Catalytic Oxidation of Methane by Wild-Type Cytochrome P450BM3 with Chemically Evolved Decoy Molecules

Biological methane oxidation is a highly desirable methodfor theconversion of natural gas into a liquid to meet the increasing demandfor fuel and chemical feedstock as well as reducing the potent greenhouseeffects of methane emissions. Because natural hemoenzymes that cancatalyze the conversion of methane to methanol have not been found,it has long been considered that hemoenzymes, including cytochromeP450s (P450s), cannot catalyze the oxidative conversion of methane.Herein, we report the catalytic oxidation of methane by wild-typeP450BM3, without any mutagenesis, in the presence of chemically evolveddummy substrates (decoy molecules) under high-pressure methane at10 MPa. Our studies showed that methane was catalytically convertedinto methanol at room temperature with a total turnover number of4.