Carbohydrate

Carbohydrates (also called saccharides) are molecular compounds

made from just three elements: carbon, hydrogen and oxygen.
Monosaccharides (e.g. glucose) and disaccharides (e.g. sucrose) are
relatively small molecules. They are often called sugars.

The term carbohydrate was originally used to describe compounds

that were literally "hydrates of carbon" because they had the
empirical formula CH2O.

In recent years, carbohydrates have been classified on the basis of

their structures, not their formulas. They are now defined as naturally
occurring optically active polyhydroxy aldehydes or polyhydroxy
ketones.
Green plants make food in the form of carbohydrates by combining
carbon dioxide and water using energy from sunlight. Carbohydrates
are chemicals containing only the elements carbon, hydrogen and
oxygen. The simplest useful form of carbohydrate produced by
photosynthesis is glucose sugar.
Monosaccharides
• Three common sugars share the same molecular formula: C6H12O6. Because of
their six carbon atoms, each is a hexose.
• Glucose, "blood sugar", the immediate source of energy for cellular respiration
• Galactose, a sugar in milk (and yogurt)
• Fructose, a sugar found in honey.
• Although all three share the same molecular formula (C6H12O6), the arrangement
of atoms differs in each case. Substances such as these three, which have
identical molecular formulas but different structural formulas, are known as
structural isomers.
• Glucose, galactose, and fructose are "single" sugars or monosaccharides. Two
monosaccharides can be linked together to form a "double" sugar or
disaccharide.
Disaccharides
• Three common disaccharides:
• sucrose — common table sugar = glucose + fructose
• lactose — major sugar in milk = glucose + galactose
• maltose — product of starch digestion = glucose + glucose
• Although the process of linking the two monomers is rather complex, the end
result in each case is the loss of a hydrogen atom (H) from one of the
monosaccharides and a hydroxyl group (OH) from the other. The resulting linkage
between the sugars is called a glycosidic bond. The molecular formula of each of
these disaccharides is C12H22O11 = 2 C6H12O6 − H2O
• All sugars are very soluble in water because of their many hydroxyl groups.
Although not as concentrated a fuel as fats, sugars are the most important source
of energy for many cells.
• Carbohydrates provide the bulk of the calories (4 kcal/gram) in most diets, and
starches provide the bulk of that. Starches are polysaccharides.
Polysaccharides
• Starches are polymers of glucose. Two types are found:
• amylose consists of linear, unbranched chains of several hundred glucose
residues (units). The glucose residues are linked by a glycosidic bond between
their #1 and #4 carbon atoms.
• amylopectin differs from amylose in being highly branched. At approximately
every thirtieth residue along the chain, a short side chain is attached by a
glycosidic bond to the #6 carbon atom (the carbon above the ring). The total
number of glucose residues in a molecule of amylopectin is several thousand.
• Starches are insoluble in water and thus can serve as storage depots
of glucose. Plants convert excess glucose into starch for storage. Rice,
wheat, potatoand corn (maize) are also major sources of starch in the
human diet.
Before starches can enter (or leave) cells, they must be digested. The
hydrolysis of starch is done by amylases. With the aid of an amylase (such
as pancreatic amylase), water molecules enter at the 1 -> 4 linkages,
breaking the chain and eventually producing a mixture of glucose and
maltose. A different amylase is needed to break the 1 -> 6 bonds of
amylopectin.
Glycogen
Animals store excess glucose by polymerizing it to form glycogen. The structure
of glycogen is similar to that of amylopectin, although the branches in glycogen
tend to be shorter and more frequent.
Glycogen is broken back down into glucose when energy is needed (a process
called glycogenolysis).
