2004 Fiscal Year Final Research Report Summary
Design and creation of reaction active multinuclear metal complex
| Project/Area Number |
14340208
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| Research Category |
Grant-in-Aid for Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
Inorganic chemistry
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| Research Institution | Kyoto University (2004)
Kyushu University (2002-2003) |
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Principal Investigator |
OHBA Masaaki Kyoto University, Faculty of Engineering, Associate Professor, 工学研究科, 助教授 (00284480)
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| Co-Investigator(Kenkyū-buntansha) |
OKAWA Hisashi Kyushu University, Faculty of Science, Professor, 理学研究院, 名誉教授 (00037219)
KODERA Masahito Doshisha University, Faculty of Engineering, Professor, 工学部, 教授 (00183806)
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| Project Period (FY) |
2002 – 2004
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| Keywords | Phosphotriesterase / Phosphodiesterase / Hydrolysis / Dinuclear complex / Function model |
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| Research Abstract |
(1)Phosphotriesterase-like hydrolytic function
Bis(μ-carboxylato)-μ-phenolatocomplexes, [M_2(L)(AcO)_2]^+(M=Mn,Co,Ni,Zn), based on ‘end-off' type dinucleating compartment ligand have been prepared as phosphotriesterase-model compounds which catalyze the hydrolysis of tris(p-nitrophenyl)phosphate (TNP)→bis(p-nitrophenyl)phosphate (BNP^-). The hydrolysis was traced by means of UV-vis and ESI mass spectra. The ability of hydrolysis depends on the metal combination of dinuclear core and decreased in the order, MnMn〜ZnZn>CoCo>>NiNi. This tendency is well explained by the order of nucleophilicity of water molecules binding to the metal centers. Actual phosphotriesterase has not MnMn but ZnZn dinuclear core as active sites, because natural abundance of Zn in the sea is more than that of Mn.
(2)Phosphodiesterase-like hydrolytic function
Hydrolysis of bis(p-nitrophenyl) phosphate (BNP^-) has been studied by using of dinuclear complexes, [M_2(L)(AcO)_2]^+ (M=Mn,Co,Ni,Zn). It was revealed that the hydrolysis progresses via [M_2(L)(AcO)(BNP)]^+ which was generated from an equilibrium [M_2(L)(AcO)_2]^++BNP^-= [M_2(L)(AcO)(BNP)]^++AcO^- and the ability of hydrolysis decreased in the order, MnMn〜CoCo>>NiNi>>ZnZn. The hydrolysis ability of ZnZn compound, [Zn_2(L)(AcO)_2]^+, is very low, because it forms ‘rigid' μ-acetato-μ-BNP core structure with BNP-, which is inconvenient to take water molecules on ZnZn core. In natural, phosphodiesterase has not CoCo but MnMn core as active sites, because natural abundance of Co in the sea is much less than that of Mn. Furthermore, the first function-model of purple acid phophatase which has FeZn core structure has been prepared successfully.
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Research Products
(12 results)
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[Journal Article] μ-Acetato-di-μ-phenolato-metal(II)cobalt(II) (Metal = Fe, Co, Ni, Cu, Zn) Complexes with Low-spin Co(II) : Synthesis, Structures and Magnetism2004
Author(s)
H.Matsumoto, N.Sekine, K.Arimura, M.Ohba, H.Sakiyama, H.Okawa
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Journal Title
Bulletin of the Chemical Society of Japan 77・7
Pages: 1343-1351
Description
「研究成果報告書概要(和文)」より
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[Journal Article] μ-Acetato-di-μ-phenolato-metal(II)cobalt(II) (Metal=Fe,Co,Ni,Cu,Zn) Complexes with Low-spin Co(II) : Synthesis, Structures and Magnetism2004
Author(s)
K.Matsumoto, N.Sekine, K.Arimura, M.Ohba, H.Sakiyama, H.Okawa
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Journal Title
Bulletin of the Chemical Society of Japan 77
Pages: 1343-1351
Description
「研究成果報告書概要(欧文)」より
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