Carbohydrates

General Biochemistry I (BCH201)

 Definition and Description
• They are the most abundant organic molecules in nature.
• The general empirical structure for carbohydrates is CH2O, hence the name “hydrates of carbon”.

• Structurally carbohydrates are polyfunctional compounds. They contain two types of functional
groups-hydroxyl and carbonyl. They may be polyhydroxy aldehydes or polyhydroxy ketones.

• Thus, Carbohydrates, also referred to as saccharides, are a group of naturally occurring carbonyl
(aldehydes or ketones) compounds (including their derivatives which produce such compounds on
hydrolysis) (aldehydes or ketones) that also contain several hydroxyl groups.

• Formation of carbohydrates in nature occurs in green plants by a process called photosynthesis.

FUNCTIONS OF CARBOHYDRATES
• Living organisms use carbohydrates as accessible energy to fuel cellular reactions. They arethe most
abundant dietary source of energy (4kcal/gram) for all living beings.

• Carbohydrates in addition to being the chief energy source, in many animals, are instant sources of
energy. Glucose is broken down by glycolysis/ Kreb’s cycle to yield ATP.

• Carbohydrates serve as energy storage forms and metabolic intermediates. They are stored as
glycogen in animals and starch in plants.

• They form structural and protective components, like in the cell wall of plants and
microorganisms. Structural elements in the cell walls of bacteria (peptidoglycan or murein), plants
(cellulose) and animals (chitin).
• Carbohydrates are intermediates in the biosynthesis of fats, proteins, vitamins, and antibiotics.

• Carbohydrates aid in the regulation of nerve tissue and is the energy source for the brain.

• Carbohydrates get associated with lipids and proteins to form surface antigens, receptor
molecules and cell membrane components that mediate some forms of intercellular
communications.

• Formation of the structural framework of RNA and DNA (ribonucleic acid and
deoxyribonucleic acid).

• They are linked to many proteins and lipids that are important in cell-cell communication,
immunity and in interactions between cells and other elements in the cellular environment.

• In animals, they are an important constituent of connective tissues.

 Classification of Carbohydrates
• The carbohydrates are divided into three major classes depending upon whether or not they
undergo hydrolysis and if they do, on the number of products formed.

1. Monosaccharides: The monosaccharides are polyhydroxy aldehydes or polyhydroxy ketones which

cannot be decomposed by hydrolysis to give simpler carbohydrates. e.g. Glucose, fructose, Galactose
etc.
2. Oligosaccharides: The oligosaccharides (Oligo: few) are carbohydrates which yield a definite
number (2-9) of monosaccharide molecules on hydrolysis.

a) Disaccharides - Which yield two monosaccharides molecules on hydrolysis. Which have molecular
formula is C12H22O11 .e.g. Sucrose, maltose etc

b) Trisaccharides - Which yield three monosaccharides molecules on hydrolysis and have molecular
formula is C18H32O16.
c) Tetrasaccharides - Which yield four monosaccharides molecules on hydrolysis and have molecular
formula is C22H42O21. eg: Stachyose [gal(α1→6)gal(α1→6)glu(α1↔2β)fru]

3. Polysaccharides: The carbohydrates which have higher molecular weight, which yield many
monosaccharide molecules on hydrolysis. E.g. Starch, glycogen, Dextrin, Cellulose etc.

In general monosaccharides and oligosaccharides are crystalline solids, soluble in water and sweet
to taste, they are collectively known as sugars, the polysaccharides on the other hand are
amorphous, insoluble in water and tasteless, they are called non-sugars.
Differences between Monosaccharides, Disaccharides and Polysaccharides
• Monosaccharides (simple sugars) can be classified according to the number of carbon atoms they contain.
Carbohydrates with an aldehyde as their most oxidized functional group are called aldoses,
whereas those with a keto group as their most oxidized functional group are called ketoses. For
example, glyceraldehyde is an aldose, whereas dihydroxyacetone is a ketose.

Carbohydrates that have a free carbonyl group have the suffix "-ose." [Note: Ketoses (with some
exceptions, for example, fructose) have an additional two letters in their suffix; “-ulose” for
example, xylulose.
Isomers and Epimers
Compounds that have the same chemical formula but have different structures are called isomers.
For example, fructose, glucose, mannose, and galactose are all isomers of each other, having the
same chemical formula, C6H12O6.

