title: Evaluation of ferryl formation by electrocatalytic oxidation of alkene using luminol chemiluminescence.
abstract: Electrochemical formation of ferryl porphyrin was examined by electrocatalytic oxidation of alkene by measuring luminol chemiluminescence using a flow-injection method. Emission was observed both below the reduction potential of Fe(III)TMPyP (-0.08 V at pH 11, -0.02 V at pH 7 and 0.15 V at pH 3) and above the oxidation potential (0.6 V at pH 11, 0.75 V at pH 7 and 1.1 V at pH 3). However, both anodic and cathodic emissions were inhibited significantly by the addition of alkene (cyclopent-2-ene-1-acetic acid) solutions downstream of the working electrode. Further, the spectra at both anodic and cathodic sides shifted to the longer wavelength (>424 nm) compared to the original spectrum of Fe(III)TMPyP (422 nm), which was not observed with the addition of alkene solution. Therefore, the results suggest that the electrochemically generated oxo-ferryl species have been engaged in catalytic oxidation of alkene before the flow reaches the observation cell.
authors.affiliation: Faculty of Pharmaceutical Sciences, Okayama University, Okayama 700-8530, Japan. sohel@juniv.edu
authors.forename: Mohammad Sohel
authors.initials: MS
authors.lastname: Rana
authors.forename: Keietsu
authors.initials: K
authors.lastname: Tamagake
mesh_terms: D000475:Alkenes / Q000032:analysis* / Q000737:chemistry; D004563:Electrochemistry; D007501:Iron / Q000032:analysis* / Q000737:chemistry; D008163:Luminescent Measurements / Q000295:instrumentation / Q000379:methods*; D010084:Oxidation-Reduction
chemical_list: D000475:Alkenes; C066317:ferryl iron; D007501:Iron