal, i.e. fructofuranose (ketones can react with alcohols to form hemiketals). The
smallest monosaccharide having the fructofuranose structure is ribose.
❖ The ring structure of sugar was proposed by Haworth and is also called Haworth
structures.

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C: Conformational representation (Chair and boat forms D-glucose):

Haworth projections are convenient for display of monosaccharide structures. Sometimes

glucose can also be represented in the form of a chair and boat. Chair form of glucose is more stable.

Van’t Hoff’s rule of ‘n’

The number of possible isomers of any given compound depends upon the number of
asymmetric carbon atoms the molecule possesses. According to Van’t Hoff’s rule of ‘n’ 2n
equals the possible isomers of that compound, where n = represents the number of asymmetric
carbon atoms in a compound.
All aldohexose have 4 asymmetric carbon atoms and according to Van't Hoff’s law (the number
of possible optical isomers are expected to have 2(4) = 16 possible isomers (allose, altrose,
glucose, mannose, gulose, idose, galactose, talose in D and L forms). However, in aqueous

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solutions many monosaccharides including glucose display the property of mutarotation. Due to
this property these sugars behave as if they have an extra asymmetric carbon atom. Carbonyl
carbon is responsible for this phenomenon. Due to this property, the number of possible isomers
for aldohexose becomes 2(5)= 32 (16 isomers occurring in α and β forms). α and β forms
usually occur in ring form and do not show an aldehyde group.

Chemical Properties of Carbohydrates with special reference to Glucose

1. Formation of Glycosides

Glycosides are molecules in which a sugar (carbohydrate) is bound to a non-sugar moiety

(non-carbohydrate). In glycoside molecules, the sugar part is known as glycone and the
non-sugar part is known as aglycone part. In the formation of glycosides, hydroxyl group (OH)
of anomeric carbon of the sugar part reacts with hydroxyl group of non sugars part through
glycosidic linkage.

The aglycone may be attached through –OH or –NH2 group forming O– or N– glycosides
respectively. O-glycosides are more common in nature. Oligosaccharides and polysaccharides
contain O-glycosidic bonds. N-glycosidic bonds occur in nucleotides and in glycoproteins.

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Right side: Methyl Glucose (methyl-⍺-D-gluco-pyranose)

2. Formation of Osazone

Osazone is a yellowish, crystalline compound, produced as a result of heating sugars

solutions with phenylhydrazine. Osazones are formed by those sugars which contain a free
aldehyde or ketone group. For example one molecule of glucose reacts with three molecules
of phenyl hydrazine to form glucosazone. On the other hand sucrose doesn’t possess free
aldehyde or ketone group and thus cannot form Osazone until it is first hydrolyzed to
monosaccharides.

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3. Formation of sugar alcohols

The aldehyde or ketone group of both aldoses and ketoses can be reduced to form the corresponding
polyhydroxy alcohols. Glucose reduces to form sorbitol and fructose reduces to form sorbitol and
mannitol.

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Monosaccharides Corresponding Alcohol

Glucose Sorbitol

Mannose Mannitol

Galactose Dulcitol

Fructose Sorbitol and mannitol

Ribose Ribitol

Glyceraldehyde Glycerol

Dihydroxyacetone Glycerol

Mannitol is frequently used in the patients of cerebral edema because it acts as osmotic diuretic
and decreases the water content of the body and thus decreases brain swelling. Sorbitol is
getting deposited in the lens of the eye especially in the patients of diabetes mellitus and
contributes to the early cataract formation.

4. Formation of sugar acid

Carbohydrates form the sugar acid on their oxidation. When glucose (aldoses) is oxidized under
proper conditions, then it yields three types of sugar acids; namely gluconic acid, glucuronic
acid, and glucaric acid.

A. Gluconic acid is formed under mild conditions and due to oxidation at C-1. Gluconic
acid is used in the formation of salts of different drugs e.g. antimalarial drugs.

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B. Glucuronic acid is formed by oxidation at C-6. Glucuronic acid is formed in the body.
It is of great physiological importance because it is used in the body as a detoxifying
agent and inactivates many substances like camphor, benzoic acid, steroid hormones and
bilirubin etc.

C. Glucaric acid is formed via oxidation of glucose at C-1 & C-6.

5. Reducing Properties of sugar in alkaline solutions

Almost all carbohydrates contain a free aldehyde or ketone group except sucrose. That is
oxidized in alkaline pH. So, they are good reducing agents in an alkaline medium. They readily
reduce oxidizing ions such as Ag, Hg, Bi, Cu, and ferricyanide.

