Effect of pH on the formation of benzyl ester bonds between glucuronic acid and dehydrogenation polymer

Abstract

The effect of pH on the addition reaction of glucuronic acid to quinone methides generated in the synthesis of dehydrogenation polymer (DHP or artificial lignin) was investigated. The DHP-glucuronic acid complexes were formed during DHP polymerization catalyzed by a mixture of laccase, β-glucosidase, and O2 within the pH range 7 to 4 in the presence of coniferin as a precursor. The structure of the product and the content of benzyl ester bonds were characterized by Fourier transform infrared spectroscopy, solid-state cross-polarization magic angle spinning carbon-13 nuclear magnetic resonance spectroscopy, ion chromatography, high performance liquid chromatography, and elemental analysis. The results showed that the pH of the reaction system had an important role in the formation of the benzyl ester bonds. Acidic conditions favored the reaction of quinone methide intermediates with carboxyl groups of glucuronic acid in the biosynthesis of DHP. However, weakly acidic conditions (pH 6) enhanced the reaction of quinone methide intermediates with glucose. In neutral conditions, the DHP-protein complex can be efficiently synthesized by the addition reaction of quinone methide intermediates with amino acids in protein.