A carbohydrate is a biomolecule consisting of carbon (C), hydrogen (H) and oxygen (O) atoms,

usually with a hydrogen–oxygen atom ratio of 2:1 (as in water) and thus with the empirical
formula (CH2O)n (only molecules with n>4 are considered carbohydrates). The term carbohydrate is
itself a combination of the “hydrates of carbon”. They are also known as “Saccharides” which is a
derivation of the Greek word “Sakcharon” meaning sugar. The definition of carbohydrates in chemistry
is as follows:
“Optically active polyhydroxy aldehydes or polyhydroxy ketones or substances which give these
on hydrolysis are termed as carbohydrates”.
Carbohydrates are one of the three macronutrients in our diet (fat and protein being the others). They
exist in many forms and are mainly found in starchy foods such as bread, pasta, and rice, as well as in
some beverages, e.g. fruit juices and sugar-sweetened drinks. Carbohydrates represent the most
important source of energy for the body, and are vital for a varied and balanced diet.

Importance/Functions

The main function of carbohydrates is to provide energy, but they also play an important role in the
structure and function of cells, tissues and organs, as well in the formation of carbohydrate structures
on the surface of cells. The different molecular classes are the proteoglycans, the glycoproteins and
the glycolipids.

1. Energy source
One of the primary functions of carbohydrates is to provide your body with energy. Most of the
carbohydrates in the foods you eat are digested and broken down into glucose before entering the
bloodstream. Monosaccharides are absorbed by the small intestine into the bloodstream, where they
are then transported to their place of use. Disaccharides are broken down by digestive enzymes into
monosaccharides. The body also needs the help of digestive enzymes to break down the long chains
of starches into their constituent sugars which are then absorbed into the bloodstream. Glucose in the
blood is taken up into your body’s cells and used to produce a fuel molecule called adenosine
triphosphate (ATP) through a series of complex processes known as cellular respiration. Cells can then
use ATP to power a variety of metabolic tasks. Starches and sugars are the main energy-providing
carbohydrate sources and supply 4 kilocalories (17 kilojoules) per gram.
2. Storage
The human body uses carbohydrates in the form of glucose. If your body has enough glucose to fulfill
its current needs, excess glucose can be stored for later use. Glucose can be converted to glycogen,
a polysaccharide similar to starch, which is stored in the liver and the muscles and is a readily available
source of energy for the body. The brain and the red blood cells need glucose as an energy source,
since they cannot directly use fat, protein, or other forms of energy for this purpose. It is for this reason
that glucose in the blood must be constantly maintained at an optimum level. Approximately 130g of
glucose are needed per day to cover the energy needs of the brain. The liver contains approximately
100 grams of glycogen. These stored glucose molecules can be released into the blood to provide
energy throughout the body and help maintain normal blood sugar levels between meals. Unlike liver
glycogen, the glycogen in your muscles can only be used by muscle cells. It is vital for use during long
periods of high-intensity exercise. Muscle glycogen content varies from person to person, but it’s
approximately 500 grams.
3. Help Preserve Muscles
Muscle cells are crucial for body movement. Severe losses of muscle mass have been associated with
poor health and a higher risk of death. When glucose from carbohydrates is lacking, muscle can also
be broken down into amino acids and converted into glucose or other compounds to generate energy.
Consuming at least some carbohydrates in the diet is one way to prevent this starvation-related loss of
muscle mass. These carbohudrates will reduce muscle breakdown and provide glucose as energy for
the brain.
 4. Promote Digestive Health
Unlike sugars and starches, dietary fiber such as cellulose and pectin is not broken down into glucose.
Instead, this type of carbohydrate passes through the body undigested. Fiber is found in oats, legumes
and the inner part of fruits and some vegetables. While passing through the body, it draws in water and
forms a gel-like substance. This increases the bulk of your stool and softens it to help make bowel
movements easier.
5. Influence Heart Health
Eating plenty of dietary fiber can benefit your heart. As soluble fiber passes through the small intestine,
it binds to bile acids and prevents them from being reabsorbed. To make more bile acids, the liver uses
cholesterol that would otherwise be in the blood.
6. Structural carbohydrates
Most of the living organisms cell wall is made up of polysaccharides like cellulose in plants and chitin
in fungi. Carbohydrates covalently linked to proteins (glycoproteins) or lipids (glycolipids) are also a
part of cell membranes, and function as adhesion and address loci for cells.