This reaction is the basis for Benedict's test and Fehling’s test.

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6. Action of acids on carbohydrates

Monosaccharides are resistant to the action of hot diluted acids. Strong acids dehydrate all
carbohydrates leading to the formation of furfural rings. These products condense with
phenols to form characteristic colored products.

This reaction is the basis of the color test, known as Molisch’s test for sugars.

7. Ester Formation

Hydroxyl groups of sugar can be esterified with phosphates, acetates, propionates and stearates
etc. Sugar phosphates are of great biological significance. Nucleoproteins of cells contain sugar
phosphate in combination with various nitrogen bases.

8. Fermentation

Fermentation is the process of converting a larger complex molecule into simple molecules by
means of enzymes. Some of the hexose sugars are converted to ethanol and CO2 by a group of
enzymes called zymases.

Glucose, fructose and mannose can be readily fermented by common baker yeast. Galactose is
fermented to a negligible amount.

9. Action of bases on carbohydrates (Lobry de Bruyn-Van Ekenstein reaction)

Dilute basic solutions at low temperature can bring about re-arrangement of groups at the
anomeric carbon atoms and its adjacent carbon atom. Glucose, fructose and mannose are
interconvertible in solutions of weak alkalinity such as Ba(OH)2 or Ca(OH)2. These
interconversions are due to the fact that all give the same Enediol Form, which tautomerizes to

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all three sugars. This interconversion of related sugars by the action of dilute alkali is referred
to as the Lobry de Bruyn-Van Ekenstein reaction. Higher concentration of bases can cause
further changes i.e. more carbon atoms show the rearrangement of the groups and even
fragmentation and polymerization occur.

Interconversions of sugars in weak alkalinity-Lobry de Bruyn-Van Ekenstein reaction

10. Amino sugars formation

A hydroxyl group of the monosaccharides can be replaced by an amino group (–NH2) forming
an amino sugar e.g. example D-glucosamine, D-galactosamine, D-fructosamine. In all these
–NH2 group is attached at C-2. These are present in nature. As they are derived by hexoses so
they are also called hexosamine.

Glucosamine is a constituent of hyaluronic acid. Galactosamine is present in chondroitin.

Mannosamine is an important constituent of mucoproteins. Aminosugars also occur in many
antibiotics e.g. erythromycin. In most cases amino sugar is N-acetylated.

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SOME IMPORTANT MONOSACCHARIDES

A. HEXOSES:
Glucose, fructose, galactose and mannose are described below:

1. D-Glucose: (Synonyms: Dextrose (because of dextrorotation), Grape Sugar)

❖ It is widely distributed in nature (fruits, sugar cane, sugar beats, dates).
❖ Human blood plasma contains 70 to 110 mg glucose/dL in the fasting condition.
❖ Because glucose represents almost 100% of monosaccharide in the blood, therefore the
term blood sugar is used for blood glucose.
❖ Principal monosaccharide utilized by the tissues for obtaining energy.
❖ Stored as glycogen in liver and muscles mainly.
❖ Glucose is 74% as sweet as sucrose. It exhibits mutarotation. It is readily fermented by
yeast.

2. D-Fructose: (Synonyms: Fruit sugar, levulose (due to levorotation) )

❖ It occurs in honey and in plant kingdom as such or as combined with glucose in sucrose.
❖ It exhibits mutarotation. When free, it occurs in pyranose form which is levorotatory,
however in sucrose it exists in the furanose form which is dextrorotatory.
❖ Animal tissues also contain it in small amounts. Seminal fluid has appreciable amounts of
fructose.
❖ Fructose is the sweetest of all sugars (173% of sucrose). It is fermented by yeast.

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3. Galactose:
❖ It mainly occurs as a part of the lactose (milk sugar) molecule in which it is combined
with glucose. It also occurs in the seed coats of legumes. It is a constituent of
galactolipids and glycoproteins.
❖ It is an aldohexose, is dextrorotatory and exhibits mutarotation.
❖ It has a 32% sweetness of sucrose. It differs from glucose only in respect to configuration
around carbon No. 4 (epimers).

D-galactose; straight chain (left) and Haworth's formula (right) showing it as

galactopyranose (1-5 ring).

