The mechanism of reaction of ebselen with superoxide in aprotic solvents as examined by cyclic voltammetry and ESR.
The mechanism of the redox reaction of ebselen with superoxide was investigated using both ESR and electrochemical techniques. The reaction with superoxide in aprotic solvents was followed by means of cyclic voltammetry and ESR spin-trapping. A decrease in the oxidation current due to superoxide as a result of the addition of ebselen was clearly observed in the cyclic voltammograms. Ebselen reduced the ESR signal intensity of 5,5-dimethyl-1-pyrroline N-oxide (DMPO)-superoxide in a dose-dependent manner. The formation of an amidyl radical in this redox reaction was confirmed by rapid mixing continuous-flow ESR. The selenonate form and the seleninate form of ebselen were identified as the final products of the reaction of ebselen with superoxide. The following mechanism for this redox reaction can be proposed: First, ebselen reacts with superoxide and is converted to an ebselen anion radical; second, the ebselen anion radical reacts with superoxide and is converted to the amidyl radical. Hydrogen abstraction by the amidyl radical occurs and gives both a seleninate form and a selenonate form.
Araki
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T
Drug Metabolism and Physicochemical Property Research Laboratory, Daiichi Pharmaceutical Co., Ltd., Tokyo, Japan. araki45s@daiichipharm.co.jp
Kitaoka
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H
D000975:Antioxidants / Q000737:chemistry*; D001393:Azoles / Q000737:chemistry*; D004563:Electrochemistry; D004578:Electron Spin Resonance Spectroscopy; D054833:Isoindoles; D009682:Magnetic Resonance Spectroscopy; D016566:Organoselenium Compounds / Q000737:chemistry*; D012997:Solvents; D013055:Spectrophotometry, Infrared; D013056:Spectrophotometry, Ultraviolet; D013481:Superoxides / Q000737:chemistry*
D000975:Antioxidants; D001393:Azoles; D054833:Isoindoles; D016566:Organoselenium Compounds; D012997:Solvents; D013481:Superoxides; C042986:ebselen