CLASSIFICATION
The building blocks of all carbohydrates are sugars and they can be classified according to how many
sugar units are combined in one molecule.

On the basis of the number of forming units, three major classes of carbohydrates can be defined:
monosaccharides, oligosaccharides and polysaccharides.

1. Monosaccharides or simply sugars are formed by only one polyhydroxy aldehydeidic or ketonic unit.
The most abundant monosaccharide is D-glucose, also called dextrose. Monosaccharide
carbohydrates are those carbohydrates that cannot be hydrolyzed further to give simpler units of
polyhydroxy aldehyde or ketone. If a monosaccharide contains an aldehyde group then it is called
aldose and on the other hand, if it contains a keto group then it is called a ketose.
2. Oligosaccharides are formed by short chains of monosaccharidic units (from 2 to 20) linked one to the
next by chemical bounds, called glycosidic bounds. The most abundant oligosaccharides are
disaccharides, formed by two monosaccharides, and especially in the human diet the most important are
sucrose (common table sugar=Glucose+Fructose), lactose (Glucose+Galactose) and maltose
(Glucose+Glucose).
3. Polysaccharides are polymers consisting of 20 to 107 monosaccharidic units; they differ each other for
the monosaccharides recurring in the structure, for the length and the degree of branching of chains or
for the type of links between units.
Polysaccharides are further divided into –
a. Homopolysaccharides if they contain only one type of monosaccharide as starch, glycogen and
chitin
b. Heteropolysaccharides, instead, contain two or more different kinds of monosaccharide (e.g.
hyaluronic acid).
Physiological classification of carbohydrates

On the basis of their degree of polymerization, they can be classified as:

1. simple: mono- and disaccharides (also known as “sugars”) and tri- and tetrasaccharides
(oligosaccharides);
2. complex: the polysaccharides.

A further classification lays the foundations on the possibility of being used directly for energy
purpose, so:

1. available, as glucose, fructose, galactose between monosaccharides, sucrose, lactose, maltose

and maltodextrin between oligosaccharides, and starch and glycogen between polysaccharides;
2. not available, as xylose (monosaccharide), lactulose and raffinose (respectively di- and
trisaccharide), fiber (cellulose, hemicellulose, lignin, pectins etc.) and resistant or not digestible
starch (polysaccharides). The members of this class, also if ingested, are not digestible nor
absorbable and will be fermented by intestinal flora with release of short chain fatty acids and
so yielding some energy.

Based on Functional Group-

Monosaccharides are classified as well based on their functional groups.

1. If a monosaccharide contains a ketone group in an inner atom, then the monosaccharide is

classified as a ketose.
2. If a monosaccharide contains an aldehyde group at an end carbon, meaning a carbon at the end
of the chain in the Fischer projection, then the monosaccharide is classified as an aldose.

Based on Number of Carbon Atoms

Monosaccharides with three carbon atoms are called trioses, those with four are called tetroses, five
are called pentoses, six are hexoses, and so on. These two systems of classification (i.e based on
functional group and number of carbon atoms) are often combined. For example, glucose is an
aldohexose (a six-carbon aldehyde), ribose is an aldopentose (a five-carbon aldehyde), and fructose is
a ketohexose (a six-carbon ketone).

STRUCTURES OF MONOSACCHARIDES

Monosaccharides exists in two forms i.e. Fischer projections and Haworth projections. The Fischer
projections are open chain (linear chain) forms and Haworth projections are sugar molecules depicted
in their cyclic forms (ring-shaped), as shown in the following image. In aqueous solutions they are
usually found in ring forms.
FISCHER PROJECTION
The Fischer projection, devised by Emil Fischer in 1891, is a two-dimensional representation of a
three-dimensional monosaccharides by projection. The open chain form of monosaccharides is
illustrated with Fischer projections. A Fischer projection shows the skeleton of the acyclic
monosaccharide (Figure 3). Glucose is an aldohexose. This means that the top of the Fischer projection
of glucose contains an aldehyde group and that there are six carbons in the polyhydroxy chain.