In glycogenolysis, Phosphate groups — not water — break the 1 -> 4 linkages
The phosphate group must then be removed so that glucose can leave the cell.
The liver and skeletal muscle are major depots of glycogen.
There is some evidence that intense exercise and a high-carbohydrate diet
("carbo-loading") can increase the reserves of glycogen in the muscles and thus
may help marathoners work their muscles somewhat longer and harder than
otherwise. But for most of us, carbo loading leads to increased deposits of fat.
Cellulose is probably the single most abundant organic molecule in the biosphere. It is the
major structural material of which plants are made. Wood is largely cellulose while cotton and
paper are almost pure cellulose.
Like starch, cellulose is a polysaccharide with glucose as its monomer. However, cellulose differs
profoundly from starch in its properties.
Because of the orientation of the glycosidic bonds linking the glucose residues, the rings of
glucose are arranged in a flip-flop manner. This produces a long, straight, rigid molecule.
There are no side chains in cellulose as there are in starch. The absence of side chains allows
these linear molecules to lie close together.
Because of the many -OH groups, as well as the oxygen atom in the
ring, there are many opportunities for hydrogen bonds to form
between adjacent chains.
The result is a series of stiff, elongated fibrils —
the perfect material for building the cell walls of plants.
This electron micrograph (courtesy of R. D. Preston) shows the cellulose fibrils in the
cell wall of a green alga. These long, rigid fibrils are a clear reflection of the nature
of the cellulose molecules of which they are composed.
Classification
Structure elucidation of glucose:
• From chemical analysis and molecular weight determination, molecular formula of glucose was
found to be C6H12O6
• With HCN it forms cyanohydrin; with phenyl hydrazine it forms hydarazone and with hydroxyl
amine it forms monooxime:
• These reactions indicate that glucose contain one carbonyl group
• Mild oxidation of glucose with bromine water gives gluconic acid (having same number of C
atoms), also glucose gives positive with tollen’s reagent,
• This means that glucose contains –CHO group CH O
• Strong oxidation gives glucaric acid (sacchric acid). H OH
• This reaction indicates that glucose contain terminal primary alcohol HO H
• With acetic anhydride glucose gives penta-acetate H OH
• It shows that glucose contains five –OH groups H OH
• Again, glucose is a stable molecule and does not liberate water on heating CH2OH
• Therefore the five –OH groups of glucose is attached to five different carbons.
• Glucose on reduction by H2/ Pt gives sorbitol, which on further reduction by HI gives n-hexane
• The cyanohydrin formed by glucose on hydrolysis gives a polyhydroxy acid which on further reduction by HI
gives n-heptanoic acid
• These suggests glucose has a straight chain of six carbons with terminal -CHO group
Drawbacks of open chain structure
• Though glucose contains a –CHO group, it does not form any additive
product with NaHSO3
• It does not change the colour of Schiff’s base
• D-(+)-glucose has two isomers viz., - and - isomer
• Penta-acetyl derivative of D-(+)-glucose does not form any oxime
• Although glucose contain five –OH groups, it forms only monomethyl
derivative with MeOH and HCl
• This monomethyl derivative exists in two isomeric forms: -D-glucoside and - D-glucoside
• Glucose shows mutarotation
• Fresh aq. soln. of natural D-(+)-glucose shows specific rotation[]D = +112o. On
keeping for some time this value gradually decreases until it reaches +52.5o &
doesn’t change any further. This spontaneous change in specific rotation is called
mutarotation.
• Considering the above facts, the ring structure of glucose was proposed
• Here the –CHO gr. and –OH gr. of the same molecule react to give
intramolecular hemiacetal structure
• As the six membered ring is a heterocyclic
one with one oxygen and five carbons –
it is called glucopyranose structure

