Oxidation of polycyclic aromatic hydrocarbons catalyzed by soybean peroxidase

Soybean peroxidase (SBP) catalyzes the oxidation of a variety of polycyclic aromatic hydrocarbons (PAHs) in the presence of water-miscible organic cosolvents, including acetonitrile, tetrahydrofuran, and dimethylformamide (DMF). Oxidation was optimal at pH 2.0–2.5, with substantially lower reactivity at pH 1.5 as well as at pH > 3.0. Despite the low pH activity optimum, SBP had an observed half-life of 120 h at pH 2.5. Conversions of greater than 90% were observed with anthracene and 9-methylanthracene in the presence of 50% (v/v) DMF. Anthracene oxidation yielded exclusively anthraquinone, thereby demonstrating that SBP catalyzes a formal six-electron oxidation of the unactivated aromatic substrate to the quinone. A mechanism is proposed to account for this reaction that includes the initial one-electron oxidation of the PAH followed by addition of water to the oxidized PAH. 9-Methylanthracene was more reactive than anthracene, and its enzymatic oxidation yielded two products: anthraquinone and 9-methanol-9,10-dihydroanthracene. The former product indicates that loss of the methyl group occurs during enzymatic oxidation. These results suggest that SBP could be useful in the conversion of PAHs into more environmentally benign materials.