CARBOHYDRATES:

Introduction and
structure

Tanzeela Ashraf
M.Phil (Pharmaceutical Chemistry) P.U
Pharm-D P.U
CONTENTS
 Introduction

 Basic Classification of carbohydrates

 Cyclic Structure

 Stereo Isomerism

 Optical Isomerism

 Monosaccharides of Biological Importance

INTRODUCTION
 introduction
 Carbohydrates are multiple aldehyde or ketone compound with multiple hydroxyl
groups.

 They are the most abundant biomolecules on earth; however in human being
they constitute almost about 1% of body weight.

 Carbohydrates Contain the Elements:

 Carbon
 Hydrogen
 Oxygen

• The general formula for a carbohydrate is (CH2O)n

 Carbohydrates is also called as the hydrates of carbon because they have the
same ratio of carbon and hydrogen as that present in water.
 DEFINITION
 A carbohydrates is defined as a polyhydroxy aldehyde or polyhydroxy
ketone or compound that yield such derivatives upon hydrolysis.
BASIC CLASSIFICATION
 Classification

Carbohydrates

Monosaccharides Disaccharides Oligosaccharides Polysaccharides

 monosaccharides
 Monosaccharides are also called as the simpler sugar because they cannot be
further hydrolyzed into simpler sugar.

 These simpler sugar also contains a single polyhydroxy aldehyde or polyhydroxy

ketone unit.

 Naturally occurring monosaccharides have three to seven carbon atoms;

 General formula : Cn(H2O)n

 Monosaccharides are further subdivided as:

 1. Depending upon whether aldehyde (– CHO) or ketone (– CO) groups

 Monosaccharides with an aldehyde carbonyl group are called as aldoses.

 Monosaccharides with a ketonic carbonyl group are called as ketoses.

 Monosaccharides (continue..)

Exampl
e
Example of aldo and keto sugar
Monosaccharides (continue..)
 2. Depending upon the number of carbon atom:
 Monosaccharides are also classified on the basis of no of carbon
atoms
Monosaccharides (continue..)
Example
 Monosaccharides

 Some of the major properties of monosaccharides

are following:
 These are white crystalline solids

 They have a sweet taste.

 They are very soluble in water.

 Disaccharides
 Those sugar which yields two or more same or different types of
monosaccharides upon hydrolysis.

 General formula : Cn(H2O)n-1

 Examples

 Maltose yields 2 molecules of glucose on hydrolysis.

 Lactose yields one molecule of glucose and one molecule of galactose on

hydrolysis.

 Sucrose yields one molecule of glucose and one molecule of fructose on hydrolysis.

 Lactulose a ketodisaccharide.
 Oligosaccharides

 Oligosaccharides :

Those sugars which yield 3 to 10 monosaccharide units on hydrolysis, e.g.

Maltotriose.
 Polysaccharides
 Polysaccharides : Those sugars which yield more than ten molecules of
monosaccharides on hydrolysis.

 General formula: (C6H10O5)n Polysaccharides

a. Homopolysaccharides b. Heteropolysaccharides
(homoglycans): (heteroglycans):

Polymer of different monosaccharide

Polymer of same monosaccharide units.
units or their derivatives.
Examples—Starch, glycogen, inulin,
Example—Mucopolysaccharides
cellulose, dextrins, dextran.
(glycosaminoglycans
STRUCTURE OF
CARBOHYDRATES
 Cyclic structures
 If the open-chain form of D-Glucose, which may be
called as Aldehydo-D-Glucose is taken, and
condense the aldehyde group on carbon-1, with the
alcoholic-OH group on carbon-5, two different forms
of glucose are formed. When the OH group extends
to right, it is called as α -D-Glucose and it extends to
left, it is called as β -D-Glucose.
 anomers
 Carbon-1, after cyclization has four different groups attached
to it and thus it becomes now asymmetric. The two cyclic
compounds, α and β have different optical rotations, but they
will not be same because the compounds as a whole are not
mirror-images of each other. Compounds related in this way
are called anomers and carbon-1, after cyclisation becomes
asymmetric is called now anomeric carbon atom.
 For example, Glucose forms a six-membered ring with two
anomeric forms:
 a-D-Glucoyranose
 b-D-Glucopyranose
 anomers (continue…)
 In glucose, the a-anomers has the —OH group of C-1 trans to
the CH2OH group attached to carbon 5.
 In glucose, the b-anomers has the —OH group of C-1 cis to the
CH2OH group attached to carbon 5.
 Mutarotation
 When an aldohexose 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
rotation characteristic of the sugar is reached. This phenomenon of
change of rotation is called as mutarotation.
 Mutarotation…..
 So Mutarotation is the change in specific rotation that accompanies the
equilibration of a and b anomers in aqueous solution.

