Fibre-bound and isolated birch xylans from wood and from kraft pulp we
re characterized according to their chemical composition, macromolecul
ar properties and solubilization in enzymatic hydrolysis. During kraft
pulping, xylans are extensively modified. Xylan isolated from kraft p
ulp contained less substituents and had a lower molecular mass than na
tive xylan isolated from wood. Reprecipitated xylan, which was a model
of the xylan adsorbed on the fibre surfaces in the kraft process, was
almost pure polyxylose. All isolated xylans were hydrolyzed efficient
ly by xylanolytic enzymes, although the solubilization decreased sligh
ly as a function of chemical processing. The fibre-bound xylans were c
onsiderably less accessible to enzymes than the isolated xylans. Despi
te high enzyme loadings, the degree of hydrolysis of fibre-bound subst
rates did not exceed 20% of the theoretical value. Due to the low side
-group content of pulp xylans, the side-group cleaving enzymes had onl
y a moderate role in increasing their total solubilization. The result
s obtained strongly suggested that the observed low solubilization of
fibre-bound xylans is mainly due to poor accessibility of enzymes to t
he fibrous material. The results are discussed in the light of new enz
ymatic applications in the pulp and paper industry.