Monosaccharides

, Dr. Shweta Hardia

By Dr. Shweta Hardia

 Monosaccharides
• Monosaccharides are the simplest
carbohydrates and are often called
single sugars. They are the building blocks
from which all bigger carbohydrates are made.
• Monosaccharides have the general molecular
formula (CH2O)n, where n can be 3, 5 or 6.

By Dr. Shweta Hardia

 Classification of Monosaccharides
• Monosaccharides may be subcategorized
as aldoses or ketoses.
• Monosaccharides may be further classified
based on the number of carbon atoms in the
backbone, which can be designated with the
prefixes tri-(3), tetr-(4), pent-(5), hex-(6), hept-
(7), etc. in the name of the sugar.

By Dr. Shweta Hardia

 Aldose
• An Aldose contains an aldehyde with two or more hydroxyl groups
attached; one of the hydroxyl groups is at end opposite to the aldehyde.
• An Aldose is a type of monosaccharides, which is a chiral molecules that
plays a key role in the development of nucleic acids.
• The two simplest forms of Aldoses are L- and D-Glyceraldehydes, which
are three-carbon structures that each contain one aldehyde and two
hydroxyl groups.
• The L and D symbols apply to the two different configurations of the
asymmetric carbon farthest from the aldehyde group.
• Aldoses can have three or more carbons.
• Aldoses are distinguishable by the carbonyl(C=O) group located at the end
of the carbon chain, which differs from ketose, which has the carbonyl
group in the middle of the carbon chain.

By Dr. Shweta Hardia

 Triose
• Trioses are monosachrides with three carbon atoms;
• aldotrioses have an aldehyde functional group at carbon number one.
• A common aldotrisose is glyceraldehyde.
• They have a single asymmetric carbon atom: D- and L-glyceraldehyde are
enantiomers of one another.
• Glyceraldehydes are one of the smallest monosaccharides.

By Dr. Shweta Hardia

 Tetroses
• Tetroses are monosaccharides with four carbon atoms. An aldotetrose has
an aldehyde functional group at carbon number one.
• The two common types of aldotetroses are D-Erythose and D-Threose. The
D configuration is more favor.
• Since D-Erythose and D-Threose are not mirror image of one another,
they are diasteroisomers of one another.
• They have a different configuration at the second carbon. They have two
asymmetric carbons and four steroisomers.

By Dr. Shweta Hardia

 Pentose
• Pentose is a type of monosaccharide which has a backbone
of five carbon atoms. At carbon position 1, there is an
aldehyde functional group attached which gives it their aldose
nature.
• Common types of 5-Carbon Aldoses include Ribose,
Arabinose, Lyxose, and Xylose

By Dr. Shweta Hardia

 Hexoses
• A hexose is a monosaccharide with six carbons, but more specifically, an
aldohexose is a hexose with an aldehyde functional group at carbon number one.
• Some common aldohexoses are Allose, Altrose, Glucose, Mannose, Gulose, Idose,
Galactose, Talose.
trick to remember
"All altruists gladly make gum in gallon tanks"

• trick to remember "All altruists gladly make gum in gallon tanks"

By Dr. Shweta Hardia

 Ketoses
• A ketose is a sugar that has a ketone group in each of its molecule.
Dihydroxyacetone, for example, has 3 carbon atoms in its backbone - it is the
simplest ketose among this category.
• It is also the only optically inactive ketose. In comparison to other aldoses,
ketones will have one less chiral carbon than aldoses even though they share
the same number of carbon atoms.
• Thus, when forming a ring, the ketone at the second carbon will be utilized
to form a ring.
• Similar to aldoses, furanose rings can take up a different conformation than a
ring. The other conformation is called the envelope form: C3-endo and C2-
endo.
• Both forms resembles an envelope.

By Dr. Shweta Hardia

• Triose : Dihydroxyacetone

• Tetroses: erythrulose

• Pentoses: ribulose,

• Hexoses: fructose,

By Dr. Shweta Hardia

 Asymmetric carbon

• An asymmetric carbon atom (chiral carbon) is

a carbon atom that is attached to four
different types of atoms or groups of atoms.

By Dr. Shweta Hardia

 Tetrahedral structure of carbon

In a tetrahedral molecular geometry, a central atom is

located at the center with four substituents that are
located at the corners of a tetrahedron.

By Dr. Shweta Hardia

 Isomerism
• All the monosaccharides have one or more
asymmetric carbon atoms with hydroxyl
groups attached known as chiral center. Thus
monosaccharides undergoes property of
Isomerism.

By Dr. Shweta Hardia

By Dr. Shweta Hardia
 Optical isomers
• Optical isomers are two compounds which
contain the same number and kinds of atoms,
and bonds (i.e., the connectivity between
atoms is the same), and different spatial
arrangements of the atoms, but which have
non-superimposable mirror images. Each non-
superimposable mirror image structure is
called an enantiomer.

