Carbohydrates:

Carbohydrates are a group of organic compounds consisting of C, H, O usually in the ratio of 1: 2: 1 and include such
well known compounds as sugars, starch, cellulose etc.

Carbohydrates were regarded as hydrates of carbon and corresponded to general formula (C.H 2O) n.
But the group name ‘carbohydrates’ was sometimes found mislead­ing because

• Some organic compounds e.g., formaldehyde (HCHO), acetic acid (CH 3COOH), lactic acid (C3H6O1) inositol (C6H12O6) etc.
correspond to the general formula but are not carbohydrates.

• Some carbohydrates e.g., rhamnose (C6H12O5), rhamnohexose (C7H14O6), digitoxose (C6H12O4) do not correspond to the above
general formula
• Besides containing C, H and O, some carbohydrates also contain nitrogen and sul­phur

Therefore, the carbohydrates are more appropriately referred to as polyhydroxyaldehydes or polyhydroxyketones and their
derivatives or the substances which yield these on hydroly­sis. But, the group name ‘carbohydrates’ is still retained
traditionally
Monosaccharide’s (Simple sugars):

Monosaccharides are polyhydroxyaldehydes or polyhydroxyketones containing 3-7 carbons.

Monosaccharide’s are the basic units, of carbohydrate which cannot be further hydrolyzed into simpler saccharides
On the basis of carbonyl group, monosaccharides are of two types
Aldoses (contain terminal aldehyde, —CHO)

Ketoses (contain subterminal ketone, > C= O).

Sugars with 3,4,5,6 and 7 carbon atoms are called trioses, tetroses, pentoses, hexoses and heptoses respectively.

2. Oligosaccharides:
i. These consist of more than one but fewer number of monosaccharide molecules joined together by glycosidic bonds.
ii. On hydrolysis, they yield the monosaccharide units which may be similar or dissimilar.
iii. These are also sweet tasting, crystalline, soluble sugars.
iv. These may or may not have a free -OH group at the reducing centre and accordingly may or may not be reducing.
oligosaccharides are grouped in following categories:
(i) Disaccharides. C12H22O11 (e.g., sucrose, maltose, lactose etc.)
(ii) Trisaccharides, C18H32O16 (e.g., raffinose, gentianose etc.)

3. Polysaccharides:
i. These consist of a large number of (often thousands) monosaccharide units to form branched or un-branched chains.
ii. These can be hydrolysed to yield monosaccharide units which are usually similar.
iii. These are usually amorphous, tasteless, non-sugars and insoluble in water.
 Polysaccharides can be grouped into two categories:
(i) Structural Polysaccharides (e.g., cellulose, hemi-cellulose, pectic substances, chitin, gum, mucilage etc.)
(ii) Storage Polysaccharides (e.g., starch, inulin, glycogen etc.)

Properties of monosaccharides:

1. All monosaccharides are colourless, crystalline, water soluble, sweet in taste and low MW organic compounds.

2. Isomerism:
Except dihydroxyacetone, all monosaccharides have asymmetric or chiral carbon atoms
(carbon atoms attached to four different atoms). This allows the formation of stereoisomers or in short, isomers.
Stereoisomers have the same structural formula but differ in spatial configuration.

The important isomers of monosaccharide’s are as follows:

D- and L-isomers:
D-sugars and L-sugars are optical isomers.

In biological systems all sugars are found in D-forms.

The optical activity is due to the asymmetric carbon atoms which can be able to rotate the plan of polarized light to
either left (levorotatory) or right (dextrorotatory).

Hence the mono saccharides are two types i.e. L-sugars and D-sugars

The D-sugars can be represented by the orientation of-OH group of asymmetric

carbon farthest from aldehyde or ketone group is on right

When it is on left, it is a member of L-sugars.

D-sugars are mirror images of L-sugars, they are called enantiomers

Open Chain and Ring Forms of Monosaccharides:

Many monosaccharide’s e.g ribose, glucose, fructose etc. exist both in open straight chain and ring form.

