Chemistry CARBOHYDRATES

Biomolecules :

All common activities of a living organism (bioactivity) involve reactions of certain organic compounds (mostly organic). Such compounds are called biomolecules. The important biomolecules are carbohydrates, lipids, proteins, vitamins, hormones, nucleic acids etc.They not only build up living system, but are also responsible for their growth, maintenance and their ability to reproduction.

The later part of 1950 resulted in classic advance in the knowledge of how living cells engage themselves with molecules such as carbohydrates additionally the metabolism of carbohydrates also became clarified. In Biochemistry Carbohydrates belong to basic category of chemical compounds.They are biological means of consuming energy or storing energy; other forms being via fat and protein.

Complex carbohydrates are known as polysaccharides. Amino acids and Peptides link in a head-to-tail style, i.e. the molecules are bounded by ionic interactions and H-bonds involving α-amino and α-carboxylate groups. Further, from several crystal structures it was confirmed that head to tail arrangement is unaffected by presence of water molecules. However, in the hydrated cases the case is different. Proteins and carbohydrates are essential constituents of our food. These biomolecules interact with each other and constitute the molecular logic of life processes. In addition, some simple molecules like vitamins and mineral salts also play an important role in the functions


Carbohydrates are the source that we rely on mostly for energy. We can encounter carbohydrates at almost every turn of our daily lives. The paper which we use is largely cellulose; so too is the cotton of our clothes and wood of our houses. So, carbohydrates meet all our basic necessities. The mystery of the energy in human body completely rests on the source carbohydrates.

Old Definition of carbohydrates
The group of compounds known as carbohydrates received their general name because of early observations that they often have the formula `C_x(H_2O)_y` - that is, they appear to be hydrates of carbon.

The above definition could not survive long due to the following reasons:

A number of compounds such as rhamnose, `(C_6H_(12)O_5)` and 2-deoxyribose `(C_5H_(10)O_4)` are known which are carbohydrates by their chemical behaviour but cannot be represented as hydrates of carbon.

There are other substances like formaldehyde `(HCHO, CH_2O)` and acetic acid `[CH_3COOH, C_2 (H_2O)_2]` which do not behave like carbohydrates but can be represented by the general formula, `C_x(H_2O)_y`.

New definition of carbohydrates
Carbohydrates are defined as polyhydroxy aldehydes or polyhydroxy ketones or substances which give these on hydrolysis and contain at least one chiral carbon atom. It may be noted here that aldehydic and ketonic groups in carbohydrates are not present as such but usually exist in combination with one of the hydroxyl group of the molecule in the form of hemiacetals and hemiketals respectively.

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.

Monosaccharides

The monosaccharides are polyhydroxy aldehydes or polyhydroxy ketones which cannot be decomposed by hydrolysis to give simpler carbohydrates. Examples are glucose and fructose, both of which have molecular formula, `C_6H_(12)O_(6)`.

`undersettext(glocose or fructose)(C_6H_(12)O_6) + H_2O overset(H^(+))->` No Reaction

The monosaccharides are the basis of carbohydrate chemistry since all carbohydrates are either monosaccharides or are converted into monosaccharides on hydrolysis. The monosaccharides are polyhydroxy aldehydes or polyhydroxy ketones. There are, therefore, two main classes of monosaccharides.

a) The Aldoses, which contain an aldehyde group `(-overset(overset(O)(||))(C)-H)`

b) The Ketoses, which contain a ketone group `(-overset(overset(O)(||))(C)-)`

The aldoses and ketoses are further divided into sub-groups on the basis of the number of carbon atoms in their molecules, as trioses, tetroses, pentoses, hexoses, etc. To classify a monosaccharide completely, it is necessary to specify both, the type of the carbonyl group and the number of carbon atoms present in the molecule. Thus monosaccharides are generally referred to as aldotrioses, aldotetroses, aldopentoses, aldohexoses, ketohexoses, etc.
The aldoses and ketoses may be represented by the following general formulas. See fig.1.

Glucose and fructose are specific examples of an aldose and a ketose. See fig.2.

See Table.

Oligosaccharides:

The oligosaccharides (Greek, oligo, few) are carbohydrates which yield a definite number (2-9) of monosaccharide molecules on hydrolysis. They include,

Disaccharides, which yield two monosaccharide molecules on hydrolysis. Examples are sucrose and maltose, both of which have molecular formula, `C_(12)H_(22)O_(11)`.

`undersettext(sucrose)(C_(12)H_(22)O_(11)) + H_2O overset(H^(+))-> undersettext(glucose)(C_6H_(12)O_6) + undersettext(fructose)(C_6H_(12)O_6)`

`undersettext(Maltose)(C_(12)H_(22)O_(11)) + H_2 O overset(H^(+))-> undersettext(glucose)(2 C_6 H_(12)O_6)`

Trisaccharides, which yield three monosaccharide molecules on hydrolysis. Example is raffinose, which has molecular formula, `C_(18)H_(32)O_(16)`.

`undersettext(reffinose)(C_(18)H_(32)O_(16)) +2 H_2O overset(H^(+))-> undersettext(glucose)(C_6 H_(12)O_6) + undersettext(fructose)(C_6 H_(12)O_6) + undersettext(galactose)(C_6 H_(12)O_6) `

Tetrasaccharides, etc.

