title: Enzymatic Specific Production and Chemical Functionalization of Phenylpropanone Platform Monomers from Lignin.
abstract: Enzymatic catalysis is an ecofriendly strategy for the production of high-value low-molecular-weight aromatic compounds from lignin. Although well-definable aromatic monomers have been obtained from synthetic lignin-model dimers, enzymatic-selective synthesis of platform monomers from natural lignin has not been accomplished. In this study, we successfully achieved highly specific synthesis of aromatic monomers with a phenylpropane structure directly from natural lignin using a cascade reaction of β-O-4-cleaving bacterial enzymes in one pot. Guaiacylhydroxylpropanone (GHP) and the GHP/syringylhydroxylpropanone (SHP) mixture are exclusive monomers from lignin isolated from softwood (Cryptomeria japonica) and hardwood (Eucalyptus globulus). The intermediate products in the enzymatic reactions show the capacity to accommodate highly heterologous substrates at the substrate-binding sites of the enzymes. To demonstrate the applicability of GHP as a platform chemical for bio-based industries, we chemically generate value-added GHP derivatives for bio-based polymers. Together with these chemical conversions for the valorization of lignin-derived phenylpropanone monomers, the specific and enzymatic production of the monomers directly from natural lignin is expected to provide a new stream in "white biotechnology" for sustainable biorefineries.
authors.affiliation: Research and Development Center for Marine Biosciences, Japan Agency for Marine-Earth Science and Technology, JAMSTEC, 2-15 Natsushima, Yokosuka, Kanagawa, 237-0061, Japan.
authors.forename: Yukari
authors.initials: Y
authors.lastname: Ohta
authors.affiliation: Research and Development Center for Marine Biosciences, Japan Agency for Marine-Earth Science and Technology, JAMSTEC, 2-15 Natsushima, Yokosuka, Kanagawa, 237-0061, Japan.
authors.forename: Ryoichi
authors.initials: R
authors.lastname: Hasegawa
authors.affiliation: Research and Development Center for Marine Biosciences, Japan Agency for Marine-Earth Science and Technology, JAMSTEC, 2-15 Natsushima, Yokosuka, Kanagawa, 237-0061, Japan.
authors.forename: Kanako
authors.initials: K
authors.lastname: Kurosawa
authors.affiliation: Research and Development Center for Marine Biosciences, Japan Agency for Marine-Earth Science and Technology, JAMSTEC, 2-15 Natsushima, Yokosuka, Kanagawa, 237-0061, Japan.
authors.forename: Allyn H
authors.initials: AH
authors.lastname: Maeda
authors.affiliation: Department of Applied Chemistry, National Defense Academy, 1-10-20 Hashirimizu, Yokosuka, Kanagawa, 239-8686, Japan.
authors.forename: Toshio
authors.initials: T
authors.lastname: Koizumi
authors.affiliation: Research Institute for Sustainable Humanosphere, RISH, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Nishimura
authors.affiliation: Research Institute for Sustainable Humanosphere, RISH, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.
authors.forename: Hitomi
authors.initials: H
authors.lastname: Okada
authors.affiliation: Research Institute for Sustainable Humanosphere, RISH, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.
authors.forename: Chen
authors.initials: C
authors.lastname: Qu
authors.affiliation: Research Institute for Sustainable Humanosphere, RISH, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.
authors.forename: Kaori
authors.initials: K
authors.lastname: Saito
authors.affiliation: Research Institute for Sustainable Humanosphere, RISH, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.
authors.forename: Takashi
authors.initials: T
authors.lastname: Watanabe
authors.affiliation: Department of Life Sciences and Green Chemistry, Saitama Institute of Technology, 1690 Fusaiji, Fukaya, Saitama, 369-0293, Japan.
authors.forename: Yuji
authors.initials: Y
authors.lastname: Hatada
mesh_terms: D000096:Acetone / Q000737:chemistry*; D055162:Biocatalysis; D032485:Cryptomeria / Q000201:enzymology; D005052:Eucalyptus / Q000201:enzymology; D005982:Glutathione Transferase / Q000378:metabolism*; D006863:Hydrogen-Ion Concentration; D008031:Lignin / Q000737:chemistry*; D011427:Propiophenones / Q000737:chemistry*; D013696:Temperature
chemical_list: D011427:Propiophenones; D000096:Acetone; D008031:Lignin; D005982:Glutathione Transferase
keywords: biomass; enzymes; lignin; molecular recognition; reaction mechanisms