title: In vitro analysis of the monolignol coupling mechanism using dehydrogenative polymerization in the presence of peroxidases and controlled feeding ratios of coniferyl and sinapyl alcohol.
abstract: In this study, dehydrogenative polymers (DHP) were synthesized in vitro through dehydrogenative polymerization using different ratios of coniferyl alcohol (CA) and sinapyl alcohol (SA) (10:0, 8:2, 6:4, 2:8, 0:10), in order to investigate the monolignol coupling mechanism in the presence of horseradish peroxidase (HRP), Coprinus cinereus peroxidase (CiP) or soybean peroxidase (SBP) with H(2)O(2), respectively. The turnover capacities of HRP, CiP and SBP were also measured for coniferyl alcohol (CA) and sinapyl alcohol (SA), and CiP and SBP were found to have the highest turnover capacity for CA and SA, respectively. The yields of HRP-catalyzed DHP (DHP-H) and CiP-catalyzed DHP (DHP-C) were estimated between ca. 7% and 72% based on the original weights of CA/SA in these synthetic conditions. However, a much lower yield of SBP-catalyzed DHP (DHP-S) was produced compared to that of DHP-H and DHP-C. In general, the DHP yields gradually increased as the ratio of CA/SA increased. The average molecular weight of DHP-H also increased with increasing CA/SA ratios, while those of DHP-C and DHP-S were not influenced by the ratios of monolignols. The frequency of β-O-4 linkages in the DHPs decreased with increasing CA/SA ratios, indicating that the formation of β-O-4 linkages during DHP synthesis was influenced by peroxidase type.
authors.affiliation: Department of Forest Sciences and Research Institute for Agriculture and Life Science, Seoul National University, 599 Gwanak-ro, Gwanak-gu, Seoul, Republic of Korea.
authors.forename: Sun-Joo
authors.initials: SJ
authors.lastname: Moon
authors.forename: Mi
authors.initials: M
authors.lastname: Kwon
authors.forename: Donha
authors.initials: D
authors.lastname: Choi
authors.forename: Keehoon
authors.initials: K
authors.lastname: Won
authors.forename: Yong Hwan
authors.initials: YH
authors.lastname: Kim
authors.forename: In-Gyu
authors.initials: IG
authors.lastname: Choi
authors.forename: Joon Weon
authors.initials: JW
authors.lastname: Choi
mesh_terms: D055162:Biocatalysis; D003302:Coprinus / Q000201:enzymology; D006735:Horseradish Peroxidase / Q000378:metabolism; D006859:Hydrogen / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry; D008970:Molecular Weight; D009195:Peroxidase / Q000378:metabolism*; D010636:Phenols / Q000737:chemistry*; D010666:Phenylpropionates / Q000737:chemistry*; D058105:Polymerization; D013025:Glycine max / Q000201:enzymology
chemical_list: D010636:Phenols; D010666:Phenylpropionates; D006859:Hydrogen; C496130:sinapyl alcohol; D006861:Hydrogen Peroxide; C010559:coniferyl alcohol; D006735:Horseradish Peroxidase; D009195:Peroxidase