chapter XIV
). But for the present, it will be sufficient to note that it seems to be necessary that the enzyme shall actually fit the molecular arrangement of the compound at all points, in the same way that a key fits its appropriate lock; or a still better illustration is that of the fitting of a glove to the hand. On the basis of the latter illustration, it is just as impossible for a dextro-enzyme to affect a levo-sugar, or for [alpha]-glucase to affect a [beta]-glucoside, as it is to fit a right-hand glove upon a left hand. Further attention will be given to these matters in later chapters.
POLYSACCHARIDES
The polysaccharides which, like the simpler saccharides, or sugars, which have thus far been studied, undoubtedly serve as reserve food for plants, are known under the general name of "starches." They are substances of high molecular weight, whose constitution is represented by the general formula (C_{6}H_{10}O_{5})_{n}. It should be noted that an exactly accurate formula should be (C_{6})_{n}(H_{12}O_{6})_{n-1}; but since the value of _n_ is very high, the simpler formula is approximately correct. The value of _n_ has not been accurately determined for any of the individual members of the group, but is probably never less than 30 and may often be 200 or more. The fact that these compounds are insoluble in most of the solvents which can be used for molecular weight determinations makes it difficult to determine their actual molecular constitution.
When completely hydrolyzed, the polysaccharides yield only hexoses. They are, therefore, technically known as "hexosans." Each individual polysaccharide which has been studied thus far yields only a single hexose, although the particular hexose obtained varies in different cases. In fact, the polysaccharides are often classified according to the hexoses which they yield on hydrolysis, into the following groups: the dextrosans, which yield glucose, and include starch, dextrin, glycogen, lichenin, etc.; the levulosans, which yield fructose, and include inulin, graminin, triticin, etc.; the mannans; and the galactans. The more common representatives of each of these groups are discussed below.
(A) THE DEXTROSANS
These are by far the most common type of polysaccharides to be found in plants.
=Starch.=--It is probable that no other single organic compound is so widely distributed in plants as is ordinary starch. It is produced in large quantities in green leaves as the temporary storage form of photosynthetic products. As a permanent reserve food material, it occurs in seeds, in fruits, in tubers, in the pith, medullary rays and cortex of the stems of perennials, etc. It constitutes from 50 to 65 per cent of the dry weight of seeds of cereals, and as high as 80 per cent of the dry matter of potato tubers.
Starch occurs in plant tissues in the form of microscopic granules, composed of concentric layers, there being apparently alternate layers of two types of carbohydrate material, which have been distinguished from each other by several different pairs of names used by different authors: thus, Nägeli uses the terms "granulose" and "amylocellulose"; Meyer, "[alpha] and [beta] amylose"; Wolff, "amylo-cellulose" and "amylo-pectin"; while Kramer asserts that the layers are alternate lamella of crystalline and colloidal starch. Many theories as to the nature of these concentric layers and their mode of deposition have been advanced, but it would not be profitable to discuss them in detail here.
For purposes of study, starch may be prepared from the ground meal of cereals, potatoes, etc., by kneading the meal in a bag or sieve of fine-meshed muslin or silk, under a slow stream of water. The starch granules, being microscopic in size, readily pass through the cloth with the water, and may be caught in any suitable container. The starch is then allowed to settle to the bottom, the water poured off and the starch collected and dried.
Starch is insoluble in water; but if boiled in water, the granules burst and a slimy opalescent mass, known as "starch paste," is obtained. This is undoubtedly a colloidal suspension of the starch in water. By various processes, such as boiling with very dilute acids, treatment with acetone, etc., starch is converted into "soluble starch" which dissolves in water to a clear solution. Soluble starch is precipitated out of solution by alcohol, or by lead subacetate solution.
Air-dried starch contains from 15 to 20 per cent of water; but this can be completely removed, without altering the starch in any way, by heating for some time at 100° C.
The starch granules from different sources vary considerably in size and shape, and can generally be identified by observation under the microscope.
The most characteristic reaction of starch is the blue color which it gives with iodine. The reaction is most marked with starch paste or soluble starch, but even dry starch granules are colored blue when moistened with a solution of iodine in water containing potassium iodide, or with tincture of iodine.
When hydrolyzed, either by boiling with dilute acids or under the influence of enzymes, starch undergoes a series of decompositions, yielding first dextrins, then maltose, and finally glucose. These transformations can be traced by the iodine color reaction, as starch will show its characteristic blue, dextrins purple or rose-red, and maltose and glucose no color with iodine.
=Dextrins= may occur in plants as transition products in the transformation of starch into sugars, or _vice versa_. Most commonly, however, they are artificial products resulting from the partial hydrolysis of starch in the laboratory or factory. They are amorphous substances, which are readily soluble in water, forming sticky solutions which are often used as adhesives ("library paste" is a common example of a very concentrated preparation of this kind). They are precipitated from solution by alcohol, but not by lead subacetate (distinction from starch). They are strongly dextrorotatory (specific rotatory power +192° to +196°); are not fermented by yeast alone, but readily undergo hydrolysis to glucose which does ferment. There are several different modifications, or forms, of dextrins, depending upon the extent to which the simplification of the starch molecule by hydrolysis is carried. Three fairly definite forms are generally recognized, as follows: _amylo-dextrin_, or soluble starch, slightly soluble in cold water, readily so in hot water, giving a blue color with iodine; _erythro-dextrin_ easily soluble in water, neutral taste, red color with iodine; and _achroo-dextrin_, easily soluble in water, sweetish taste, no color with iodine.