4. D-Mannose:
❖ It is a part of the molecule of the prosthetic polysaccharide of many glycoproteins.
❖ If ingested, it is absorbed and in the body it is converted to glucose.
❖ It shows chemical reactions similar to glucose, it cannot be differentiated from glucose by
configuration around carbon No.2; in other words it is an epimer of glucose in respect to
carbon No. 2.

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B. PENTOSES
Pentoses are monosaccharides containing a chain of five carbon atoms. Ribose is a constituent of
the ribonucleic acid (RNA) of the cell and of many important substances found in cells, such as
ATP, GTP, NAD NADP, FAD and coenzyme A.
Pentoses have the following properties:
1. They may be aldoses or ketones.
2. They possess strong reducing properties
3. They form osazone crystals with phenylhydrazine
4. With acids they are converted to furfurals
5. They are not fermented by yeast
6. Several pentoses have important physiological roles as given below:
● Ribose and ribulose as phosphates are intermediates in the pentose phosphate pathway of
glucose metabolism.
● D-arabinose and D-xylose are found in glycoproteins.

Deoxy-D-ribose

DISACCHARIDES

The disaccharides consist of two monosaccharide units joined covalently by an O-glycosidic

linkage. The most common disaccharides are sucrose maltose and lactose

1. Sucrose: (Synonyms: Saccharose, Table sugar, Cane sugar)

❖ Upon hydrolysis yields 1 molecule of each D-glucose and D-fructose. Because sucrose,
unlike maltose and lactose, contains no free anomeric carbon atom (both potential

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aldehyde and ketone groups on anomeric carbon are blocked from activity), therefore it is
without reducing properties which appear only when it has been hydrolyzed, yielding its
constituent monosaccharides. For the same reason, sucrose does not form osazone
crystals and also does not show the property of mutarotation.

❖ Sucrose is dextrorotatory because it has in its molecule glucose which is dextrorotatory

and fructose which being in furanose form is also dextrorotatory. When sucrose is
hydrolyzed, its fructose is released in its pyranose form which is levorotatory. On
hydrolysis, sucrose becomes levorotatory. This is because out of glucose and fructose
which result from hydrolysis of sucrose in equal amounts, the levorotatory activity of
fructose is more than dextrorotatory activity of glucose. Because in this process the
rotation has been reversed, this process is called inversion and the products of sucrose
hydrolysis are called invert sugar.
❖ Honey is very rich in invert sugar because the honey bee has an enzyme invertase which
converts sucrose into invert sugar. Inversion can be brought about by hydrolysis with
dilute acids or with a specific enzyme called invertase or sucrase.
❖ Invert sugar is 30% more sweet than sucrose.
❖ Sucrose, like other disaccharides, can be utilized in the body only if taken by mouth
because the specific intestinal enzyme, sucrase, hydrolyzes it to glucose and fructose
which are then absorbed. If given by an intravenous injection, it is not metabolized and is
rapidly excreted in urine.

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2. Maltose: (Synonyms: Malt sugar)

❖ It is formed by an O-glycosidic linkage (1→4) between one molecule of ⍺-D-glucose
with another molecule of ⍺-D-glucose with the elimination of one water molecule.

Maltose (α form)
❖ Because of the presence of a free anomeric carbon atom, it is a reducing sugar, forms
osazones which have characteristic appearance ‘Sunflower’ like and shows mutarotation.
❖ It is 32% as sweet as sucrose.
❖ It is formed in vivo by the action of salivary amylase on starch and in vitro by partial
hydrolysis of starch by acids. Further acid hydrolysis of starch or the action of the
enzyme maltase will result in the production of glucose. Maltose is present in various
baby and invalid foods.

Note: Another disaccharide containing two molecules of ⍺-D-glucose is isomaltose, however in

this case the two ⍺-D-glucose molecules have 1-6 linkage.

3. Lactose: (Synonyms: Milk sugar (lac milk))

❖ It is formed as a result of O-glycosidic linkage between one molecule of β-D-galactose
and I molecule of D-glucose through β1→4 linkage.

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❖ In nature it occurs exclusively in milk. The enzyme lactase present in the intestinal
mucosal cells hydrolyzes lactose to its constituent monosaccharides.
❖ It is the least sweet sugar (16% of sucrose).
❖ It is a reducing sugar, it forms osazone crystals (hedgehog shape or powder puff
appearance) and shows mutarotation.

