Homopolysaccharides

In general, homopolysaccharides have a well-defined chemical structure, although the molecular weight of an individual amylose or xylan molecule may vary within a particular range, depending on the source; molecules from a single source also may vary in size, because most polysaccharides are formed biologically by an enzyme-catalyzed process lacking genetic information regarding size.

The basic structural component of most plants, cellulose, is widely distributed in nature. It has been estimated that 50 billion to 100 billion tons of cellulose are synthesized yearly as a result of photosynthesis by higher plants. The proportion of cellulose to total carbohydrate found in plants may vary in various types of woods from 30 to 40 percent, and to more than 98 percent in the seed hair of the cotton plant. Cellulose, a large, linear molecule composed of 3,000 or more β-d-glucose molecules, is insoluble in water.

The chains of glucose units composing cellulose molecules are frequently aligned within the cell-wall structure of a plant to form fibre-like or crystalline arrangements. This alignment permits very tight packing of the chains and promotes their structural stability but also makes structural analysis difficult. The relationships between cellulose and other polysaccharides present in the cell wall are not well established; in addition, the presence of unusual chemical linkages or nonglucose units within the cellulose structure has not yet been established with certainty.

During the preparation of cellulose, raw plant material is treated with hot alkali; this treatment removes most of the lignin, the hemicelluloses, and the mucilaginous components. The cellulose then is processed to produce papers and fibres. The high resistance of cellulose to chemical or enzymatic breakdown is important in the manufacture of paper and cloth. Cellulose also is modified chemically for other purposes; e.g., compounds such as cellulose acetate are used in the plastics industry, in the production of photographic film, and in the rayon-fibre industry. Cellulose nitrate (nitrocellulose) is employed in the lacquer and explosives industries.

The noteworthy biological stability of cellulose is dramatically illustrated by trees, the life-span of which may be several thousand years. Enzymes capable of breaking down cellulose are generally found only among several species of bacteria and molds. The apparent ability of termites to utilize cellulose as an energy source depends on the presence in their intestinal tracts of protozoans that can break it down. Similarly, the single-celled organisms present in the rumina of sheep and cattle are responsible for the ability of these animals to utilize the cellulose present in typical grasses and other feeds.

Xylans are almost as ubiquitous as cellulose in plant cell walls and contain predominantly β-d-xylose units linked as in cellulose. Some xylans contain other sugars, such as l-arabinose, but they form branches and are not part of the main chain. Xylans are of little commercial importance.

The term starch refers to a group of plant reserve polysaccharides consisting almost exclusively of a linear component (amylose) and a branched component (amylopectin). The use of starch as an energy source by humans depends on the ability to convert it completely to individual glucose units; the process is initiated by the action of enzymes called amylases, synthesized by the salivary glands in the mouth, and continues in the intestinal tract. The primary product of amylase action is maltose, which is hydrolyzed to two component glucose units as it is absorbed through the walls of the intestine.

A characteristic reaction of the amylose component of starch is the formation with iodine of a complex compound with a characteristic blue colour. About one iodine molecule is bound for each seven or eight glucose units, and at least five times that many glucose units are needed in an amylose chain to permit the effective development of the colour.

The amylopectin component of starch is structurally similar to glycogen in that both are composed of glucose units linked together in the same way, but the distance between branch points is greater in amylopectin than in glycogen, and the former may be thought of as occupying more space per unit weight.

Carbohydrates. 1. Schematic amylopectin structure. 2.Schematic glycogen structure.

The applications of starches other than as foods are limited. Starches are employed in adhesive manufacture, and starch nitrate has some utility as an explosive.

Glycogen, which is found in all animal tissues, is the primary animal storage form of carbohydrate and, indirectly, of rapidly available energy. The distance between branch points in a glycogen molecule is only five or six units, which results in a compact treelike structure. The ability of higher animals to form and break down this extensively branched structure is essential to their well-being; in conditions known as glycogen storage diseases, these activities are abnormal, and the asymmetrical glycogen molecules that are formed have severe, often fatal, consequences. Glycogen synthesis and breakdown are controlled by substances called hormones.

Large molecules—e.g., pectins and agars—composed of galactose or its uronic-acid derivative (galacturonic acid) are important because they can form gels. Pectins, which are predominantly galacturonans, are produced from citrus fruit rinds; they are used commercially in the preparation of jellies and jams. Agar is widely employed in biological laboratories as a solidifying agent for growth media for microorganisms and in the bakery industry as a gelling agent; it forms a part of the diet of people in several areas of East Asia.

Dextrans, a group of polysaccharides composed of glucose, are secreted by certain strains of bacteria as slimes. The structure of an individual dextran varies with the strain of microorganism. Dextrans can be used as plasma expanders (substitutes for whole blood) in cases of severe shock. In addition, a dextran derivative compound is employed medically as an anticoagulant for blood.

Chitin is structurally similar to cellulose, but the repeating sugar is 2-deoxy-2-acetamido-d-glucose (N-acetyl-d-glucosamine) rather than glucose.

Carbohydrates. structure of N-acetyl-D-glucosamine.

Sometimes referred to as animal cellulose, chitin is the major component of the outer skeletons of insects, crustaceans, and other arthropods, as well as annelid and nematode worms, mollusks, and coelenterates. The cell walls of most fungi also are predominantly chitin, which comprises nearly 50 percent of the dry weight of some species. Since chitin is nearly as chemically inactive as cellulose and easily obtained, numerous attempts, none of which has thus far been successful, have been made to develop it commercially. The nitrogen content of the biosphere, however, is stabilized by the ability of soil microorganisms to degrade nitrogen-containing compounds such as those found in insect skeletons; these microorganisms convert the nitrogen in complex molecules to a form usable by plants. If such microorganisms did not exist, much of the organic nitrogen present in natural materials would be unavailable to plants.