 For example, a solution prepared by dissolving crystalline a-D-

glucopyranose in water has a specific rotation of +112°, which gradually
decreases to an equilibrium value of +52.7° as a-D-glucopyranose reaches
equilibrium with b-D-glucopyranose.

 A solution of b-D-glucopyranose also undergoes mutarotation, during which

the specific rotation changes from +18.7° to the same equilibrium value of
+52.7°.
 Mutarotation…..
 The equilibrium mixture of glucose consists of:
 64% (two-third) b-D-glucopyranose ,

 36% (one-third) a-D-glucopyranose and

 only a trace (0.003%) of the open-chain form.

 Mutarotation is common to all carbohydrates that exist in

hemiacetal forms.
 Epimers and epimerization
 Two sugars which differ from one another only in configuration
around a single carbon atom are termed Epimers.

 Examples

 Glucose and galactose are examples of an epimeric pairs which

differ only with respect of C4.

 Similarly, mannose and glucose are epimers in respect of C2.

 Epimerization: Process by which one epimer is converted to other is

called epimerization and it requires the enzyme epimerase, e.g.
conversion of galactose to glucose in liver.
Epimers and epimerization
 Monosaccharides of biological importance
 Trioses: Both D-glyceraldehyde and di hydroxy acetone 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.

 Tetroses: Erythrose-4-P occurs as an intermediate in hexose monophosphate

shunt which is an alternative pathway for glucose oxidation.

 Pentoses: Two pentoses, ribose and deoxyribose, are extremely important

because they are used in the synthesis of nucleic acids (DNA and RNA).

 D-Ribose is a component of a variety of complex molecules, including ribonucleic

acids (RNAs) and energy-rich compounds such as adenosine triphosphate (ATP).

 2-Deoxy-D-ribose (along with phosphate groups) forms the long chains of

deoxyribonucleic acid (DNA).
Stereochemistry of
carbohydrates
 Stereochemistry of carbohydrates

 Stereochemistry: The branch of chemistry that deals with the three

dimensional arrangement of atoms in space.

 The presence of asymmetric carbon atoms in a compound gives rise to the

formation of isomers of that compound.

 Asymmetric carbon: A carbon atom to which four different atoms or groups

of atoms are attached is said to be asymmetric.

 Stereoisomer: are the compounds that have the same molecular and
structural formula but differ in the orientation of the atoms in space.

 Example:Two such isomers of glucose exist i.e.

 D-Glucose and L-Glucose are mirror image of each other

Stereochemistry of carbohydrates

 D & L designations are based on the configuration about the single

asymmetric carbon in glyceraldehyde.
 If the OH group present at right side it is D-glyceraldehyde and if the OH
group present at the left side then it is designated as the L-
glyceraldehyde.
 CONTINUE
 For sugars with more than one chiral center, D or L refers to the
asymmetric carbon farthest from the aldehyde or keto group.

 Most naturally occurring sugars are D isomers.

 It should be clearly understood that D

And L doesn’t signifies the dextrorotatory

And levorotatory but it only signifies the

Configuration (the arrangement of atoms in

relevant to space) of the sugar.

 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.
OPTICAL ISOMERISM
 Optical activity and Optical Isomer
Some compounds rotate the plane polarized light toward left or right .These
compounds are called as the optical isomers and this property is known as
the optical activity.

Optical isomer are of two types

 Enantiomers

 Diastereomers
 ENANTIOMERS
 Enantiomers are stereoisomers that are non-superimposable mirror
images of each other.

 D and L sugars are referred to as enantiomers.

 If two objects are superimposable,

it means you can not tell

them apart, they are identical.

 If two objects are

Non superimposable,

then you can always

distinguish them.
 ENANTIOMERS……..
 Enantiomers are said to be optically active.

because of the way they interact with plane-polarized light.

