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As the name implies, polysaccharides are large high-molecular weight molecules constructed by joining monosaccharide units together by glycosidic bonds. They are sometimes called glycans. The most important compounds in this class, cellulose, starch and glycogen are all polymers of glucose. This is easily demonstrated by acid-catalyzed hydrolysis to the monosaccharide. Since partial hydrolysis of cellulose gives varying amounts of cellobiose, we conclude the glucose units in this macromolecule are joined by beta-glycoside bonds between C-1 and C-4 sites of adjacent sugars. Partial hydrolysis of starch and glycogen produces the disaccharide maltose together with low molecular weight dextrans, polysaccharides in which glucose molecules are joined by alpha-glycoside links between C-1 and C-6, as well as the alpha C-1 to C-4 links found in maltose. Polysaccharides built from other monosaccharides (e.g. mannose, galactose, xylose and arabinose) are also known, but will not be discussed here.
Over half of the total organic carbon in the earth's biosphere is in cellulose. Cotton fibers are essentially pure cellulose, and the wood of bushes and trees is about 50% cellulose. As a polymer of glucose, cellulose has the formula (C6H10O5)n where n ranges from 500 to 5,000, depending on the source of the polymer. The glucose units in cellulose are linked in a linear fashion, as shown in the drawing below. The beta-glycoside bonds permit these chains to stretch out, and this conformation is stabilized by intramolecular hydrogen bonds. A parallel orientation of adjacent chains is also favored by intermolecular hydrogen bonds. Although an individual hydrogen bond is relatively weak, many such bonds acting together can impart great stability to certain conformations of large molecules. Most animals cannot digest cellulose as a food, and in the diets of humans this part of our vegetable intake functions as roughage and is eliminated largely unchanged. Some animals (the cow and termites, for example) harbor intestinal microorganisms that breakdown cellulose into monosaccharide nutrients by the use of beta-glycosidase enzymes.
Cellulose is commonly accompanied by a lower molecular weight, branched, amorphous polymer called hemicellulose. In contrast to cellulose, hemicellulose is structurally weak and is easily hydrolyzed by dilute acid or base. Also, many enzymes catalyze its hydrolysis. Hemicelluloses are composed of many D-pentose sugars, with xylose being the major component. Mannose and mannuronic acid are often present, as well as galactose and galacturonic acid.
Starch is a polymer of glucose, found in roots, rhizomes, seeds, stems, tubers and corms of plants, as microscopic granules having characteristic shapes and sizes. Most animals, including humans, depend on these plant starches for nourishment. The structure of starch is more complex than that of cellulose. The intact granules are insoluble in cold water, but grinding or swelling them in warm water causes them to burst.
The released starch consists of two fractions. About 20% is a water soluble material called amylose. Molecules of amylose are linear chains of several thousand glucose units joined by alpha C-1 to C-4 glycoside bonds. Amylose solutions are actually dispersions of hydrated helical micelles. The majority of the starch is a much higher molecular weight substance, consisting of nearly a million glucose units, and called amylopectin. Molecules of amylopectin are branched networks built from C-1 to C-4 and C-1 to C-6 glycoside links, and are essentially water insoluble. Representative structural formulas for amylose and amylopectin are shown above. The branching in this diagram is exaggerated, since on average, branches only occur every twenty five glucose units.
Hydrolysis of starch, usually by enzymatic reactions, produces a syrupy liquid consisting largely of glucose. When cornstarch is the feedstock, this product is known as corn syrup. It is widely used to soften texture, add volume, prohibit crystallization and enhance the flavor of foods. Glycogen is the glucose storage polymer used by animals. It has a structure similar to amylopectin, but is even more highly branched (about every tenth glucose unit). The degree of branching in these polysaccharides may be measured by enzymatic or chemical analysis.
Prof. Steven Farmer (Sonoma State University)
William Reusch, Professor Emeritus (Michigan State U.), Virtual Textbook of Organic Chemistry