title: Epoxy ceriporic acid produced by selective lignin-degrading fungus Ceriporiopsis subvermispora.
abstract: Ceriporiopsis subvermispora is a selective white rot basidiomycete which degrades lignin in wood at a distance far from enzymes. Low molecular mass metabolites play a central role in the oxidative degradation of lignin. To understand the unique wood-decaying mechanism, we surveyed the oxidized derivatives of ceriporic acids (alk(en)ylitaconic acids) produced by C. subvermispora using high-resolution liquid chromatography multiple-stage mass spectrometry (HR-LC/MS(n)). The analysis of the precursor and product ions from the extract suggested that an epoxidized derivative of ceriporic acid is produced by the fungus. To identify the new metabolite, an authentic compound of ceriporic acid epoxide was synthesized in vitro by reacting (R)-3-[(Z)-hexadec-7-enyl]-itaconic acid (ceriporic acid C) with m-chloroperbenzoic acid. The precursor and product ions from the natural metabolite and authentic epoxide were identical and distinguishable from those of hydroxy and hydroperoxy derivatives after reduction with NaBD(4). Feeding experiments with [U-(13)C]-glucose, 99% and the subsequent analyses of the first and second generation product ions demonstrated that the oxidized ceriporic acid was (R)-3-(7,8-epoxy-hexadecyl)-itaconic acid. To our knowledge, this study is the first to report that natural alkylitaconic acid bears an epoxy group on its side chain.
authors.affiliation: Laboratory of Biomass Conversion, Research Institute for Sustainable Humanosphere, Kyoto University, Gokasho, Uji, Kyoto, Japan.
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Nishimura
authors.forename: Yuichi
authors.initials: Y
authors.lastname: Setogawa
authors.forename: Takahito
authors.initials: T
authors.lastname: Watanabe
authors.forename: Yoichi
authors.initials: Y
authors.lastname: Honda
authors.forename: Takashi
authors.initials: T
authors.lastname: Watanabe
mesh_terms: D002247:Carbon Isotopes / Q000378:metabolism; D055453:Coriolaceae / Q000378:metabolism*; D003998:Dicarboxylic Acids / Q000138:chemical synthesis / Q000378:metabolism*; D004852:Epoxy Compounds; D005947:Glucose / Q000378:metabolism; D008031:Lignin / Q000378:metabolism; D053719:Tandem Mass Spectrometry
chemical_list: D002247:Carbon Isotopes; D003998:Dicarboxylic Acids; D004852:Epoxy Compounds; C488844:ceriporic acid C; D008031:Lignin; D005947:Glucose