 An enantiomer that rotates plane-polarized light in a clockwise

direction (to the right) is said to be dextrorotatory (+)
enantiomer.

 An enantiomer that rotates plane-polarized light in a

counterclockwise direction (to the left) is said to be
levorotatory (-) enantiomer.
 DIASTEREOMERS
 Stereoisomers that are not mirror images of each other are described as
diastereomers .

superimposable objects are achiral

(a molecule that has a plane of symmetry)

 RACEMIC MIXTURE
 When equal amounts of dextrorotatory and
laevorotatory isomers are present, the resulting
mixture has no optical activity, since the activities of
each isomer cancels each other. Such a mixture is
said to be Racemic.

 Resolution: The separation of optically active isomers

from a racemic mixture is called resolution.
Optical Activity
Monosaccharides of
biological importance
 Monosaccharides of biological importance
 2-deoxyribose differs from ribose by the absence of one oxygen
atom, that in the –OH group at C2.

 Both ribose and 2-deoxyribose exist in the usual mixture of open-

chain and cyclic hemi acetal forms.
Monosaccharides of biological importance
 Hexoses:
 D-Glucose (dextrose, grape sugar)
 Of the monosaccharides, the hexose glucose is the most
important nutritionally and the most abundant in nature.
 Glucose is present in honey and fruits such as grapes, figs,
and dates.
 Ripe fruits, particularly ripe grapes (20%–30% glucose by
mass), are a good source of glucose, which is often
referred to as grape sugar.
 Glucose is also known as blood sugar because it is the
sugar transported by the blood to body tissues to satisfy
energy requirements.
 Monosaccharides of biological importance
 The normal concentration of glucose in human blood is in the range of
70 –100 mg/ dL.

 All tissues use glucose as a primary source of energy.

 Erythrocytes and brains cells utilize glucose solely for energy.

D-Galactose:

 D-Galactose is seldom encountered as a free monosaccharide.

 In the human body, galactose is synthesized from glucose in the

mammary glands to produce lactose (milk sugar).

 D-Galactose is sometimes called brain sugar because it is a component of

glycoproteins (protein–carbohydrate compounds) found in brain and
nerve tissue.
 Monosaccharides of biological importance

 Like glucose, galactose is an aldohexose; it differs from glucose

only in the spatial orientation of the – OH group at carbon 4.
 Monosaccharides of biological importance
D-Fructose

 D-Fructose, often called levulose or fruit sugar, occurs in honey and

many fruits.

 Aqueous solutions of naturally occurring D-fructose

rotate plane-polarized light to the left; hence the name

levulose.

 D-fructose is present in honey in equal amounts

with glucose.
Monosaccharides of biological importance

 Fructose is sweeter than sucrose and is an ingredient

in many sweetened beverages and prepared foods.
 As a phosphate, it is an intermediate in glucose
metabolism.
 Seminal fluid is rich in fructose and sperms utilize fructose for
energy.
 Monosaccharides of biological importance
 Iodocompounds:
 An aldose when heated with conc. HI loses all of its oxygen and is
converted into an iodocompound.
 Acetylation or ester formation:
 The ability to form sugar esters, e.g. acetylation with acetyl chloride
(CH3– COCl) indicates the presence of alcohol groups. Due to alcoholic –OH
groups, it can react with anhydrides and chlorides of many organic and
inorganic acids, like acetic acid, phosphoric acid, sulphuric and benzoic acids
to form esters of corresponding acids.
 Osazone formation:
It is a useful means of preparing crystalline derivatives of sugars. They are
obtained by adding a mixture of phenylhydrazine hydrochloride and sodium
acetate to the sugar solution and heating in a boiling water bath for 30 to 45
minutes. The solution is allowed to cool slowly (not under tap water) by itself.
Crystals are formed
 Monosaccharides of biological importance
 These are fine, yellow needles in fan-shaped aggregates or sheaves or
crosses, typically described as Bundle of Hay. Melting point = 204 to
205°C.

 Oxidation to produce the sugar acids:

 Monosaccharide oxidation can yield three different types of acidic sugars.

a) Aldonic acids

b) Aldaric acids

c) Alduronic acid

 The oxidizing agent used determines the product.