The D and L Notation

The D/L system (named after Latin dexter means right and laevus means left). On a Fischer projection
of a monosaccharide, the penultimate ("next-to-last") carbon (alternatively, the last stereogenic carbon)
of D sugars are depicted with hydrogen on the left and hydroxyl on the right. L sugars will be shown
with the hydrogen on the right and the hydroxyl on the left.

HAWORTH PROJECTION

The predominant forms of ribose, glucose, fructose, and many other sugars in solution are not open
chains. Rather, the open-chain forms of these sugars cyclize into rings. In general, an aldehyde can
react with an alcohol to form a hemiacetal.

For an aldohexose such as glucose, the C-1 aldehyde in the open-chain form of glucose reacts with the
C-5 hydroxyl group to form an intramolecular hemiacetal. The resulting cyclic hemiacetal, a six-
membered ring, is called pyranose because of its similarity to pyran (Figure).
Similarly, a ketone can react with an alcohol to form a hemiketal.

The C-2 keto group in the open-chain form of a ketohexose, such as fructose, can form an
intramolecular hemiketal by reacting with either the C-6 hydroxyl group to form a six-membered cyclic
hemiketal or the C-5 hydroxyl group to form a five-membered cyclic hemiketal. The five-membered
ring is called a furanose because of its similarity to furan.

Alpha and Beta Notation

Glucose in a ring form can have two different arrangements of the hydroxyl group (−OH) around the
anomeric carbon (carbon 1 that becomes asymmetric in the process of ring formation). If the hydroxyl
group is below carbon number 1 in the sugar, it is said to be in the alpha (α) position, and if it is above
the plane, it is said to be in the beta (β) position.
 Anomeric Carbon

In the cyclic form of a sugar, the anomeric carbon is the carbon that was part of the carbonyl group in
the straight-chain structure. For example, the linear structure of glucose is

When the chain converts to a ring, C-1 becomes a chiral centre.

C-1 is the anomeric carbon.

In D-fructose, the carbonyl group is at C-2.

Here, C-2 is the anomeric carbon.

Mutarotation
The term “mutarotation” originates from the observed change in the optical rotation of the α- and β-
anomers of glucose upon dissolution in water. T he α- and β- forms slowly interconvert until equilibrium is
established.
 The alpha (α) anomer of D-glucose has a specific rotation of +112 degrees in water.
 The beta (β) anomer of D-glucose has a specific rotation of +19 degrees. (18.7 actually, but
rounding up to 19).
When either anomer is dissolved in water, the value of the specific rotation changes over time,
eventually reaching the same value of +52.5°.
 The specific rotation of α-D-glucopyranose decreases from +112° to +52.5°.
 The specific rotation of β-D-glucopyranose increases from +19° to +52.5°.
This behaviour is called mutarotation (literally, “change in rotation”).
 The equilibration occurs via the ring opening of the cyclic sugar at the anomeric center with the acyclic
form as the intermediate.

When the solutions whose specific rotations have changed to +52.5° are analyzed, they are found to
no longer consist of 100% alpha (α) or 100% beta (β) anomers, but instead a ratio of alpha (α) (36%)
and beta (β) (64% ) isomers.

REDUCING AND OXIDISNG PROPERTIES OF MONOSACCHARIDES

OXIDATION-

1. Glucose on oxidation with Br2 gives gluconic acid.

Br2+H2O HOBr+HBr

2. Glucose on further oxidation with HNO3 gives glucaric acid.(Saccharic acid)

3. Glucose on oxidation with hydrogen peroxide (H2O2) gives glucoronic acid.

Here only primary alcohol get oxidised to carboxylic group.
 Disaccharides
Disaccharides are those carbohydrates which on hydrolysis with acids or enzymes give two molecules
of monosaccharides which can either be same or different. The oxide linkage is formed after the loss
of the water molecule and then the two monosaccharides are formed by that linkage. When
two monosaccharide units are joined via the oxygen atom then that linkage is called a glycosidic
linkage.
In cyclic monosaccharides, Hydroxyl group formed as a result of formation of hemiacetal (i.e. –OH
group present on anomeric carbon) is more reactive than other –OH group on the glucose ring. This
reactive –OH group can reacts with C-1,C-2,C-3,C-4 or C-6 of another monosaccharide and form C1-
1,C1-2,C1-3,C1-4 or C1-6 linkage.
Disaccharides are formed from two monosaccharides and can be classified as either reducing or non
reducing. In a disaccharide molecule, if only one anomeric carbon of one monosaccharide unit is
involved in formation of glycosidic bond i.e. one anomeric carbon of other monosaccharide unit is free
then such disaccharide is called Reducing Sugar. E.g Maltose. End with free anomeric carbon is
reducing end and other is called non reducing end.
If both the anomeric carbons of two monosaccharide unit is involved in formation of glycosidic bond
i.e. no anomeric carbon of any monosaccharide unit is free then such disaccharide is called Non-
Reducing Sugar. E.g. Sucrose