If two monosaccharides differ in configuration around only one specific carbon atom (with the
exception of the carbonyl carbon), they are defined as epimers of each other. For example,
glucose and galactose are C-4 epimers –their structures differ only in the position of the -OH
group at carbon 4.

Note: The carbons in sugars are numbered beginning at the end that contains the carbonyl
carbon— that is, the aldehyde or keto group.

Glucose and mannose are C-2 epimers. However, galactose and mannose are NOT epimers – they
differ in the position of -OH groups at two carbons (2 and 4) and are, therefore, defined only as
isomers
• Enantiomers
• A special type of isomerism is found in the pairs of structures that are mirror images of each
other. These mirror images are called enantiomers, and the two members of the pair are
designated as a D- and an L-sugar.

• The vast majority of the sugars in humans are D-sugars and the enzymes responsible for their
metabolism are specific for this configuration. In solution, glucose is dextrorotatory—hence the
alternative name dextrose.

• The L and D forms of the sugar depends on the orientation of the -H and -OH groups around
the carbon atom adjacent to the terminal primary alcohol carbon (carbon 5 in glucose)
determines whether the sugar belongs to the D or L series.

• When the -OH group on this carbon is on the right, then sugar is the D-isomer; when it is on
the left, then it is the L-isomer.
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 will be
rotated either to the right, dextrorotatory (+); or to the left, levorotatory (-). The direction of
rotation is independent of the stereochemistry of the sugar, so it may be designated D (-), D (+),
L (-), or L (+). For example, the naturally occurring formof fructose is the D (-) isomer.
• Pyranose and furanose ring structures:
• The stable ring structures of monosaccharides are similar to the ring structures of either pyran (a
six-membered ring) or furan (a five-membered ring). For glucose in solution, more than 99% is in
the pyranose form.

• "Pyranose" is used to refer to the pyran ring structure (6membered ring with 5 carbons and 1
oxygen)

• For five membered rings (four carbons and 1 oxygen) the structure is a furanose ring.

• Cyclization is reversible.

• The resulting chirality of the aldehyde carbon (or keto carbon in ketoses) in the cyclic structure
can be either the α or β- form. This carbon is termed the anomeric carbon, and the - and -
forms are anomers.

• The ring structure representations are termed "Haworth Projections". Cyclic structures can also
be represented using Fischer diagrams.
 Cyclization of Monosaccharides and Anomeric carbon
• Less than one percent of each of the monosaccharides with five or more carbons exists in the open-chain (acyclic)
form. Rather, they are predominantly found in a ring form, in which the aldehyde (or ketone) group has reacted with an
alcohol group on the same sugar.

• Formation of a ring results in the creation of an anomeric carbon at carbon 1 of an aldose or at carbon 2 of a ketose.
These structures are designated the α or β or configurations of the sugar, for example, α-D-glucose and β-D-
glucose. These two sugars are both glucose, but they are anomers of each other.

• Enzymes are able to distinguish between these two structures and use one or the other preferentially. For example,
glycogen is synthesized from whereas cellulose is synthesized from α-D-glucopyranose whereas cellulose is synthesized
from β-D-glucopyranose.

• The cyclic α and β anomers of a sugar in solution are in equilibrium with each other, and can be spontaneously
interconverted (a process called mutarotation).

• In the α configuration, the OH on the anomeric C projects to the same side as the ring in a modified Fischer projection
formula. In a Haworth projection formula of the α configuration, this OH is trans to the CH2OH group. Since the α
and β forms are not mirror images, they are referred to as diastereomers.
• Reducing Sugar
• The α and β refer to the configuration at the anomeric carbon atom. When the anomeric carbon of the
second residue takes part in the formation of the glycosidic bond, as in sucrose, the residue becomes a
glycoside known as a furanoside or pyranoside.

• As the disaccharide no longer has an anomeric carbon with a free potential aldehyde or ketone group, it
no longer exhibits reducing properties, where as the anomeric end of the glucose residue is not involved
in the glycosidic linkage it and, therefore, lactose remains a reducing sugar.

• If the oxygen on the anomeric carbon of a sugar is not attached to any other structure, that sugar can
act as a reducing agent and is termed a reducing sugar.

