Studies on the dehydrogenative polymerizations (DHPs) of monolignol β-glycosides: Part 4. Horseradish peroxidase-catalyzed copolymerization of isoconiferin and isosyringin

Abstract

Abstract Horseradish peroxidase (HRP)-catalyzed dehydrogenative copolymerization of guaiacyl (G)-type monolignol glycoside (isoconiferin, coniferyl alcohol γ-O-β-d-glucopyranoside, iso-G) and syringyl (S)-type monolignol glycoside (isosyringin, sinapyl alcohol γ-O-β-d-glucopyranoside, iso-S) were performed in continuous dehydrogenation mode (end-wise polymerization) to result in the formation of water-soluble lignin-like copolymers (iso-G/S-DHPs) in a homogeneous phase. The yield of iso-G/S-DHP increased with increasing iso-G content in the mixture of monomers from 23% (iso-G/iso-S 0:100) to 81% (iso-G/iso-S 50:50). The degree of polymerization (DP) of the resulting iso-G/S-DHP also increased proportionally from 7 (iso-G/iso-S 0:100) to 27 (iso-G/iso-S 50:50) as the iso-G content increased. It is obvious that iso-G plays an important role in the polymerization of iso-S. A similar tendency was also observed in conventional copolymerization of coniferyl alcohol (G-alc) and sinapyl alcohol (S-alc). The highest DP for DHP obtained in the conventional system was only ∼10 due to the heterogeneous reaction system. As the HRP-catalyzed monomer consumption rate of iso-S was greatly enhanced by addition of iso-G as a co-monomer, radical transfer from iso-G to iso-S seems to be plausible. Conventional copolymerization of G-alc and S-alc also supports this view. Spectroscopic studies and alkaline nitrobenzene oxidation analyses indicated that iso-G/S-DHPs had typical lignin structures composed of both G and S units. It was confirmed that the copolymerization behavior of the glycosides iso-G and iso-S in a homogeneous phase are well reflected by that of the monolignols G-alc and S-alc in a heterogeneous phase. Results also indicated that the presence of G-type co-monomers sensitively affects the polymerization of S-type monomers.