Some Current Problems in Hemicellulose Chemistry

No complete picture of biological materials can be given without reference to their original condition in their natural environment. Brief consideration will, therefore, be given to the biosynthesis of the hemicelluloses and to their relationship, in the plant, to cellulose and lignin. Since much of our present knowledge of the chemistry of the hemicelluloses is based upon examination of materials isolated by alkaline extraction from plant tissues which, in many cases, have been previously treated to remove lig- 

Woods contain a number of acyl (mainly acetyl) groups, and it is probable that these are associated with the xylan components of the hemicellulose fraction. Evidence for the original esterification of aspen-wood xylan comes from the observation that the isolated xylan (obtained by alkaline extraction) is readily cleaved by periodate, whereas only a small proportion of the D-xylose residues in the wood itself are oxidized under similar conditions.66 Hemicelluloses still containing acyl groups may be extracted from wood holocelluloses by means of dimethyl sulfoxide, and further quantities 

Glycosides are generally considered to be stable toward alkali, although several types of alkali-labile glycosides are known.161 Recently, however, the alkaline hydrolysis of glycosides that are stable under normal conditions has been demonstrated to occur under drastic conditions.162 This type 

The value of number-average molecular weights of methylated polysaccharides, used in conjunction with methylation end-group assays in the assessment of the degree of branching, has been stressed previously (see p. 435). Etherification is, however, normally carried out under alkaline con- 

Although most polysaccharides may be acylated without degradation, acyl derivatives of xylans29 are often unsatisfactory for molecular-weight determinations owing to their poor solubility characteristics. Mixed esters of xylans143 are often superior in this respect, but there are obvious difficulties in the differential analysis of acyl groups. Hemicellulose nitrates have been used for measurements of molecular size,168 but xylan nitrates,29 like xylan acetates, are reported to have poor solubility characteristics. 

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