Xylans acidic, structure

Most of the glucuronoxylans have single 4-0-methyl-o -D-glucopyranosyl uronic acid residues (MeGlcA) attached always at position 2 of the main chain Xylp units (Fig. 2). This structural type is usually named as 4-0-methyl-D-glucurono-D-xylan (MGX). However, the glucuronic acid side chain may be present in both the 4-0-methylated and non-methylated forms (GlcA). 

The heteroxylans (CHX) present in cereals, seeds, gum exudates, and mucilages are structurally more complex [6]. They have a (1 4)-)0-d-xylopyranose backbone decorated, except of the single uronic acid and arabinosyl residues with various mono- and oligoglycosyl side chains. Reinvestigations of CHX isolated from corn bran [52] have confirmed that the xylan backbone is heavily substituted (at both positions 2 and 3) with y0-D-Xylp, y0-L-Ara/, of-D-GlcpA residues and oligosaccharide side chains (1), (3) and (4). 

The floss silk from Chorisia speciosa furnished a polysaccharide with a main chain of (1 -> 4) linked P-Xylp substituted at 0-2 by 5 % of uronic acid. The xylan structure also was interposed with a-Rhap units in small amounts. The defatted seeds furnished on aqueous extraction a major fraction, ((9-acetyl, 10 % and protein, 45 %) wich was hydrolysed and analysed by p.c. and GLC, showing Rha (20 %), Ara (16 %), Gal (64 %) and also uronic acids (45 %). Partial hydrolysis gave rise to a polysaccharide free of arabinose, with 46 % of uronic acids. Methylation analysis (GLC -MS) indicated a chain of (1 4) - linked Gal/ (42 % of 2,3,6-Me3-Gal). 

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. 

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). 

The specificity of a xylanase preparation may be determined from the isolation and characterization of oligosaccharides formed from xylan hydrolysis. While the oligosaccharides released were mainly dependent on the specificity of the xylanase, the complex structure of the heteroxylan also determines the extent of hydrolysis and the site of cleavage. Two types of xylooligosaccharides are usually produced acidic (from glucuronoxylans) and neutral (from arabino- and arabinoglucurono-xylans). The specificity of the action of several purified xylanases on various heteroxylans is shown below ... 

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