Modified wood fibres open new perspectives to create value-added products based on renewable raw materials. An interesting option is the targeted modification of fibre surfaces by oxidative enzymes. This two-stage functionalisation method consists of enzymatic activation of fibre surfaces followed by addition of radicalised compounds reacting preferentially by radical coupling. In this work, the activation of bleached and unbleached softwood TMPs with laccase isolated from Trametes hirsuta was studied. The formation and stability of the radicals were studied by EPR spectroscopy. The reaction of the radicals with 3-hydroxytyramine hydrochloride and the type of chemical linkages were investigated. EPR, ESCA and FTIR spectroscopy were used for analysis. Bleached TMP was radicalised more efficiently than unbleached TMP. The radicals were unstable, as 90% of them were quenched within a few hours. Their lifetime was, however, found to be adequately long for performing coupling reactions. Bonding of new compounds to pulps via radical reactions thus seems to be possible.
The actinobacterium Streptomyces cyaneus CECT 3335 was evaluated for its ability to delignify spruce wood chips (Picea abies) after 2 weeks of incubation prior to refiner mechanical pulping. Weight loss of the chips during the treatment ranged from 2% to 3%. Chemicalanalysis of the treated wood showed an increase in acid-soluble lignin content concomitant with a notable increase in the acid/aldehyde+ketone [AC/(AL+KE)] ratio of the lignin compared with the control. Structural alterations in wood cell walls were observed by optical and scanning microscopy using astra blue-safranin staining and cryosections stained with gold/palladium, respectively. A gradual loss of lignin from the lumen towards the middle lamella and incipient defiberization could be observed. The estimation of specific energy for the defibration and refining stages of treated pulp showed a 24% reduction in the energy required, largely due to a 30% saving in the defibration of chips. The analysis of handsheets obtained from treated pulp showed a notable improvement in some strength properties, such as breaking length, tear index and stretch. In addition, the high Gurley air resistance value indicates more packing of the voids of the fiber network. These results demonstrate for the first time the suitability of Streptomyces cyaneus for biomechanical pulping purposes.