Commercial dextrin, which is much used in the preparation of mucilages and adhesive pastes, is prepared by heating dry starch to about 250° C. It is composed chiefly of achroo-dextrin, mixed with varying quantities of erythro-dextrin and glucose.
=Glycogen=, or "animal starch," is one of the most widely distributed reserve foods of the animal body; in fact, it is the only known form of carbohydrate-reserve in animal tissues. But it is present only rarely in plants. It occurs in certain fungi, particularly in yeasts. In the animal body, glycogen is found in all growing cells; also in the muscles and blood; but most largely in the liver, where it is stored in large quantities. The glycogen found in yeasts is identical with that found in animal tissues. The quantity of glycogen in a yeast cell increases rapidly as the yeast grows during the fermentation process.
Glycogen is a white, amorphous compound, readily soluble in hot water, forming an opalescent solution similar in appearance to the solutions of soluble starch. It is strongly dextrorotatory (specific rotatory power +190°), is colored brown by iodine, and is hydrolyzed to dextrin and maltose, and finally to glucose.
=Lichenin=, =para dextran=, and =para isodextran= are dextrosans which have been isolated from various lower plants. They all yield glucose when completely hydrolyzed. They resemble starch in chemical properties, but differ from it in physical form, etc.
(B) LEVULOSANS
=Inulin= replaces starch as the reserve food carbohydrate in a considerable number of natural orders of plants, particularly in the Compositae. It is the carbohydrate of the tubers of the dahlia and artichoke and of the fleshy roots of chicory. It is often found associated with starch in monocotyledonous plants, such as many species of _Iris_, _Hyacinthus_, and _Muscari_. Among the monocotyledons, starch seems to be the characteristic carbohydrate reserve of aquatic, or moisture-loving, species, while inulin is more common among those which prefer dry situations.
Inulin may be prepared from the tubers of dahlias or artichokes, by boiling the crushed tubers with water containing a little chalk (to precipitate mineral salts, albumins, etc.) filtering and cooling the filtrate practically to the freezing point, which precipitates the inulin.
Inulin is a white, tasteless, semi-crystalline powder, which is soluble in hot water, from which it may be precipitated by alcohol or by freezing. It forms no paste like that of starch or dextrin, and gives no color with iodine. It is levorotatory, and when hydrolyzed by acids or by the enzyme _inulinase_ yields fructose; in fact, inulin bears the same relation to fructose that starch does to glucose.
=Graminin, irisin, phlein, sinistrin, and triticin= are all inulin-like polysaccharides, which have been found in the plants after which they are named. Their solutions are, as a rule, sticky or gummy in consistency, which suggests that these compounds bear the same relation to inulin that dextrins do to starch.
(C) MANNOSANS, OR MANNANS
=Mannan= bears the same relation to mannose that starch does to glucose and inulin to fructose. It occurs as a reserve food substance in many plants. It has been reported as present in moulds, and in ergot; in the roots of asparagus, chicory, etc.; in the leaves and wood of many trees, such as the chestnut, apple, mulberry, and many conifers; also as a part of the so-called "hemi-celluloses" which are present in the seeds of many plants, notably the palms, the elders, cedar, larch, etc.
It is a white, amorphous powder, which is difficultly soluble in water, is strongly dextrorotatory (specific rotatory power +285°), and when hydrolyzed yields mannose.
=Secalin= (or carubin) is a substance which is found in the seeds of barley, rye, etc., which is similar to mannan, but is optically inactive.
(D) GALACTANS
These bear the same relation to galactose that the preceding dextrosans do to their constituent hexoses. Four different galactans have been isolated from plant tissues; they are all white, amorphous solids which dissolve with difficulty in water, forming gummy solutions.
Both galactans and mannans commonly occur associated with cellulose and hemi-celluloses in the seeds or other storage organs of plants. They are practically indigestible by animals, as the proper enzymes to hydrolyze them are not present in the digestive tract; hence, they are commonly classed with the indigestible cellulose as the "crude fiber" of plants which are to be used as food by animals.
PHYSIOLOGICAL USE AND BIOLOGICAL SIGNIFICANCE OF CARBOHYDRATES
If the organic compounds produced by plants be classified with reference to their uses in metabolism into the three groups known, respectively, as temporary foods, storage products, and permanent structures, it is clear that the carbohydrates which have been discussed in this chapter may fall into either one of the first two of these classes. There can be no doubt that the first products of photosynthesis, whichever ones they may be in different plants, may be directly used as temporary foods, to furnish the energy and material for the building up of permanent structures. Also, there can be no doubt that these same carbohydrates are translocated to the storage organs and accumulated for later use by the same plant (as, for example, in the case of the perennials), or by the next generation of the plant (when the storage is in the endosperm adjoining the embryo of the seed).