Glucose may be considered as an example of

ring- chain tautomerism
Mutarotation
• The α- and β- anomers of carbohydrates are typically stable solids.
• However, in aqueous solution, they quickly equilibrate to an equilibrium mixture
of the two forms.
• For example, in aqueous solution, glucose exists as a mixture of 36% α- and 64%
β- (>99% of the pyranose forms exist in solution).
• The equilibration occurs via the ring opening of the cyclic sugar at the anomeric
center with the acyclic form as the intermediate.

• Or, in a simplified form with all the

"extra" hydroxy groups removed:
Action of phenylhydrazine on glucose (formation of
Osazone):
Structure elucidation of fructose
• From qualitative & quantitative analysis, fructose is found to have molecular
formula C6H12O6
• It is found to have five –OH groups on five different carbons
• It forms cyanohydrin & oxime: it contains carbonyl group
• On oxidation with HNO3 it gives glycolic acid & tartaric acid (each having lesser
number of C atoms): carbonyl group is ketonic in nature
• Formation of glycolic acid & tartaric acid also indicate ketonic group is present at
position – 2
• Fructose on reduction by Na/Hg and water gives hexahydric acid+ sorbitol +
mannitol; which on further reduction by HI/red P gives 2-iodo-hexane: In fructose
six C atoms are present in a straight chain.
• Fructose on treatment with HCN gives cyanohydrin which on hydrolysis followed
by reduction with HI & P gives n-butylmethylacetic acid/ 2-methyl hexanoic acid.
Formation of this compound again indicates that the ketonic group in fructose is
present at secondposition
Configuration of fructose
• The above structure of fructose has three asymmetric carbon
• 23=8 isomers
• The exact configuration of fructose is established by the fact that it forms
the same osazone as glucose thereby indicating that configuration of C3 to
C6 atoms of fructose is same as that of glucose.
• Therefore open chain structure of fructose may be written as
• Ring Structure
• Fructose exhibits mutarotation & forms two methyl fructosides ( & 
forms)
• The commercial& natural free fructose is most probably -isomer with a
pyranose ring. But fructose found in sucrose and inulin is present as
furanose ring, which on hydrolysis is converted to pyranose ring
Action of phenylhydrazine on Fructose (formation of
Osazone):
Conversion of glucose to fructose or conversion of aldoses to ketoses
Lobry de Bruyn–van Ekenstein transformation
• The Lobry de Bruyn–van Ekenstein transformation is relevant for the industrial
production of certain ketoses and was discovered in 1885 by Cornelis Adriaan
Lobry van Troostenburg de Bruyn and Willem Alberda van Ekenstein.
• The reactions are usually base catalyzed, but can also take place under acid or
neutral conditions. A typical rearrangement reaction is that between the aldose
glyceraldehyde and the ketose dihydroxyacetone in a chemical equilibrium.
• The carbon atom at which the initial deprotonation takes place is a stereocenter.
If, for example, D-glucose (an Aldose) rearranges to D-fructose, the ketose, the
stereochemical configuration is lost in the
enol form. In the chemical reaction the enol can be protonated from two faces,
resulting in the backformation of glucose
or the formation of the epimer D-mannose.
The final product is a mix of D-glucose,
D-fructose and D-mannose.
 Inversion of Sugar
• The value of specific rotation for sugar i.e. sucrose is + 66.5o. Thus sucrose is
dextro rotatory.
• On hydrolysis by invertase enzyme or dilute acid it produces equimolar mixture of
glucose & fructose. Specific rotation of this mixture is -19.75o.
• As the direction of specific rotation changes it may appear that sucrose molecule
has been inverted. But in reality no change in the configuration of sucrose takes
place. It gets hydrolysed and produces glucose & fructose, specific rotation of
which are =52.5o and -92o.
• Thus the specific rotation is the solution is actually average of the above two.
• C12H22O11 (sucrose, Specific rotation = +66.5°) + H2O (water, no rotation) →
C6H12O6 (glucose, Specific rotation = +52.7°) + C6H12O6 (fructose, Specific rotation
= −92°)
• net: +66.5° converts to −19.65° (half of the sum of the specific rotation of
fructose and glucose)

• Compared with its precursor, sucrose, inverted sugar is alluringly and its products tend to retain
moisture and are less prone to crystallization. Inverted sugar is therefore valued by bakers, who
refer to the syrup as invert syrup