Monosaccharides

General characteristics of Carbohydrates

The term carbohydrate is derived from the French
term : hydrate de carbone
Compounds composed of C, H, and O
Empirical formula (CH2O)n when n = 5 then C5H10O5
Not all carbohydrates have this empirical formula:
e.g. deoxysugars, amino sugars etc
Carbohydrates are the most abundant compounds
found in nature (cellulose: 100 billion tons annually)

General characteristics
-They have large number of hydroxyl groups
(polyhydroxy)
-In addition they may contain-an aldehyde group
(polyhydroxyaldehydes) or a keto group(polyhydroxyketones).

C O

-Their derivatives
may H
also
Ccontain
O nitrogen, phosphorus
or sulfur.
H COH

HYDROXYL GROUP

ALDEHYDE GROUP

KETO GROUP

Functions of Carbohydrates
1) Sources of energy, especially for brain cells and Red blood
cells.
2) Intermediates in the biosynthesis of other basic
biochemical entities (fats and proteins)
3) Associated with other entities such as glycosides, vitamins
and antibiotics)
4) Form structural tissues in plants and in microorganisms
5) Participate in biological transport, cell-cell recognition,
activation of growth factors, modulation of the immune
system

Classification of
carbohydrates
1) Monosaccharides
(monoses or glycoses)
Trioses, Tetroses, Pentoses, Hexoses

2) Oligosaccharides
Di, tri, tetra, penta, up to 9 or 10
Most important are the disaccharides
3) Polysaccharides or glycans
a)Homopolysaccharides
b) Heteropolysaccharides

Monosaccharides
-Also known as simple sugars
-Classified either by the number of carbon atoms or by the
nature of functional group-aldoses or ketoses
-Most of the carbohydrates (99%) are straight chain compounds
-D-glyceraldehyde is the simplest of the aldoses (aldotriose)
-All other sugars have the ending ose (glucose, galactose,
ribose, lactose, etc)

MONOSACCHARIDES
1-According toNOMENCLATURE
number of carbons they contain in
their backbone structuresIt is a variable prefix followed by the suffix(-ose)
(Trioses=3C), (Tetroses=4C), (Pentoses=5C),
(Hexoses=6C),(Heptoses=7C).
2- According to nature of reactive group - Aldose
sugars e.g. glyceraldehyde or a ketose sugars
e.g.dihydroxyacetone depending on the presence
of Aldehyde or keto group.
CH 2OH

C O

CH 2OH
D-Glyceraldehyde

Dihydroxyacetone.

Monosaccharides
Name
Relevant examples
Classification
3

Triose

Tetros
e
Pentos
e

5
6
9

Hexose
Nonose

Glyceraldehyde, Dihydroxyacetone
Erythrose ,Erythrulose
Ribose, Ribulose, Xylulose
Glucose, Galactose, Mannose, Fructose
Neuraminic acid
also called Sialic acid

Aldose sugars

n - denotes the number of asymmetric carbon

atoms

Ketose sugars

n - denotes the number of asymmetric carbon

atoms

Asymmetric carbon atom

-It Is the carbon atom that is attached to

4 different groups.
-All monosaccharides have it except
dihydroxyacetone.
-Different isomers are possible based on
the presence of number of asymmetric
carbon atoms

CH 2OH

C O

CH 2OH
Dihydroxyaceton
e.

parent compound of the carbohydrates, the three-carbon

sugar glycerose (glyceraldehyde), also called reference

Isomerism in Monosaccharides

sugar.

The orientation of the H and OH groups around the

carbon atom adjacent to the terminal primary alcohol
carbon ( as carbon 5 in glucose) determines whether the
sugar belongs to the D or L series.

When OH is on the right side the sugar is D isomer;

when it is on the left, it is the L isomer.

