title: Acetate anion-triggered peroxygenation of non-native substrates by wild-type cytochrome P450s.
abstract: Cytochrome P450SPα (P450SPα) and cytochrome P450BSβ (P450BSβ) belonging to the CYP152 family of enzymes (CYP152s) can utilize H2O2 efficiently as an oxidant for the generation of compound I. Although P450SPα and P450BSβ have very high substrate specificity and catalyse hydroxylation of long-chain fatty acids exclusively, we found that they can oxidize non-native substrates such as styrene simply by including medium chain length n-alkyl carboxylic acids as "decoy molecules." Although we had assumed that acetic acid did not serve as a decoy molecule, P450SPα and P450BSβ efficiently catalysed oxidation of non-native substrates when the reaction was carried out at a high concentration of acetate anion. The turnover rate for epoxidation of styrene catalysed by P450BSβ in the presence of 1 M acetate anion reached 590 ± 30 min(-1).
authors.affiliation: Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan. shoji.osami@a.mbox.nagoya-u.ac.jp p47297a@nucc.cc.nagoya-u.ac.jp.
authors.forename: Hiroki
authors.initials: H
authors.lastname: Onoda
authors.forename: Osami
authors.initials: O
authors.lastname: Shoji
authors.forename: Yoshihito
authors.initials: Y
authors.lastname: Watanabe
mesh_terms: D000085:Acetates / Q000737:chemistry*; D000595:Amino Acid Sequence; D000838:Anions; D002384:Catalysis; D020134:Catalytic Domain; D003577:Cytochrome P-450 Enzyme System / Q000737:chemistry*; D004305:Dose-Response Relationship, Drug; D005227:Fatty Acids / Q000737:chemistry; D006859:Hydrogen / Q000737:chemistry; D006861:Hydrogen Peroxide / Q000737:chemistry; D006900:Hydroxylation; D006899:Mixed Function Oxygenases / Q000737:chemistry; D008969:Molecular Sequence Data; D009281:Naphthalenes / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry*; D019308:Palmitic Acid / Q000737:chemistry; D010544:Peroxidases / Q000737:chemistry; D011994:Recombinant Proteins / Q000737:chemistry; D017386:Sequence Homology, Amino Acid; D013056:Spectrophotometry, Ultraviolet; D020058:Styrene / Q000737:chemistry; D013343:Styrenes / Q000737:chemistry
chemical_list: D000085:Acetates; D000838:Anions; D005227:Fatty Acids; D009281:Naphthalenes; D011994:Recombinant Proteins; D013343:Styrenes; D019308:Palmitic Acid; D020058:Styrene; D006859:Hydrogen; D003577:Cytochrome P-450 Enzyme System; D006861:Hydrogen Peroxide; C448759:1-methoxynaphthalene; D006899:Mixed Function Oxygenases; C019081:fatty acid alpha-hydroxylase; D010544:Peroxidases; C437763:cytochrome P-450 CYP152A1 (Bacillus subtilis); D010100:Oxygen