POLYSACCHARIDES
Polysaccharides which are also called glycans are of two types homopolysaccharides and
heteropolysaccharides.

A. Homopolysaccharides

1. Starch:
❖ It is the storage carbohydrate in plants and is the main form in which carbohydrates are
ingested by man formed by the polymerization of a large number of ⍺-D glucose
molecules. It is a polyglucose also called glucosan or glucan.
❖ It contains two types of polysaccharide units, amylose and amylopectin.
❖ In Amylose carbon No. 1 of the first glucose is attached to the carbon No. 4 of the second
through an oxygen bridge with the elimination of a water molecule and so on. Amylose
has 50 to 5,000 glucose units and it constitutes 15 to 20% mass of starch.

A part of the amylose chain. ⍺ -D-glucose residues (50 to 5000 units) are attached to each
other by a 1→4 glycosidic linkages.
❖ Amylopectin is more abundant than amylose and forms 80 to 85% of starch. It is made
up of two types of linkages 1→4 linkages (97%) and 1→6 linkages resulting in the
branching of the molecule. In 1→6 linkage carbon No. 1 is that of a terminal glucose
molecule of the straight chain while carbon No. 6 belongs to a non-terminal glucose

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residue. Each straight chain contains from 24 to 30 glucose units. The amylopectin
molecule is much bigger than amylose as it may have upto 1 million glucose units.

A part of amylopectin molecule showing many ⍺1→4 linkages and one a 1→6 glycosidic linkage at the
branching site.

❖ It gives a purple or blue-violet color with iodine. Because free aldehyde groups are not
found in starch, therefore it does not act as a reducing substance. Due to the same reason
starch does not form osazone crystals.
❖ Action of acids on starch: Acids completely hydrolyze starch to glucose, it passes
through the following stages which give reactions with iodine as indicated.

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❖ Action of enzymes on starch: The enzymes hydrolyzing starch are called amylases
(amylum starch). Both saliva and pancreatic juice have such enzymes called salivary
amylase and pancreatic amylase respectively. They hydrolyze starch into maltose,
maltotriose and ⍺-dextrins.

Enzyme (amylase) hydrolysis ends at maltose with traces of dextrins. For formation of glucose, it
requires the enzyme maltose. But if the hydrolysis is accomplished by acids much of the starch will be
converted into glucose.

2. Dextrins
When starch is partially hydrolysed by the action of acids or enzymes, it is broken down into a
number of products of lower molecular weight known as dextrins. They generally have a sweet
taste.

3. Dextrans
It is a polymer of D-Glucose. It is synthesized by the action of Leuconostoc mesenteroides, a
non-pathogenic gram +ve cocci in a sucrose medium.
Dextrans are used in medicine as plasma substitutes or extenders in the treatment of hypovolemic
shock. Dextrans occur in nature forming an adhesive coat around certain bacteria.

4. Cellulose
❖ Cellulose is a polymer of glucose. It is not hydrolyzed readily by dilute acids, but heating
with fairly high concentrations of acids yields the disaccharide Cellobiose and
D-Glucose. Cellobiose is made up of two molecules of D-Glucose linked together by
β1→4 Glycosidic linkage.
❖ In human beings no cellulose splitting enzyme is secreted by GI mucosa, hence it is not
of any nutritional value. It provides fiber and bulk to the food. This roughage serves to
satisfy the appetite and in addition it stimulates intestinal peristalsis.

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❖ Hemicellulose: It is the general name for a group of high mol. wt. carbohydrates that
resemble cellulose, but are more soluble and more easily decomposed. These are found in
plant cell walls and can be extracted with dilute alkalies and are precipitated by dilute
acids.

On the left is Haworth's formula of B-D-glucose. On right is shown ẞ 1→4 linkage between two
adjacent B-D-glucose residues forming a cellubiose unit.
5. Glycogen
❖ Glycogen is the reserve carbohydrate of the animal, hence it is called animal starch. It
occurs mainly in the liver and the muscle.
❖ Its structure closely resembles that of amylopectin in that it is a polymer of ⍺-D-glucose
units and in its molecule both 1→4 as well as 1→6 linkages are present. However,
glycogen is a much more branched molecule than amylopectin because the chains are
shorter, having 12 to 14 glucose residues. In addition, the glycogen molecule is very
compact.
❖ Glycogen gives a red color with iodine.
6. Chitin:
❖ It consists of N-acetyl-D-glucosamine units joined by β1→4 glycosidic linkages.
❖ It is a component of the exoskeleton of crustaces and insects and is also present in
mushrooms.

