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Synthetic and Electrochemical Studies of Porphyrin Derivatives and Developement of Artificial Metalloenzymes

Research Project

Project/Area Number 62470026
Research Category

Grant-in-Aid for General Scientific Research (B)

Allocation TypeSingle-year Grants
Research Field 有機化学一般
Research InstitutionTokyo Metropolitan University

Principal Investigator

SATO Takeo  Tokyo Metropolitan University, Faculty of Science, 理学部, 教授 (50087045)

Co-Investigator(Kenkyū-buntansha) KIJIMA Masashi  Tokyo Metropolitan University, Faculty of Science, 理学部, 助手 (70177822)
Project Period (FY) 1987 – 1988
Project Status Completed (Fiscal Year 1988)
Budget Amount *help
¥5,900,000 (Direct Cost: ¥5,900,000)
Fiscal Year 1988: ¥1,200,000 (Direct Cost: ¥1,200,000)
Fiscal Year 1987: ¥4,700,000 (Direct Cost: ¥4,700,000)
KeywordsPorphyrin / Iron Complex / Model of Metalloenzyme / Cyclic voltammetry / Cytochrome P450 / ヘモグロビンM / チトクロムP450 / 酵素モデル / 電解合成
Research Abstract

meso-Diphenyletioporphyrin II (DPEP) was prepared and its redox behaviors were studied by cyclic voltammetryin comparison with meso- tetraphenylporphine (TPP), octaethylporphyrin (OEP), and protoporphyrin IX dimethylester (PPIXDME). the redox potentials and basicity data of DPEP were found to be similar to those of OEP and PPIXDME.
Redox behavior of high-spin meso-diaryletioporphyrin II (DAEP) iron(III) complexes were investigated through both of equatorial and axial ligand effects. The redox potentials due to porphyrin ring were affected only by the equatorial ligands, whereas the axial ligands affected remarkably the metal redox reactions of high-spin ferric porphyrins, whether the redox potentials due to porphyrin ring or metal could be learned by examining the dependence of the redox potentials on substituents.
Redox behaviors of high-spin phenoxy and phenylthio Fe(III) porphyrins were investigated by cyclic voltammetry. The hetero-anion-ligated Fe(III) porphyrins showed a new anodic peak not observed for corresponding Fe(III) porphyrin chloride. High-spin Fe(III) porhpyrins were oxidized by controlled potential electrolysis to give the single-electron oxidation products, which were characterized by spectrophotometric (UV,V,IR) and electron spin rsonance (ESR) measurements. The single-electron oxidation products of phenoxide-ligated Fe(III) porphyrins were not Fe(III) prphyrin -cation radical of Fe(IV) prphyrin but a high-spin Fe(III) porphyrin ligated a single-electron oxidized phenoxide at an axial position.

Report

(3 results)
  • 1988 Annual Research Report   Final Research Report Summary
  • 1987 Annual Research Report
  • Research Products

    (12 results)

All Other

All Publications (12 results)

  • [Publications] 木島正志,宮森清勝,佐藤武雄: Journal of Organic Chemistry. 52. 706-707 (1987)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 木島正志,宮森清勝,佐藤武雄: Journal of Organic Chemistry. 53. 1719-1722 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 木島正志,宮森清勝,佐藤武雄: Journal of Organic Chemistry. 53. 4147-4148 (1988)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Masashi,Kijima; Kiyokatsu,Miyamori; Takeo,Sato: "A Highly Selective Photoinduced Dimerization of Olefins Catalyzed by Alkylcobaloximes" Journal of Organic Chemistry. 52. 706-707 (1987)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Masashi,Kijima;Kiyokatsu,Miyamori; Takeo,Sato: "Highly Selective Photoinduced Dimerization of Alkyl Pyruvates Catalyzed by Cobaloxime" Journal of Organic Chemistry. 53. 1719-1722 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] Masashi,Kijima; Kiyokatsu,Miyamori; Takeo,Sato: "Homolytic Alkyl Group Transfer Reaction of Photoactivated Alkylcobaloximes into Thiols." Journal of Organic Chemistry. 53. 4147-4148 (1988)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1988 Final Research Report Summary
  • [Publications] 木島正志・宮森清勝・佐藤武雄: Journal of Organic Chemistry. 52. 706-707 (1987)

    • Related Report
      1988 Annual Research Report
  • [Publications] 木島正志・宮森清勝・佐藤武雄: Journal of Organic Chemistry. 53. 1719-1722 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] 木島正志・宮森清勝・佐藤武雄: Journal of Organic Chemistry. 53. 4147-4148 (1988)

    • Related Report
      1988 Annual Research Report
  • [Publications] 木島正志;宮森清膝;佐藤武雄: Joural of Organic Chemistry. 52. 706-707 (1987)

    • Related Report
      1987 Annual Research Report
  • [Publications] 木島正志;宮森清膝;佐藤武雄: Journal of Organic Chemistny. 53. (1988)

    • Related Report
      1987 Annual Research Report
  • [Publications] 木島正志;秋元啓;佐藤武雄: Journal of American Chemistry.

    • Related Report
      1987 Annual Research Report

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Published: 1987-04-01   Modified: 2016-04-21  

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