By Dr. Shweta Hardia

 D and L isomers
• Stereoisomers of monosaccharides of all carbon-chain length may be
categorized into two divisions. These groups vary in the configuration or
orientation of the –H and –OH groups around the chiral center (C-5 in
glucose) farthest away from the carbonyl carbon and near to the terminal
primary alcohol carbon that determines D or L isomers of a sugar.
• If the hydroxyl (-OH) group around the chiral carbon (for example C-5 in
glucose) is present on the right side in a projection formula of a
monosaccharide, the sugar is a D isomer.
• Most of the hexoses found in living organisms are D isomers and the
specific enzymes are responsible for metabolism of a sugar with this
configuration.
• When hydroxyl (-OH) group attached to the chiral carbon (for example C-5
in glucose) at the left side, then it is called the L isomer . A few sugars
found naturally in their L isomer; for example L-arabinose.

By Dr. Shweta Hardia

 Enantiomers

• Those sugars are enantiomers which have chiral

centers and are mirror images of each other. Thus
D and L isomers of sugar, for example glucose, are
enantiomers .
• For examples, aldopentoses contain three
asymmetric carbons and eight stereoisomers
hence four pairs of enantiomers occur.
• Similarly, aldohexoses contain four asymmetric
carbons and 16 stereoisomers hence eight pairs
of enantiomers occur.
By Dr. Shweta Hardia
 How to determine the number of
stereoisomers of a sugar?
• Usually, a molecule has ‘n’ chiral centers so it
may contain 2n stereoisomers. For example,
Glyceraldehyde with one chiral center
has 21 = 2 stereoisomers (One is D- and
another is L-isomer).
• The aldohexoses have four chiral centers so it
is found in 24 = 16 stereoisomers out which
eight are D-isomers and eight are L-isomers.

By Dr. Shweta Hardia

 Diastereomers
• Diastereomers are stereoisomers that are not related as
object and mirror image and are not enantiomers.
• Unlike enatiomers which are mirror images of each other
and non-sumperimposable, diastereomers are not
mirror images of each other and non-superimposable.
• Diastereomers can have different physical properties and
reactivity. They have different melting points and boiling
points and different densities.
• They have two or more stereocenters.

By Dr. Shweta Hardia

By Dr. Shweta Hardia
 Epimers
• When two diastereoisomers of a sugar vary only in the
configuration of the –H and –OH groups on one carbon
atom (chiral center) are called epimers.
• In biology, the main epimers of glucose are mannose
and galactose, created through epimerization at
carbons 2 and 4, respectively.
• For examples, D-glucose and D-mannose differ only in
orientation of the –H and –OH groups around one
chiral center at C-2, are epimers.
• In the same way, D-glucose and D-galactose are
epimers in which orientation of the –H and –OH groups
differ at C-4.

By Dr. Shweta Hardia

 Optical isomers
• A vital characteristic of asymmetric centers in sugars is their
ability to rotate the plane-polarized light i.e. confers optical
activity.
• When a ray of plane-polarized light is travel through a sugar
solution, it will rotate either to the right, dextrorotatory (+) or to
the left, levorotatory (−) and the sugar called as optical isomer.
• The direction of rotation is irrespective of the stereochemistry (D
and L isomers) of the sugar, thus it is named as D(−), D(+), L(−), or
L(+). For instance, the naturally occurring isomer of fructose is the
D(−) isomer.
• It is not necessary that all sugars of the same configuration (D- or L-
) will have the same sign of optical rotation. For example, D-glucose
is dextrorotatory: D(+) isomer, whereas D-fructose is levorotatory:
D(−) isomer which are naturally occurring forms. Therefore, another
name for glucose is dextrose exercised in clinical practice.

By Dr. Shweta Hardia

 Racemization
• The process by which an optically active
substance is transformed into the
corresponding racemic modification is known
as racemization;
• The converse process, by which a racemic
modification is separated into the two
enantiomorphs, is known as resolution.

By Dr. Shweta Hardia

 The Cyclic Structure of Monosaccharides:
Haworth Structures
• The cyclic structure of monosaccharides is commonly represented using
Haworth projections, named after the English chemist Sir Walter N.
Haworth.
• The open-chain form of D-glucose is converted to a cyclic form through a
ring closure reaction involving the -OH group on carbon five and the C-1
carbonyl carbon.
• The carbonyl group at C-1 reacts with the hydroxyl group at C-5 to give a
six-membered ring containing oxygen. The newly formed ring is a rigid
structure that has two planes, one above the ring, the other below.
• When the ring closes, the C-5 -OH loses the hydrogen and the oxygen is
incorporated into the ring. The C-1 carbonyl carbon loses its double bond
to oxygen and becomes a single bond to -OH.
• The newly formed -OH at C-1 (formerly the carbonyl carbon) can be drawn
above or below the ring producing two different isomers. These two
isomers are called anomers named (alpha) and β (beta) anomers. In the
anomer, the C-1 hydroxyl group is below the ring, in the β anomer, the C-1
hydroxyl group is above the ring

By Dr. Shweta Hardia

Anomers

By Dr. Shweta Hardia

Fructose anomers

By Dr. Shweta Hardia

 Mutarotation
• Mutarotation is the change in the optical rotation because of the change in the
equilibrium between two anomers, when the
corresponding stereocenters interconvert. Cyclic sugarsshow mutarotation as α
and β anomeric forms interconvert. The optical rotation of the solution depends
on the optical rotation of each anomer and their ratio in the solution.
• Mutarotation was discovered by French chemist Dubrunfaut in 1846, when he
noticed that the specific rotation of aqueous sugar solution changes with time.

By Dr. Shweta Hardia

By Dr. Shweta Hardia