Xylans branching

The amount of softwood xylan sorbed from alkati at kraft cooking temperatures (100—170°C) is proportional to the quantity of hemiceUulose present and inversely to the extent of branching (57). At neutral pH, the presence of carboxyl groups inhibits sorption compared to a control, but no difference is observed when ionization is suppressed (58). 

Derivatives of hemicellulose components have properties similar to the ceUulosic equivalents but modified by the effects of thek lower molecular weight, more extensive branching, labile constituents, and more heterogeneous nature. Acetates, ethers, carboxymethylxylan (184), and xylan—poly(sodium acrylate) (185) have been prepared. 

P -D-xylan with 3-hnked a-L-arabiaose branches (1 4)-P -D-xylan with 2-Unked 4-0-methyl-a-D-glucuronic acid and arabiaose branches... 

These results may be explained on the basis that xylan possesses a linear chain of 1,4-linked anhydroxylose units. However, it should be pointed out that on hydrolysis of the oxidized xylan, some D-xylose is found in addition to the expected glyceraldehyde and glyoxal.I04(b) While it is possible that the oxidation reaction is not complete, another explanation is that a branched xylan chain may be present. If branching occurs on a pentose chain unit, only one free hydroxyl would remain on the unit hence, it would not be oxidized or degraded during the course of the periodate reaction. 

D-xylopyranose units. This structural concept is substantiated by estimation of the formic acid obtained when the xylan is oxidized by periodate ions. On hydrolysis of the fully oxidized xylan there is obtained a small amount of D-xylose which presumably occupied the branch points in the polysaccharide and consequently was protected from periodate oxidation by possessing no adjacent free hydroxyl groups. 

Other workers140 have also examined the products derived by hydrolysis of periodate-oxidized xylan. Both wheat straw and com cob xylan, after oxidation and hydrolysis, yield small amounts of L-arabinose and D-xylose. These sugars are obtained even after the xylans have been subjected to extended periods of oxidation. It is concluded that the D-xylose constituted branch points in the xylan. Likewise, the L-arabi-nose molecules must not have been terminal units in a xylan chain but must have been either interior units in the xylan molecule or have constituted an araban-like polysaccharide which is in combination or admixture with the xylan polysaccharide. 

Other abundant carbohydrates, such as hemicelluloses and pectin, are usually highly branched and thus not very suitable for fiber and film production. Hemicelluloses and some pectins are also acetylated in the native state, which makes them more resistant to enzymatic hydrolysis (20,21) and changes their solubility properties (9-77,75). Branching does not, however, preclude their utilization in such potentially large markets as thickeners and adhesives. Xylans, for example, show such a strong adhesion to cellulose fibers that they are very difficult to remove completely by both acidic and alkaline pulping processes (22). 

Both D-glucuronic acid and/or its 4-O-methyl ether and arabinose are also present in cereal xylans (4). Endospermic arabinoxylans of annual plants, often referred to as pentosans, are because of their branched structures more soluble in water and dilute alkali than xylans of lignocellulosic materials. They also have at least one, or even two, substituents per xylose residue (5). 

Pentosan polysulfate (1 —> 4)-/3-linked xylan oligosaccharide that is branched in the center with a single /3-(l — 2)-4-O-methyl-ct-D-glucuronate residue... 

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