Glucuronoxylans

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). 

Recently, the alkah-soluble hemicelluloses of hardwood dissolving pulps have been investigated [28]. Their composition and molecular properties depended on the pulp origin and steeping conditions. The MGX of the j8-fraction from press lye had a low uronic acid content (ratio of MeGlcA to Xyl is about 1 20). The molecular weight of the hemicellulose fractions varied between 5000 and lOOOOg/mol. 

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Most frequently, SEC with dextran-, pullulan-, or polystyrene calibration standards has been used to characterize the molecular properties of xylans. However, as for viscometric studies [108], a sufficient solvent ionic strength is a prerequisite for useful SEC measurements of charged polysaccharides, including glucuronoxylans [111-113]. An advantage of the SEC technique is that the presence of protein and phenolic components or oxidative changes can be detected by simultaneous ultraviolet (UV) detection. 

Glucuronoxylans can be partly acetylated and have units substituted with a-(l—>2)-4-0-methyl-D-glucopyranosyl uronic acid (MeGlcUA). They are found in hardwood, depending on the treatment. 

Arabino)glucuronoxylans have a substitution with a-(l—>3)-L-arabinofuranosyl (ArbF) next to MeGlcUA. They are typical for softwoods. 

Fig. 37.— 13C-N.m.r. Spectrum of Glucuronoxylan of Herpetomonas samuelpessoai (D20, 70°). (Chemical shifts are in 8C, relative to external tetramethylsilane.)...

The only major accessory enzyme purified thus far for the xylanase was an a-(l,3)-L-arabinosidase with a molecular weight of 66,(XX) and isoelectric point of 4.1 (publication in preparation). The enzyme was not capable of acting on intact xylans. However, it acted on the end-products of arabinoxylan (but not glucuronoxylan) degradation by the xylanase, doubling the total extent of degradation. 

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 ... 

Figure 2. Hydrolysis products of beechwood O-acetylglucuronoxylan (Fig. 2a), beechwood glucuronoxylan (Fig. 2b), and wheat straw arabinoxylan (Fig. 2c), as analyzed by gel permeation chromatography. The hydrolysis was carried out at pH 5 at 45°C for 24 h using 10.000 nkat of the 20 kDa xylanase of T. reesei. X = xylose X2 = xylobiose Xmga — 4-O-methyl-glucuronosyl substituted xylo-oligosaccharides X = xylo-oligosaccharides DP > 20.

Glucuronoxylan Even if hemicelluloses in various hardwood species differ from each other both quantitatively and qualitatively, the major component is an 0-acetyl-4-0-methylglucuronoi3-D-xylan, sometimes called glucuronoxylan. Often the xylose-based hemicelluloses in both softwoods and hardwoods are termed simply xylans. 

Fig. 3-15. Abbreviated formula of glucuronoxylan. Sugar units /3-D-xylopyranose (Xylp), and 4-O-methyl-a-D-glucopyranosyluronic acid (GlcpA). R is an acetyl group (CH3CO).

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