D and L Isomers Of
Glyceraldehyde

D-Glyceraldehyde

L-Glyceraldehyde

Isomers of Monosaccharides(D and L)

1) Most of the monosaccharides occurring in mammals are D

sugars, and the enzymes responsible for their metabolism are
specific for this configuration.
2) Simple monosaccharides with four, five, six, and seven carbon
atoms have multiple asymmetric carbons, they exist as
diastereoisomers, isomers that are not mirror images of each
other.
Some sugars naturally occur in the L form e.g.
L-Arabinose and L-Fucose are found in glycoproteins, while L- Xylulose is
produced during the metabolism of Glucose in Uronic acid pathway. It is
subsequently converted to its D form.

D and L Isomers of Fructose

Isomerism in
Monosaccharides

2) Optical Isomerism-

The presence of asymmetric carbon atoms also confers optical

activity on the compound. When a beam of plane-polarized light is
passed through a solution of an optical isomer, it rotates either to
the right, dextrorotatory (+), or to the left, levorotatory (). The
direction of rotation of polarized light is independent of the
stereochemistry of the sugar, so it may be designated D(), D(+),
L(), or L(+). For example, the naturally occurring form of fructose
is the D() isomer. In solution, glucose is dextrorotatory, and
glucose solutions are sometimes known as dextrose.

POLARIMETRY
Measurement of optical activity in chiral or asymmetric
molecules using plane polarized light is called Polarimetry.
The measurement of optical activity is done by an
instrument called Polarimeter.

Specific rotation of various carbohydrates at 20 oC

D-Glucose +52.7
D-Fructose -92.4
D-Galactose +80.2
L-Arabinose +104.5
D-Mannose +14.2
D-Xylose +18.8
Lactose +55.4
Sucrose +66.5
Maltose +130.4
Invert sugar -19.8
Dextrin +195

Isomers differing as a result of variations in configuration of the OH and H on carbon atoms 2, 3, and 4 of glucose
are known as epimers. Biologically, the most important epimers of glucose are mannose and galactose, formed by
epimerization at carbons 2 and 4, respectively. Mannose and Galactose are not epimers of each other as they differ in
configuration around 2 carbon atoms.

Isomers of Monosaccharides
3) Epimers-

Epimer carbons are the middle asymmetric

carbons other than the sub terminal one (related to D&L
forms ).The differences in orientation of OH group around only
one of these epimer carbons will produce epimers.
Isomers differing as a result of variations in configuration of the OH and
H on carbon atoms 2, 3, and 4 of glucose are known as epimers.
Biologically, the most important epimers of glucose are mannose and
galactose, formed by epimerization at carbons 2 and 4, respectively.
Mannose and Galactose are not epimers of each other as they differ in
configuration around 2 carbon atoms.

Epimers of Glucose

Isomers of Monosaccharides(Aldoses)
CH 2OH

C O

CH 2OH

Isomers of Monosaccharides
(Ketoses)

CH 2OH

C O

CH 2OH

Isomers of monosaccharides
4) Pyranose and furanose ring
structuresThe ring structures of monosaccharides are similar to the ring
structures of either pyran (a six-membered ring) or furan (a fivemembered ring)
For Glucose in solution, more than 99% is in the Pyranose form

Isomers of monosaccharides
5) AnomersThe ring structure of an aldose is a hemiacetal, since it is
formed by combination of an aldehyde and an alcohol group.
Similarly, the ring structure of a ketose is a hemiketal. The
ring can open and reclose allowing the rotation to occur
around the carbon bearing the reactive carbonyl group
yielding two possible configurations- and of the
hemiacetal and hemiketal. The carbon about which this
rotation occurs is called Anomeric carbon and the two
stereoisomers are called Anomers. Crystalline glucose is -Dglucopyranose.

Anomers

Haworth Projection
of -D-Glucose

Cyclic Fischer Projection

of -D-Glucose

Anomers

When drawn in the Haworth projection, the

configuration places the hydroxyl downward. While
the is the reverse.

