title: Mononuclear and dinuclear monoperoxovanadium(v) complexes with a hetero ligand. 1.(1) Self-decomposition reaction, detection of reactive oxygen species, and oxidizing ability.
abstract: A mononuclear peroxovanadium(V) complex with histamine-N,N-diacetate (histada), K[VO(O(2))(histada)], and a dinuclear peroxovanadium(V) complex with 2-oxo-1,3-diaminopropane-N,N,N',N'-tetraacetate (dpot), Cs(3)[(VO)(2)(O(2))(2)(dpot)], were prepared and characterized. The self-decomposition reaction was examined for these peroxovanadium(V) complexes as well as for K[VO(O(2))(cmhist)] (cmhist = N-carboxymethylhistidinate). The reaction profiles depicted by the absorbance change in the UV-vis spectrum show a sigmoid shape with an induction period. The induction period is reduced by the addition of acid, fluoride, thiocyanate, VO(2+), VO(2)(+), and trolox compared to the solution containing perchlorate. On the other hand, the induction period was elongated by the addition of chloride, bromide, and 2-tert-butyl-p-cresol. These behaviors are discussed on the basis of a radical chain mechanism. The self-decomposition reactions have also been followed by the (1)H and (51)V NMR and EPR spectra. These spectral studies as well as the UV-vis spectral study indicate that vanadium(V) is partly reduced to vanadium(IV) in the self-decomposition process. The histada complex yields a mixed-valence dinuclear complex in a concentrated solution, and the dpot complex yields a mixed-valence tetranuclear complex. The reduction of vanadium ion suggests that the peroxo ligand may act as a reducing agent. In order to know the fate of the peroxo ligand, we tried to detect superoxide anion and hydroxyl radical, which were anticipated to be produced in the self-decomposition process. The formation of superoxide anion was spectrophotometrically confirmed using two independent methods, including the reduction of cytochrome c and the reduction of sodium 4-[3-(iodophenyl)-2-(4-nitrophenyl)-2H-5-tetrazolio]-1,3-benzene disulfonate (WST-1). The formation of hydroxyl radical was confirmed by an EPR spin trapping technique. The oxidizing abilities of the peroxovanadium(V) complexes toward bovine serum albumin (BSA) were also evaluated. In the protein carbonyl assay, it was found that the total amount of protein carbonyl in BSA was increased by the reaction with the peroxovanadium complexes in the concentration-dependent manner. In addition, the oxidation of sulfhydryl group in BSA induced by the peroxovanadium complexes was confirmed.
authors.affiliation: Department of Chemistry, Faculty of Science, Toyama University, Gofuku 3190, Toyama 930-8555, Japan. kanamori@sci.toyama-u.ac.jp
authors.forename: Kan
authors.initials: K
authors.lastname: Kanamori
authors.forename: Kazuya
authors.initials: K
authors.lastname: Nishida
authors.forename: Nanako
authors.initials: N
authors.lastname: Miyata
authors.forename: Toshiyuki
authors.initials: T
authors.lastname: Shimoyama
authors.forename: Kaori
authors.initials: K
authors.lastname: Hata
authors.forename: Chie
authors.initials: C
authors.lastname: Mihara
authors.forename: Ken-Ichi
authors.initials: K
authors.lastname: Okamoto
authors.forename: Yuriko
authors.initials: Y
authors.lastname: Abe
authors.forename: Shingo
authors.initials: S
authors.lastname: Hayakawa
authors.forename: Seiichi
authors.initials: S
authors.lastname: Matsugo
mesh_terms: D000818:Animals; D002417:Cattle; D018360:Crystallography, X-Ray; D045304:Cytochromes c / Q000737:chemistry; D006632:Histamine / Q000737:chemistry; D006863:Hydrogen-Ion Concentration; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D017382:Reactive Oxygen Species / Q000737:chemistry; D012710:Serum Albumin, Bovine / Q000737:chemistry*; D013778:Tetrazolium Salts / Q000737:chemistry; D014639:Vanadium / Q000737:chemistry*
chemical_list: C110656:2-(4-iodophenyl)-3-(4-nitrophenyl)-5-(2,4-disulfophenyl)-2H-tetrazolium; D008024:Ligands; D009942:Organometallic Compounds; D017382:Reactive Oxygen Species; D013778:Tetrazolium Salts; D014639:Vanadium; D012710:Serum Albumin, Bovine; D006632:Histamine; D045304:Cytochromes c