 Monosaccharides of biological importance
 Oxidation of the aldehyde end of
 an aldose with mild oxidizing agent
 such as bromine gives
 an aldonic acid.

 For example, the oxidation of the

 aldehyde end of D-glucose with
 bromine produces D-gluconic acid.
 Monosaccharides of biological importance
 Oxidation of both ends of an aldose (the aldehyde and the
terminal primary alcohol group) with Strong oxidizing agent such as
nitric acid produces a dicarboxylic acid.

 Such polyhydroxy dicarboxylic acids are known as aldaric or

saccharic acid.

 For glucose, this oxidation produces glucaric acid.

 Monosaccharides of biological importance
 In biochemical systems, enzymes can oxidize the primary alcohol
end of an aldose such as glucose, without oxidation of the
aldehyde group, to produce an alduronic acid.

 For D-glucose, such an oxidation produces D-glucuronic acid.

 Monosaccharides of biological importance
 Oxidation reactions are often used as a test for the presence of an
aldehyde group in a carbohydrate.

 Benedict’s test and Fehling’s test both employ a solution of Cu2+ ions
in aqueous base.

 When the carbohydrate is oxidized, the blue Cu2+ ion is reduced to

Cu2O, which forms a brick red precipitate.

Monosaccharides of biological importance

 Reduction of suger to alcohol:

 The monosaccharides may be reduced to their corresponding alcohols
by reducing agents such as Na-Amalgam. Similarly, ketoses may also be
reduced to form keto alcohol.
 For example, the reduction of D-glucose gives D-glucitol.
 D-Glucitol, also known by the common name D-sorbitol, is used as the
sweetener.
 D-Sorbitol accumulation in the eye is a major factor in the formation of
cataracts due to diabetes.
Monosaccharides of biological importance
 Important reactions of
monosaccharides
 The sugar alcohols formed from mannose, fructose and
galactose are:
 D-Mannose D-Mannitol
 D-Fructose D-Mannitol + D-Sorbitol
 D-Galactose D-Dulcitol
 D-Xylose D-Xylitol
 Mannitol is frequently used medically as an osmotic diuretic
to reduce cerebral edema.
 Monosaccharides of biological importance
 Actions of acids on carbohydrates: Polysaccharides and the
compound carbohydrates in general are hydrolyzed into their
constituent monosaccharides by boiling with dilute mineral acids
(0.5 to 1.0 N) such as HCl or H2SO4.

 • With conc. mineral acids the

monosaccharides are decomposed.

 • Pentoses yield the cyclic aldehyde “furfural” .

 Monosaccharides of biological importance
 Glycoside formation:

 Cyclic monosaccharides (hemiacetals and hemiketals) readily react

with alcohols in the presence of acid solution to form acetals and
ketals, which are called glycosides.

 A glycoside produced from glucose is called a glucoside, that from

galactose is called a galactoside, and so on.

 For example, glucose reacts with methanol to produce methyl glucoside.

Important reactions of
monosaccharides
 Monosaccharides of biological importance
 The bond between the anomeric carbon atom of the
monosaccharide and the oxygen atom of the –OR group is called
a glycosidic bond.

 Disaccharides and polysaccharides form as a result of glycosidic

bonds between monosaccharide units.
 Monosaccharides of biological importance
4. Phosphate Ester Formation

 The hydroxyl groups of a monosaccharide can react with acids and

derivatives of acids to form esters.

 The phosphate esters are particularly important because they are the
usual intermediates in the breakdown of carbohydrates to provide energy.

 Phosphate esters are frequently formed by transfer of a phosphate group

from ATP to give the phosphorylated sugar and ADP.

 For example, specific enzymes in the human body catalyze the

esterification of the hemiacetal group (carbon 1) and the primary alcohol
group (carbon 6) in glucose to produce the compounds glucose 1-phosphate
and glucose 6-phosphate, respectively.
Important reactions of
monosaccharides
END OF THE PRESENTATION

 Thanks For Your Concentration

 ANY QUESTIONS
"There are naïve questions, tedious questions,
ill-phrased questions, questions put after
inadequate self-criticism. But every question is
a cry to understand the world.
There is no such thing as a
dumb question".

CARL SAGAN..
American
Astronomer