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Alteration in the oxidation and degradation of dimethylsulfide (DMS) in the atmosphere is a key factor for the sources of atmospheric sulfur oxidation products. Previous studies suggest that H2O2 is a key intermediate in DMS oxidation by atmospheric oxidants, including singlet oxygen, ozone, and chlorine. DMS is also known to react nonenzymatically with the heme iron of cytochrome P450 2E1 (CYP2E1) to produce 2,2′-dismethylsulfinylbis(2,4-xylyl)imine (DMSI), which is subsequently isomerized to a reactive species. In this work, the catalytic roles of CYP2E1 in the oxidation of DMS by hydroxyl radicals were investigated. Kinetic studies demonstrated that DMS is the direct oxidant for CYP2E1 with an apparent turnover number (kcat) of 0.36 min(-1) and a Michaelis-Menten constant (Km) of 99 microM. The conversion of DMS to DMSO by CYP2E1 was investigated using stopped-flow spectrophotometry. The data indicated that the two-step mechanism for DMS degradation by CYP2E1 is similar to the reported mechanism for HO2-mediated oxidation of DMS. The nonenzymatic reaction of CYP2E1-mediated DMS oxidation is the conversion of DMS to DMSO followed by the elimination of H2O2. The nonenzymatic oxidation of DMS has a kcat of 1.5 min(-1) and Km of 93 microM. The nonenzymatic reaction of CYP2E1 with DMS is faster than the oxidation of H2O2 by CYP2E1, which suggests
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