Researches on Cellulose | Page 6

hexosones, glycuronic acid, and perhaps, most important of all, levulose itself, all of which are susceptible of condensation to furfural or furfurane derivatives, as well as to those unsaturated compounds, constituents of plant tissues which are already furfurane derivatives.
From the chemical point of view such terms are perhaps superfluous. But physiological relationships have a significance of their own; and there is a physiological or functional cohesion marking this group which calls for recognition, at least for the time, and we therefore propose to retain the term furfuroid.[1]
~General Experimental Methods.~--In the investigation of the cellulose group it is clear that methods of ultimate hydrolysis are of first importance. None are so convenient as those which are based on the action of sulphuric acid, more or less concentrated (H{2}SO{4}.3H{2}O - H{2}SO{4}H{2}O). Such methods have been frequently employed in the investigations noted in this volume. We notice a common deficiency in the interpretation of the results. It appears to be sufficient to isolate and identify a crystalline monose, without reference to the yield or proportion to the parent substance, to establish some main point in connection with its constitution. On the other hand, it is clear that in hydrolysing a given cellulose-complex we ought to aim at complete, i.e. quantitative, statistics. The hydrolytic transformation of starch to dextrins and maltose has been followed in this way, and the methods may serve as a model to which cellulose transformations should be approximated. In fact, what is very much wanted is a systematic re-examination of the typical celluloses in which all the constants of the terms between the original and the ultimate monose groups shall be determined. Such constants are similar to those for the starch-dextrose series, viz. opticity and cupric reduction. Various methods of fractionation are similarly available, chiefly the precipitation of the intermediate 'dextrins' by alcohol.
Where the original celluloses are homogeneous we should thus obtain transformation series, similarly expressed to those of starch. In the case of the celluloses which are mixtures, or of complex constitution, there are various methods of either fractionating the original, or of selectively attacking particular monoses resulting from the transformation. By methods which are approximately quantitative a mixture of groups, such as we have, for instance, in jute cellulose, could be followed through the several stages of their resolution into monoses. To put the matter generally, in these colloidal and complex carbohydrates the ordinary physical criteria of molecular weight are wanting. Therefore, we cannot determine the relationship of a given product of decomposition to the parent molecule save by means of a quantitative mass-proportion. Physical criteria are only of determining value when associated with such constants as cupric reduction, and these, again, must be referred to some arbitrary initial weight, such as, for convenience, 100 parts of the original.
Instead of adopting these methods, without which, as a typical case, the mechanism of starch conversions could not have been followed, we have been content with a purely qualitative study of the analogous series obtainable from the celluloses under the action of sulphuric acid. A very important field of investigation lies open, especially to those who are generally familiar with the methods of studying starch conversions; and we may hope in this direction for a series of valuable contributions to the problem of the actual constitution of the celluloses.
FOOTNOTES:
[1] In this we are confirmed by other writers. See Tollens, J. für Landw. 1901, p. 27.

SECTION I. GENERAL CHEMISTRY OF THE TYPICAL COTTON CELLULOSE
(p. 3)[2] ~Ash Constituents.~--It is frequently asserted that silica has a structural function sui generis in the plant skeleton, having a relationship to the cellulosic constituents of the plant, distinct from that of the inorganic ash components with which it is associated. It should be noted that the matter has been specifically investigated in two directions. In Berl. Ber. 5, 568 (A. Ladenburg), and again in 11, 822 (W. Lange), appear two papers 'On the Nature of Plant Constituents containing Silicon,' which contain the results of experimental investigations of equisetum species--distinguished for their exceptionally high 'ash' with large proportion of silica--to determine whether there are any grounds for assuming the existence of silicon-organic compounds in the plant, the analogues of carbon compounds. The conclusions arrived at are entirely negative. In reference to the second assumption that the cuticular tissues of cereal straws, of esparto, of the bamboo, owe their special properties to siliceous components, it has been shown by direct experiment upon the former that their rigidity and resistance to water are in no way affected by cultivation in a silica-free medium. In other words, the structural peculiarities of the gramine? in these respects are due to the physical characteristics chiefly of the (lignified) cells of the hypodermal tissue, and to the composition and arrangement of the cells of the cuticle.
'Swedish' filter papers of modern make are so