Disaccharides

Carbohydrates which upon hydrolysis give two molecules of the same or different monosaccharides are called disaccharides. Their general formula is `C_(12)H_(22)O_(11)`. The three most important disaccharides are sucrose, maltose, and lactose. Each one of these on hydrolysis with either an acid or an enzyme gives two molecules of the same or different monosaccharides as shown below:

`undersettext(Sucrose)(C_(12)H_(22)O_(11)) + H_2O undersettext(or invertase)overset(H^(+))-> undersettext(Glucose)(C_6H_(12)O_6) + undersettext(fructose)(C_6H_(12)O_6)`

`underset(Maltose)(C_(12)H_(22)O_(11)) + H_2O undersettext(or Maltose)overset(H^(+))-> undersettext(Glucose)(C_6H_(12)O_6) + undersettext(Glucose)(C_6H_(12)O_6)`

`undersettext(Lactose)(C_(12)H_(22)O_(11)) + H_2O undersettext(or Lactose)overset(H^(+))-> undersettext(Glucose)(C_6H_(12)O_6) + undersettext(Glactose)(C_6H_(12)O_6)`

Disaccharides may also be considered to be formed by a condensation reaction between two molecules of the same or different monosaccharides with the elimination of a molecule of water. This reaction involves the formation of an acetal from a hemiacetal and an alcohol – in which one of the monosaccharides acts as the hemiacetal while the other acts as the alcohol.

Sucrose

It is formed by condensation of one molecule of glucose and one molecule of fructose. Unlike maltose and lactose, it is non-reducing sugar since both glucose (C1 - α) and fructose (C2 -β) are connected to each other through their reducing centres. Its structure is shown below:
Hydrolysis: (Invert Sugar or Invertose). Hydrolysis of sucrose with hot dilute acid yields D-glucose and D-fructose. See fig.1.

Sucrose is dextrorotatory, its specific rotation being +66.5%, D-glucose is also dextrorotatory, [α]D = +53°, but D-fructose has a large negative rotation, [α]D = -92°. Since D-fructose has a greater specific rotation than D-glucose, the resulting mixture is laevorotatory. Because of this the hydrolysis of sucrose is known as the inversion of sucrose, and the equimolecular mixture of glucose and fructose is known is invert sugar or invertose. See fig.2.

Polysaccharides

The polysaccharides are carbohydrates of high molecular weight which yield many monosaccharide molecules on hydrolysis. Examples are starch and cellulose, both of which have molecular formula, `(C_6H_(10)O_5)_n` .

`undersettext(starch)((C_6H_(10)O_5)_n) +nH_2O overset(H^(+))-> undersettext(glucose)(nC_6H_(12)O_6)`

In general, the 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. The carbohydrates may also be classified as either reducing or non-reducing sugars. All those carbohydrates which have the ability to reduce Fehling’s solution and Tollen’s reagent are referred to as reducing sugars, while others are non-reducing sugars. All monosaccharides and the disaccharides other than sucrose are reducing sugars.Polysaccharides are formed when a large number (hundreds to even thousands) of monosaccharide molecules join together with the elimination of water molecule. Thus, polysaccharides may be regarded as condensation polymers in which the monosaccharides are joined together by glycosidic linkages.

Some important polysaccharides are:

1. Cellulose

2. Starch

3. Glycogen

4. Gums and

5. Pectins

6. Starch

It is a polymer of glucose. Its molecular formula is (C6H10O5)n where the value of n (200 – 1000) varies from source to source. It is the chief food reserve material or storage polysaccharide of plants and is found mainly in seeds, roots, tubers, etc. Wheat, rice, potatoes, corn, bananas etc., are rich sources of starch.
Starch is not a single compound but is a mixture of two components – amylose (10 to 20%) and amylopectin (20 to 80%). Both amylose and amylopectin are polymers of α-D-glucose.

Amylose is a linear polymer of α-D-glucose. It contains about 200 glucose units which are linked to one another through α-linkage involving C1 of one glucose unit with C4 of the other as shown below: See fig.1.

Amylopectin, on the other hand, is a highly branched polymer. It consists of a large number (several branches) of short chains each containing 20-25 glucose units which are joined together through α-linkages involving C1 of one glucose unit with C4of the other. The C1 of terminal glucose unit in each chain is further linked to C6 of the other glucose unit in the next chain through C1 – C6 α-linkage. This gives amylopectin a highly branched structure as shown below- See fig.2.

Hydrolysis: Hydrolysis of starch with hot dilute acids or by enzymes gives dextrins of varying complexity, maltose and finally D-glucose. Starch does not reduce Tollen’s reagent and Fehling’s solution.

Uses: It is used as a food. It is encountered daily in the form of potatoes, bread, cakes, rice etc. It is used in coating and sizing paper to improve the writing qualities. Starch is used to treat textile fibres before they are woven into cloth so that they can be woven without breaking. It is used in manufacture of dextrins, glucose and ethyl alcohol. Starch is also used in manufacture of starch nitrate, which is used as an explosive.

 
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