There is no known explanation as to why different species of plants make use of different carbohydrates for these purposes; or why certain species elaborate starch out of the same raw materials from which other species produce sugars, inulin, or glycogen, etc.
In general, starch is the final product of photosynthesis in most green plants; but there are many exceptions to this. The polysaccharides, which are generally insoluble, must be broken down into the simpler soluble sugars before they can be translocated to other organs of the plant for immediate, or future, use. When they reach the storage organs, they may be recondensed into insoluble polysaccharides, or stored as soluble sugars. Examples of the latter type of storage are, sucrose in beet roots, glucose in onion bulbs, etc. Sometimes, this habit of storage seems to be a species characteristic; as potatoes store starch, while beets, growing in the same soil and under exactly the same environment, store sugar. But in other cases, the nature of the carbohydrate stored undoubtedly is correlated with the external temperatures at the time of storage. It has been shown that cold, which tends to physiological dryness, very frequently favors the storage of sugars instead of starches. Thus, in temperate zones, among aquatic, or moisture-loving plants, those species which hibernate during the winter at the bottom of lakes or ponds and are killed by temperatures below freezing, store starch and no sugar; while in the same ponds, the species whose storage organs pass the winter above the level of the water and can withstand temperatures as low as -7° C. contain sugar during the winter months, even if they contain starch during warmer periods. Similarly, sugars often appear in the leaves and stems of conifers during the winter months, only to disappear, or be replaced by starch, when spring approaches. This same phenomenon is noticeable in arctic plants, which generally contain but small proportions of starch and relatively large amounts of sugars.
Similarly, the phenomenon of the turning sweet of potatoes when exposed to low temperatures has often been noted. The change of the starch in potato tubers to sugar is most rapid at the temperature of 0° C., and ceases at 7°, or above. Also, if potatoes in which the maximum amount of sugar is present (not over one-sixth of the total starch can be converted into sugar) are exposed to a higher temperature the sugar soon disappears.
In general, however, it may be said that each particular species of plant has its own particular preference for a specific carbohydrate as its reserve food material, and elaborates the proper enzymes to make it possible to utilize this particular carbohydrate for its metabolic needs.
Again, the question as to whether the storage of energy-producing materials for the use of the next generation shall be in the form of carbohydrates or of fats seems to be definitely connected with the size of the seed, and the consequent available storage space (see page 138). Animals habitually use the space-conserving form of fats for their energy-storage, while plants more commonly use carbohydrates for this purpose, except in the case of those small seeds in which sufficient energy cannot be stored in carbohydrate form to develop the young seedling to the point where it can manufacture its own food. As a general rule, nuts, which contain the embryo of slow-growing seedlings, and need large proportions of energy reserve, are characteristically _oily_ instead of _starchy_ in type.
But, aside from temperature reactions and space requirements, there is no law which has yet been discovered which determines the character of the energy-storage compound which any given species of plant will elaborate. The process of photosynthesis would seem to be identical in all cases, at least up to the point of the production of the first hexose sugar; but the transformation of glucose into other monosaccharides, disaccharides, and polysaccharides seems to be a matter which obeys no rule or law.
Finally, there remains to be considered the occurrence and uses of sugars in the fleshy tissues of fruits. These tissues have, of course, no direct function in the life history of the plant. They surround the seed, but they must decay or be destroyed before the seed can come into the proper environment for germination and growth. In most fruits, starch is the form in which the carbohydrate material is first deposited in the green tissue, but as the fruit ripens the starch rapidly changes into sugars, with the result that the fruit takes on a flavor which makes it much more attractive as a food for men and animals. This purely biological significance of the presence of sugars (and of the other substances which give desirable flavors to fruits, vegetables, etc.), can have no possible relation to the physiological needs of the individual plant, however.
It is apparent that the production of these immense stores of reserve food by plants makes them useful as food for animals, and it is, of course, the storage parts of the plants which are most useful for this purpose. This biological relationship needs no further emphasis.
REFERENCES
ABDERHALDEN, E.--"Biochemisches Handlexikon, Band 2 ... Die Einfachen Zuckerarten, Inuline, Cellulosen, ...," 729 pages, Berlin, 1911, and "Band 8--1 Ergänzungsband (same title as Band 2)--" 507 pages; Berlin, 1914.
ARMSTRONG, E. F.--"The Simple Carbohydrates and Glucosides," 233 pages. _Monographs_ on Biochemistry, London, 1919 (3d ed.).
FISCHER, E.--"Untersuchung ueber Kohlenhydrate und Fermente, 1884-1908," 912 pages, Berlin, 1909.
MACKENSIE, J. E.--"The Sugars and their Simple Derivatives," 242 pages, 17 figs., London, 1913.
TOLLENS, B.--"Kurzes Handbuch der Kohlenhydrate," 816 pages, 29 figs., Leipzig, 1914 (3d ed.).
##