Changes in chemical structures of wheat straw auto-hydrolysis lignin by 3-hydroxyanthranilic acid as a laccase mediator

Abstract

3-Hydroxyanthranilic acid (3-HAA), as a potential natural laccase mediator, was shown to mediate the oxidation of non-phenolic lignin subunits. The problem of cost and toxicity of artificial mediators could be solved to some extent by a further study about the detailed changes of lignin chemistry structures in laccase 3-HAA system (LHS). In this work, wheat straw auto-hydrolysis lignin (AL) was prepared. Oxidations of AL by LHS and laccase 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) system were then investigated, respectively. Various structural changes of AL during the oxidation were characterized by different methods including phenolic hydroxyl group determination, nitrobenzene oxidation, ozonation, gel permeation chromatography, ultraviolet-visible spectroscopy, Fourier transform infrared spectroscopy and two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy. The changes in AL chemical structures were found in LHS, including unit removal, bond cleavage and biopolymerization. Compared to laccase ABTS system, a selective removal of guaiacyl-type lignin in LHS was observed, based on the results of nitrobenzene oxidation and 2D NMR analysis. The selective removal of guaiacyl-type lignin was due to improved aromatic ring cleavage and weaken lignin biopolymerization. The selectivity of guaiacyl-type lignin removal in LHS plays an important role, especially for improving bioconversion efficiency of laccase for guaiacyl-rich lignocellulosic biomass.

Keywords: 3-Hydroxyanthranilic acid; Auto-hydrolysis lignin; Biopolymerization; Guaiacyl unit; Laccase.