| Project/Area Number |
13440198
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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 | Kyushu University |
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Principal Investigator |
HISAEDA Yoshio Kyushu University, Faculty of Engineering, Professor, 工学研究院, 教授 (70150498)
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| Co-Investigator(Kenkyū-buntansha) |
SHIMAKOSHI Hisashi Kyushu University, Faculty of Engineering, Research Associate, 工学研究院, 助手 (00284539)
HAYASHI Takashi Kyushu University, Faculty of Engineering, Associate Professor, 工学研究院, 助教授 (20222226)
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| Project Period (FY) |
2001 – 2003
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| Project Status |
Completed (Fiscal Year 2003)
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| Budget Amount *help |
¥14,900,000 (Direct Cost: ¥14,900,000)
Fiscal Year 2003: ¥2,800,000 (Direct Cost: ¥2,800,000)
Fiscal Year 2002: ¥5,000,000 (Direct Cost: ¥5,000,000)
Fiscal Year 2001: ¥7,100,000 (Direct Cost: ¥7,100,000)
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| Keywords | pyrrole ligand / porphyrin / porphycene / corrin ring / hemiporphycene / crystal structure / myoglobin / modified electrode / コリン / コバルト錯体 / 臭素化 / トリフルオロメチル基 / 軸配位平衡 / コバルト-炭素結合 / ポルフィリン異性体 / 付加・酸化タンデム反応 / 酸素化反応 / 配位平衡 / 有機金属錯体 |
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| Research Abstract |
Macrocyclic structure with tetrapyrrole skeleton is great interest because of its unique structure and function. In this study, porphycene and hemiporphycene which are structural isomers of porphyrin have been synthesized. Each structure was-determined by X-ray crystal analyses. These ligands complex with various transition metal, and especially substiution effect with macrocycle skeleton of its iron and cobalt complex was studied. The cobalt(II) complexes of a series of peripheral substituted porphycene ligands with bromine have been synthesized and its various properties have been investigated by means of CV,UV-VIS and NMR spectroscopies. Linear relationships between the number of bromine and various physicochemical properties were observed.
Reconstituted myoglobin with iron porphycene as an artificial prosthetic group exhibits an extremely high molecular oxygen affinity and low autooxidation rate. This study showed that the modification of the heme framework will serve as an effective method for the creation of a unique functionalized hemoprotein.
Hydrophobic vitamin B12 which is tetrapyrrole pigment was immobilized onto various electrode by a sol-gel reaction. The complex was physically retained in a silica gel film which is formed on an electrode. The immobilized complex exhibits the Co(II)/Co(I) redox couple and retain its electrochemical activity. This electroactive complex shows a high reactivity towards organic halides, and the controlled-potential electrolysis of benzyl bromide using the sol-gel modified electrode at -1.2 V vs. Ag/AgCl in aqueous solution afforded dehalogenated products, bibenzyl and toluene, with a total turnover number over 1000 for 1 hour.
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