The influence of laccase on the chemo-enzymatic synthesis of lignin graft-copolymers

Abstract

The mechanism unterlying the chemo-enzymatic graft copolymerization of lignin with acrylic compounds was studied. When lignin sulfonate (LS) was incubated with the phenoloxidase laccase in the presence of a peroxide species ( t-butylhydroperoxide, i.e. t-BHP), the decrease of the phenolic groups was significantly higher than when LS was incubated with laccase or t-BHP, separately. The enzymatic oxidation of the phenolic groups did lead to the formation of quinones; however, the number of quinone groups formed in LS in the presence of t-BHP was not significantly higher than in its absence. Still, a certain proportion of the quinones formed in the presence of t-BHP appeared to be further oxidized resulting in an opening of the aromatic rings. In addition, the rate of LS polymerization, i.e. its increase in M w instigated by laccase, was significantly reduced in the presence of t-BHP even though the activity of laccase was only slightly affected by the peroxide. Incubation of LS with laccase prior to the grafting reaction resulted in a significant increase of the spin concentration as detected in the EPR spectra. In spite of a high steady state concentration of radicals, the generation rate of these radicals in pre-incubated LS was lower than in unpretreated LS. Thus, the polymer yields obtained with pre-incubated LS were lower than those obtained with unpretreated LS.