If the ring is 5-membered it is called as furanose sugar. Sugar with a 6-membered ring is called as pyranose sugar

Ring-forms are two types, pyranose and furanose.

Pyranose is 6-membered sugar ring similar to pyran with five carbon atom and one oxygen atom.

While furanose is 5-membered sugar ring similar to furan with four carbon atom and one oxygen atom
Glycosidic bond:
Glycosidic bond is a covalent bond formed by the condensation reaction between a sugar and the -OH group of a second
compound which may or may not be the sugar

Glycosidic bonds are of two types i.e. O- glycosidic bond (-C-0- C) and N-Glycosidic bond (-C-N-C).
Sugar can be joined to each other by O-glycosidic bonds to form disaccharides, oligosaccharides and polysaccharides
Disaccharides (Double sugars):

Disaccharides are composed of 2 monosaccharide’s linked by O-glycosidic bond.

The physiologically important disaccharides are:

Maltose (malt sugar) = Glucose + Glucose
Lactose (milk sugar) = Galactose + Glucose
Sucrose (cane sugar) = Glucose + Fructose

Maltose is a reducing disaccharide composed of two glucose units linked by α1,4-glycosidic bond.
The reducing property of maltose is due to free aldehyde group of C-l of second glucose.
Maltose is an enzymatic hydrolysis product of starch.
It is formed in the germinating cereals by enzyme diastase (an amylase)
and also formed during starch digestion by α-amylases of salivary and pancreatic juices

Lactose is also a reducing disaccharide consists of galactose joined to glucose by a β 1,4 glycosidic bond.
Its reducing nature is due to free aldehyde of C-l of glucose residue.
Lactose present naturally in milk of mammals where its concentrations vary from 0-7%, depending on species.

Sucrose is a non-reducing disaccharide as it lacks any free reducing group in contrast to other sugars.
It is commercially extracted from sugarcane and beet roots.
It is the principal form of carbohydrate transported from source (leaves) to sink (site of utilization) in higher plants.
Sucrose is dextrorotatory but on hydrolysis by sucrase produces a mixture of equal amount of glucose and fructose which
is laevorotatory.
Structural Polysaccharides:
They are the macromolecules that perform architectural functions in plant cell wall and skeleton of animals
 Cellulose is the structural polysaccharide of plant cell walls, some protists and tunic of urochordates.

Each cellulose chain is a linear glucan of about 2000-25,000 D-glucose residues joined by β1→4 glycosidic linkages
Chitin (fungal cellulose):
Chitin is the main structural polysaccharides of the exoskeletons of arthropods and also in the cell wall of most fungi and algae
. Chitin is a linear polymer of N-acetyl-glucosamine (NAM) residues in/β→4 linkage. Structurally chitin is similar to cellulose.
It becomes hard when impregnated with CaCO3 and proteins. Chitin is soft leathery and provides strength and elasticity
Storage Polysaccharides:
These polysaccharides serve as reserve food. At the time of need, they are hydrolyzed to release sugars available to the living
cells for respiration and biosynthesis.
(i) Dextran:
It is the storage polymer in bacteria and yeasts. Dextran is a glucosan where the glucose resides are linked by αl-6
linkage

with occasional branches occur by αl-4 linkages. Dextrans are non-toxic hence used chemically as substitute of plasma
proteins.
(ii) Levan:

It is the storage polysaccharides in bacteria. Levan is a fructosan composed of fructose residue joined by 2-6 linkages.
(iii) Starch (=amylum):

Starch is a mixture of glucans that synthesized as end product of photosynthesis.

It is stored in form of insoluble granules (starch grains) in chloroplasts, amyloplasts and cytoplasm of plant cells.

Glycogen (animal starch):

Glycogen in the storage polysaccharide of animals that present in all cells but most prevalent in
liver and muscles where it occurs as cytoplasmic granules usually associated with SER.