Hemicelluloses are one of the main constituents of plant cell walls and thereby one of the most abundant biopolymers on earth. They can be obtained as by-products from different wood based processes, most importantly from the mechanical pulping. Hemicelluloses have interesting properties in e.g. barrier film applications. However, their relatively low molecular weight after isolation and co-extraction with lignin has limited their use. In this work, we present a novel technique for increasing the molecular weight of different wood hemicelluloses from mechanical pulping process waters as well as from pre-hydrolysis extracts. This is achieved by enzyme-catalyzed cross-linking of aromatic moieties bound to the hemicelluloses. The cross-linking treatment resulted in significantly improved mechanical properties in barrier films made with spruce galactoglucomannan. To our knowledge, this is the first time that wood hemicelluloses have been cross-linked by utilizing the bound aromatic moieties and creates new possibilities for utilizing this raw material source.

In this study we were mirroring suggested in vivo phenomena of lignin-hemicellulose complex formation in vitro, by cross-linking Norway spruce (Picea abies) galactoglucomannans, xylans and lignin moieties to high molecular weight complexes by laccase treatment. We were able to observe the oxidation and cross-linking of non-condensed guaiacyl-type phenolic moieties attached to both of the hemicelluloses by P-31 NMR and size-exclusion chromatography. We suggest that hemicelluloses-lignin complexes form covalently linked structural units during the early stages of lignification via radical enzymatic cross-linking catalyzed by laccase. This work shows that the hemicellulose molecules in wood are covalently linked to two or more lignin units thereby making them suited for forming network structures.

Hemicelluloses with high molecular mass are needed for the manufacture of value added products such as food packaging barrier films. In this work such molecules were recovered from chemithermomechanical pulp (CTMP) process water using an innovative three-stage process comprising membrane separation and enzymatic treatment with laccase. Microfiltration followed by ultrafiltration was found to be a suitable combination in the first stage, providing a concentrated and purified hemicellulose fraction suitable for enzymatic treatment. In both membrane processes a high average flux (260 and 115 l/m(2) h) and a low fouling tendency were observed. A marked increase in the average molecular mass of hemicelluloses with bound lignin moieties was achieved by laccase treatment in the second stage. The enzymatically crosslinked hemicelluloses were finally recovered in the third stage using ultrafiltration. In the final high molecular mass solution the hemicellulose concentration was 54 g/l, the contribution of hemicelluloses to the total solids content 43%, and the viscosity of the solution 27 mPa s. The results demonstrate that a hemicellulose fraction of high quality can be produced from CTMP process water, and that this could constitute a suitable feedstock for the production of, for example, barrier films for renewable packaging.