Anomers

When drawn in the Fischer projection, the

configuration places the hydroxyl attached to the
anomeric carbon to the right of the ring, While the
is the reverse

Mutarotation

Carbohydrates can change spontaneously between

the and configurations through the formation of
intermediate open chain. This will lead to a process
known as mutarotation. It is the gradual change of
specific optical rotation of sugar.I
n solution

Isomers of Monosaccharides
6) Aldose-ketose isomerism
Fructose has the same molecular formula as glucose but differs in its
structural formula, there is a potential keto group at position 2 (the anomeric
carbon of fructose), whereas there is a potential aldehyde group at position
1, the anomeric carbon of glucose.
Glucose and Fructose are Aldose ketose isomers

Structural representation of
sugars
1) Fischer projection: straight chain representation
2) Haworth projection: simple ring in perspective
Conformational representation:
3) Chair and boat conformations

Rules for drawing Haworth

projections

1) Draw either a six or 5-membered ring including

oxygen as one atom.
2) Most aldohexoses are six-membered
aldotetroses, aldopentoses, ketohexoses are 5membered

Rules for drawing Haworth

projections
Number the ring clockwise starting next to the oxygen

if the substituent is to the right in the Fischer

projection, it will be drawn down in the Haworth
projection (Down-Right Rule)

Rules for drawing Haworth

projections

In Haworth configuration all groups to the right of

carbon backbone in Fischer projection are oriented
down while all groups to the left of carbon
backbone are oriented up, except those around
C5,the reverse orientation occurs.

Rules for drawing Haworth projections

When drawn in the Haworth projection, the

configuration places the hydroxyl downward. While
the is the reverse.

Pyranose and Furanose forms of Glucose

Pyranose and Furanose forms of Ribose

Chair and Boat Conformations

Chair and boat conformations of a pyranose

sugar

2 possible chair conformations of -Dglucose

Reactions of monosaccharides
1)Osazone formation
2) Reduction
3) Oxidation
4) Action of alkali
5) Action of acid
6)Glycoside formation
7)Ester formation

Formation of osazones

-Used for the identification of sugars

-Consists of reacting the monosaccharide with phenyl hydrazine
-A crystalline compound with a sharp melting point and a characteristic shape is
obtained
D-fructose and D-mannose give the same needle shaped osazone crsytals as Dglucose
-Seldom used these days for identification
-HPLC or mass spectrometry is used now a days for the
identification of sugars

Formation of osazones

Aldoses may be oxidized to 3 types of acids

1) Aldonic acids: aldehyde group is converted to a carboxyl
group Glucose Gluconic acid, Galactose-Galactonic acid
and Mannose- Mannonic acid

Oxidation reactions

2) Uronic acids: aldehyde is left intact and primary alcohol at

the other end is oxidized to COOH
Glucose --- Glucuronic acid
Galactose --- Galacturonic acid
Mannose-----Mannuronic acid
3) Saccharic acids: (glycaric acids) oxidation at both ends of
monosaccharide)
Glucose ---- Gluco saccharic acid
Galactose --- Mucic acid
Mannose --- Mannaric acid

Oxidation Products Of DGlucose

Reduction
-Either done catalytically (hydrogen and a catalyst) or enzymatically
-The resultant product is a polyol or sugar alcohol
-Glucose forms sorbitol (glucitol)
-Mannose forms mannitol
-Fructose forms a mixture of mannitol and sorbitol
-Glyceraldehyde forms glycerol

Sructures of some sugar

alcohols

Action of strong acids on monosaccharides

-Monosaccharides are normally stable to dilute acids, but are
dehydrated by strong acids
-D-ribose when heated with concentrated HCl yields furfural
-D-glucose under the same conditions yields 5hydroxymethyl furfural
- Forms the basis of Molisch test, Seliwanoff test and Bials
Test

Action of Alkalies on sugars

-In mild alkaline conditions Enediols are formed
- Enediols are highly reactive sugars and are powerful reducing
agents.
-This allows the interconversion of D-mannose, D-fructose and Dglucose
-This interconversion reaction is known as Lobry de Bruyn- Van
Eckenstein transformation.
- Strong alkalis cause CARAMELISATION (Decomposition)of sugars.

