Hemicellulose mannans

During the past decade, MALDI-TOF MS has proven to be an effective tool for the analysis of oligo- and polymeric mannoglucans (for extensive reviews see [222,223]). SEC/MALDI mass spectrometry was employed in the analysis of hemicelluloses isolated by microwave heat-fractionation from spruce and aspen wood [94]. These methods allowed the separation and characterization of the oligo- and polysaccharide fractions derived from the xylan and mannan components of both woods [224]. 

Usually it is considered that xylan has been effectively removed if the extracted residue compares in composition to a-cellulose. Yet, even a-cellulose contains small amounts of xylan as well as other hemicelluloses such as mannan.67 69 Beta and 7-cellulose are mixtures which contain pentosans along with other alkali-soluble extractives.1M0... 

Galactans, mannans (hemicelluloses, cell-wall storage)... 

The experiments were repeated under similar conditions with the same and another mannanase fraction of Yamazaki s, with sprucewood holocellulose prepared in a slightly different way (19). After three weeks incubation, about 19% of the mannan was dissolved away, and the loci of hemicellulose removal were revealed by electron microscopy. In these experiments, the bulk of hemicelluloses was obviously removed by the buffer solution. In addition to mannose, glucose and galactose derived from mannan, xylose and glucose were found in the reaction solutions in appreciable amounts. 

The combined action of xylanase and mannanase on sprucewood holocellulose increased the hydrolysis of hemicelluloses without any detectable attack of cellulose. At the end of the experiments—i.e., after 48 hr of xylanase incubation followed by 32 hr of combined xylanase-mannanase incubation—about half the hemicelluloses present in the starting material were selectively converted into low-molecular-weight sugars. The amount of mannan removed was two times higher than after 80 hr of incubation with mannanase only. Unexpectedly, the xylan dissolution was scarcely increased by the combined action of the two hemicellulases. 

About a quarter of the mannan in the sprucewood holocellulose seems to be accessible to the mannanase. More mannan can be hydrolyzed only when the second hemicellulose becomes at least partly dissolved. The remaining mannan—less than half the initial amount— appears to be removable only together with cellulose degradation. In beechwood holocellulose, most of the main hemicellulose—i.e., the xylan —can be hydrolyzed rather selectively by the sole action of xylanase. This phenomenon could be due to the different molecular size of the two hemicellulases, mannanase about 24 A, xylanase about 18 A (JO), resulting in better diffusing conditions for the xylanase. However, the porosity of the... 

B. Hemicelluloses-arabans, xylans, mannans, glucosans, and uronic acid substances... 

The hemicelluloses are polymolecular, random-coil, often branched hetero-glycans interspersed with cellulose microfibrils and starch granules in vivo. Glucose, xylose, and arabinose are the prominent sugars, although lesser quantities of galactan, mannan, etc., and minor concentrations of acetic, ferulic and uronic acids, etc., are in evidence. Heterogeneity extends to dimensions and conformation. 

Table 15.8 presents the feedstock composition expressed in key components cellulose, hemicellulose (xylan, arabinan, mannan, galactan) and lignin. 

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