• Such sugars can react with chromogenic agents (for example, Benedict's reagent or Fehling's solution)
causing the reagent to be reduced and colored, with the anomeric carbon of the sugar becoming
oxidized. [Note: Only the state of the oxygen on the anomeric carbon determines if the sugar is
reducing or nonreducing—the other hydroxyl groups on the molecule are not involved.
 Glycosidic Bonds
• Monosaccharides can be joined to form disaccharides, oligosaccharides and polysaccharides.
• Important disaccharides include lactose (galactose + glucose), sucrose (glucose + fructose) and
maltose (glucose + glucose).
• The bonds that link sugars are called glycosidic bonds. These are formed by enzymes known as
glycosyltransferases that use nucleotide sugars such as UDP-glucose as substrates.
• Glycosidic bonds between sugars are named according to the numbers of the connected carbons
and also with regard to the position of the anomeric hydroxyl group of the sugar involved in the
bond.
• If this anomeric hydroxyl is in the α configuration, the linkage is an α-bond. If it is in the β
configuration, the linkage is a β-bond.
• Lactose, for example, forming a glycosidic bond between carbon 1 of β-galactose and carbon 4
of glucose. The linkage is, therefore, a β (1→4) glycosidic bond.
• Reactions of Carbohydrates

• Osazone formation: Osazone are carbohydrate derivatives when sugars are reacted with an
excess of phenylhydrazine. e.g. Glucosazone

• Benedict’s test: Reducing sugars when heated in the presence of an alkali gets converted to
powerful reducing species known as enediols. When Benedict’s reagent solution and reducing
sugars are heated together, the solution changes its color to orange-red/ brick red.

• Oxidation: Monosaccharides are reducing sugars if their carbonyl groups oxidize to give
carboxylic acids. In Benedict’s test, D-glucose is oxidized to D-gluconic acid thus, glucose is
considered a reducing sugar.

• Reduction to alcohols: The C=O groups in open-chain forms of carbohydrates can be

reduced to alcohols by sodium borohydride, NaBH4, or catalytic hydrogenation (H2, Ni,
EtOH/H2O). The products are known as “alditols”.
• Polysaccharides
• Monosaccharides can undergo a series of condensation reactions, adding one unit after another
to the chain until very large molecules (polysaccharides) are formed. This is called condensation
polymerisation, and the building blocks are called monomers.

• The majority of carbohydrate material in nature occur in the form of polysaccharides (also
known as glycans). Other molecules that contain polysaccharide structures are also referred to
as polysaccharides.
• - Homopolysaccharide. A polysaccharide whose monosaccharide units are identical.
• - Heteropolysaccharide. A polysaccharide made up of different monosaccharides
• The most common constituent of polysaccharides is D-Glucose
• Homopolysaccharides composed of glucose are called glucans; Those composed of mannose
are called mannans; etc.
• The characterization of polysaccharides includes their length, the type of
monosaccharide units, the linkages and branched nature
• The properties of a polysaccharide molecule depend on:
• i. Its length (though they are usually very long)
• ii. The extent of any branching (addition of units to the side of the chain rather than one of its
ends)
• iii. Any folding which results in a more compact molecule
• iv. Whether the chain is 'straight' or 'coiled’

• Starch is a glucan that has two polysaccharide forms: one is a linear molecule with α-1-4
linkages called amylose. The other is a branched form of amylose, where the branches have α -
1-6 linkages, called amylopectin.

• Starch, Glycogen and Cellulose are all polymers of glucose. They differ in the type of glucose
present and the bonds which link glucose monomers together, whereas Inulin is the polymer of
glucose and fructose
• Starch and Glycogen are made from alpha-glucose. This is an isomer of glucose in which
the hydroxyl (-OH) group attached to carbon number 1 is below the plane of the ring.
Whereas Cellulose are β-glucose monomer.
• The major form of storage polysaccharide in animals is glycogen (found in the liver and
skeletal muscle).
• The most common storage polysaccharide in plants is starch.
• Yeast and bacteria make dextran as a storage polysaccharide. It is composed of α-1-6
linkages of D-glucose, with branched chains (1-2, 1-3 or 1-4 linkages between glucose units).
Important component of dental plaque (from bacteria).