-Enediols obtained by the action of bases are quite

susceptible to oxidation when heated in the
presence of an oxidising agent. It forms the basis
of Benedicts and Fehling test for the detection of
reducing sugars
-Copper sulfate is frequently used as the oxidising
agent and a red precipitate of Cu2O is obtained
-Sugars which give this reaction are known as
reducing sugars
Fehlings solution : KOH or NaOH and CuSO4
Benedicts solution: Na2CO3 and CuSO4

Action of Alkalies on sugars

Important derivatives of
monosaccharides

1-Amino sugars

They are formed by replacing the hydroxyl group

(at C2 usually) of monosaccharides by amino
group. The most common amino sugars are
glucosamine and galactosamine.
-Glucosamine is present in Heparin, Hyaluronic
acid and blood group substances.
-Galactosamine is present in Chondroitin of
cartilages and tendons.

Amino Sugars
-The amino group may be condensed with active acetate
forming N-acetyl glucosamine.
-They are components of glycosaminoglycans and some
glycosphingolipids (lipids).
-N-acetyl Mannosamine- it is a component of glycoproteins and
gangliosides(Lipids) of cell membrane.
- A polymer of N-Acetyl Glucosamine is a component of chitin
- N-Acetyl Galactosamine is a component of Chondroitin
sulphate.

Amino Sugar acids

Amino sugar acids are produced by condensation

of amino sugar with Pyruvic or lactic acid.
e.g.Muramic acid is produced by the condensation
of lactic acid with D- Glucosamine. Certain
bacterial cell walls contain Muramic acid.
N-Acetyl Neuraminic acid is formed from the
condensation of Pyruvic acid with N-Acetyl
Mannosamine.

2-Deoxy

sugars

-Are formed by removal of an oxygen atom usually from

2 nd carbon atom
-one quite ubiquitous deoxy sugar is 2-deoxy ribose
which is the sugar found in DNA
-6-deoxy-L-mannose (L-rhamnose) is used as a
fermentative reagent in bacteriology

Deoxy Sugars

Sugar acids
3-Sugar
acids
-Are formed by the oxidation of aldehyde
C1(Aldonic acid)
-or terminal hydroxyl group at C6 of aldose
sugar(uronic acid)
-or both (saccharic) to form carboxylic group.
-Glucuronic and Iduronic acids are the
components of glycosaminoglycans.
-L-ascorbic acid(vitamin C) is a sugar acid.
-Glucuronic acid is involved in detoxification of
bilirubin and other foreign compounds.

4-Sugar alcohols
Are formed by the reduction of the carbonyl group (aldehyde or ketone ) of
monosaccharide

5-Sugar Esters
- Hydroxyl groups of sugars can be esterified to form Acetates,
phosphates, benzoates etc.
-Sugars are phosphorylated at terminal C1 hydroxyl group or
at other places .At terminal hydroxyl: Glucose-6-P or ribose-5-P.
At C1 hydroxyl group: Glucose-1-P .At both places: Fructose 2,6
bisphosphate
- Metabolism of sugars inside the cells starts with
phosphorylation.
-Sugar phosphates are also components of nucleosides and
nucleotides.

They are formed by the reaction of the hydroxyl

group of anomeric carbon (hemiacetal or
hemiketal) with the hydroxyl group of any other
molecule with the elimination of water. A
glycosidic bond is formed.
2nd molecule may be:
Another sugar(glycon)disaccharide polysaccharide.
A non carbohydrate moiety (aglycon) as
Methanol, glycerol, sterols .etc.

6-Glycosides

Condensation reactions: Acetal and Ketal formation

Significance of Glycosides
1) Cardiac Glycosides- These include derivatives of digitalis
and strophanthus such as oubain.
2)Streptomycin is used as an antibiotic
3) Phloridzine -displaces Na+ from the binding site of carrier
protein and prevents the binding of sugar molecule and
produces Glycosuria.