title: Mixed regiospecificity compromises alkene synthesis by a cytochrome P450 peroxygenase from Methylobacterium populi.
abstract: Intensive interest has focused on enzymes that are capable of synthesizing hydrocarbons, alkenes and alkanes, for sustainable fuel production. A recently described cytochrome P450 (OleTJE) from the CYP152 family catalyzes an unusual carbon-carbon scission reaction, transforming Cn fatty acids to Cn-1 1-alkenes. Here, we show that a second CYP152, CYP-MP from Methylobacterium populi ATCC BAA 705, also catalyzes oxidative substrate decarboxylation. Alkene production is accompanied with the production of fatty alcohol products, underscoring the mechanistic similarity of the decarboxylation reaction with canonical P450 monooxygenation chemistry. The branchpoint of these two chemistries, and regiospecificity of oxidation products, is strongly chain length dependent, suggesting an importance of substrate coordination for regulating alkene production.
authors.affiliation: University of South Carolina, Department of Chemistry and Biochemistry, 631 Sumter Street, Columbia, SC 29208, United States.
authors.forename: Jose A
authors.initials: JA
authors.lastname: Amaya
authors.affiliation: University of South Carolina, Department of Chemistry and Biochemistry, 631 Sumter Street, Columbia, SC 29208, United States.
authors.forename: Cooper D
authors.initials: CD
authors.lastname: Rutland
authors.affiliation: University of South Carolina, Department of Chemistry and Biochemistry, 631 Sumter Street, Columbia, SC 29208, United States. Electronic address: makrist@mailbox.sc.edu.
authors.forename: Thomas M
authors.initials: TM
authors.lastname: Makris
mesh_terms: D000475:Alkenes / Q000737:chemistry* / Q000378:metabolism*; D003577:Cytochrome P-450 Enzyme System / Q000378:metabolism*; D020580:Methylobacterium / Q000201:enzymology*; D010084:Oxidation-Reduction; D010544:Peroxidases / Q000378:metabolism*; D013237:Stereoisomerism
chemical_list: D000475:Alkenes; D003577:Cytochrome P-450 Enzyme System; D010544:Peroxidases; C066418:cytochrome P-450 peroxygenase
keywords: Cytochrome P450; Hydrocarbon biosynthesis; Monooxygenase; Oxidative decarboxylation; Oxygen activation