B. Heteropolysaccharides
These polysaccharides contain in their molecules certain groups in addition to carbohydrates.
These are
1) Glycosaminoglycans (GAGs)
2) Glycoconjugates
3) Mucilages

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1. GlycosAminoGlycans (GAGs):
❖ Glycosaminoglycans (GAG) are usually composed of amino sugar and uronic acid units
as the principal components, though some are chiefly made up of amino sugar and
monosaccharide units without the presence of uronic acid.
❖ Carbohydrate content varies. When carbohydrate content is > 4 percent, they are called
Mucoproteins and when < 4 percent they are called Glycoproteins.
❖ Some important GAGs include
● Hyaluronic acid: It has been isolated from several tissues and even bacteria. It
helps in the lubrication of the joints of animals, it is also found in the vitreous
humor of the eye to which it gives a glassy appearance. In tissues it forms an
important part of the extracellular matrix of skin and connective tissue's cement
substance that resists penetration by bacteria.
● Chondroitin sulfates: These are the most abundant GAGs in the body and are
found in the ground substance of tissues especially tendons, ligaments and walls
of the aorta and occur as combined cartilage protein.
● Heparin: It is a naturally occurring anticoagulant found intracellularly in mast
cells lining the arterial vasculature of liver, spleen, lungs, thymus.

2. Glycoconjugates
This class of carbohydrates includes proteoglycans, glycoproteins and glycolipids:
● Proteoglycans: Proteoglycans are conjugated proteins. Proteins called “core” proteins
are covalently linked to glycosaminoglycans (GAGs).
● Glycoproteins: Any protein that is attached to a carbohydrate group or chain is referred
to as a glycoprotein.
● Glycolipids: Certain oligosaccharides can bind covalently with lipids that form the outer
surface of the plasma membrane to form glycolipids.

3. MUCILAGES
These are complex colloidal materials present in plants and possess the property of forming gels
or have adhesive properties. These include

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● Agar: It is a vegetable mucilage obtained from sea weeds. Agar forms a sol in hot water
which sets (i.e. gels) on cooling. 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 because agar gel is not liquefied by bacteria.
● Vegetable gums: These are carbohydrate materials containing hexoses or pentoses or
both in glycosidic union and a carbohydrate acid group. It is used in the preparation of
pharmaceuticals, in confections and as an adhesive.
● Pectins: The term pectins is used to represent substances which at a certain pH value and
in the presence of sugar cause the formation of jellies. Pectins occur widespread in nature
but are found especially in the pulp of citrus fruits, apples, beets and carrots.

Importance of Carbohydrates

1. Carbohydrates are widely distributed in plants and animals and have important
structural and metabolic roles.
2. Most dietary carbohydrate is absorbed into the bloodstream as glucose, and other sugars
are converted into glucose in the liver. Glucose is the major metabolic fuel of mammals
and universal fuel of the fetus.
3. It is the precursor for synthesis of all the other carbohydrates in the body, including
glycogen for storage; ribose and deoxyribose in nucleic acids; and galactose in lactose
of milk. Glucose is also present in glycolipids and in glycoproteins.
4. Various diseases associated with carbohydrate metabolism include diabetes mellitus,
galactosemia, glycogen storage diseases, and lactose intolerance.
5. Oligosaccharides are present in combination with proteins at all cell membranes.
6. These are also present in secreted proteins such as antibodies and blood clotting factors.
7. Complexes of carbohydrates with proteins act as receptors on cell membranes which are
thus involved in molecular recognition.
8. Carbohydrate derivatives (heparin) are used in the development of the nervous system.
9. Ribose is an integral part of high energy phosphate compounds i.e., ATP, GTP
(guanosine triphosphate), UTP (uridine triphosphate) and CTP (cytidine triphosphate)
and secondary messengers such as cAMP (cyclic adenosine monophosphate) and cGMP
((cyclic guanosine monophosphate).

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Reference Books:

Essentials of Medical biochemistry by Mushtaq Ahmed

Chatterjea, M. N., and Rana Shinde. Textbook of medical biochemistry, 2011.
Murray, K., et al. "Harper's illustrated biochemistry. 28." Citeseer, New York, United States
(2009)

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