1. Maltose:
Maltose is also one of the disaccharides which have two α -D-glucose units which are connected by
the first carbon of the glucose and also linked to the fourth carbon of another glucose unit i.e. C1-4
glycosidic linkage. In the solution, a free aldehyde can be produced at the first carbon of the second
glucose of the solution and it is a reducing sugar as it shows reducing properties.

Non Reducing End Reducing End

2. Sucrose
The sucrose molecule is unique among the common disaccharides in having an α-1,β-2-glycosidic
(head-to-head) linkage. Because this glycosidic linkage is formed by the OH group on the anomeric
carbon of α-D-glucose and the OH group on the anomeric carbon of β-D-fructose, it ties up the
anomeric carbons of both glucose and fructose.
This linkage gives sucrose certain properties that are quite different from those of maltose and lactose.
As long as the sucrose molecule remains intact, neither monosaccharide “uncyclizes” to form an open-
chain structure. Sucrose does not undergo reactions that are typical of aldehydes and ketones.
Therefore, sucrose is a nonreducing sugar.

Polysaccharides
A long chain of monosaccharides linked by glycosidic bonds is known as a polysaccharide (poly– =
“many”). The chain may be branched or unbranched, and it may contain different types of
monosaccharides. The molecular weight may be 100,000 daltons or more depending on the number of
monomers joined. Starch, glycogen, cellulose, and chitin are primary examples of polysaccharides. A
polysaccharide is also called a glycan.

Types of Polysaccharides
Polysaccharides can be broadly classified into two classes:
 Homo-polysaccharides – are made up of one type of monosaccharide units. ex: cellulose, starch,
glycogen.
 Hetero-polysaccharides – are made up of two or more types of monosaccharide units. ex.
hyaluronic acid and they provide extracellular support for organisms.
Starch
Starch is the most important source of carbohydrates in the human diet and accounts for more than
50% of our carbohydrate intake. It occurs in plants in the form of granules, and these are particularly
abundant in seeds (especially the cereal grains) and tubers, where they serve as a storage form of
carbohydrates.
Starch is a mixture of two polymers: amylose and amylopectin. Natural starches consist of about 10%–
30% amylose and 70%–90% amylopectin.
Amylose is a linear polysaccharide composed entirely of D-glucose units joined by the α-1,4-
glycosidic linkages. Amylose is not a straight chain of glucose units but instead is coiled like a spring,
with six glucose monomers per turn.
Amylopectin is a branched-chain polysaccharide composed of glucose units linked primarily by α-
1,4-glycosidic bonds but with occasional α-1,6-glycosidic bonds, which are responsible for the
branching. A molecule of amylopectin may contain many thousands of glucose units with branch
points occurring about every 25–30 units.

Glycogen
Glycogen is a large, branched polysaccharide that is the main storage form of glucose in animals and
humans. Glycogen is as an important energy reservoir; when energy is required by the body, glycogen
in broken down to glucose, which then enters the glycolytic or pentose phosphate pathway or is
released into the bloodstream.
Glycogen is a branched polymer of glucose. Glucose residues are linked linearly by α-1,4 glycosidic
bonds, and approximately every ten residues a chain of glucose residues branches off via α-1,6
glycosidic linkages. The α-glycosidic bonds give rise to a helical polymer structure.

Glycogen is an analogue of starch, which is the main form of glucose storage in most plants, but starch
has fewer branches and is less compact than glycogen.

This figures shows the structure of glycogen. Green circles represent α-1,6 linkages at branch points,
and red circles represent the nonreducing ends of the chain.