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2003 Fiscal Year Final Research Report Summary

Development of Novel Tetrapyrrole Ligands and Their Metal Complexes with New Functions

Research Project

Project/Area Number 13440198
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionKyushu University

Principal Investigator

HISAEDA Yoshio  Kyushu University, Faculty of Engineering, Professor, 工学研究院, 教授 (70150498)

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)
Project Period (FY) 2001 – 2003
Keywordspyrrole ligand / porphyrin / porphycene / corrin ring / hemiporphycene / crystal structure / myoglobin / modified electrode
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.

  • Research Products

    (66 results)

All Other

All Publications (66 results)

  • [Publications] H.Shimakoshi, et al.: "Synthesis and Redox Behavior of Dialkylated Dicobalt Complexes Having Two Discrete Salen Units"Tetrahedron Letters. Vol.42. 1949-1951 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Hitomi, et al.: "Interprotein Electron Transfer Reaction Regulated by an Artificial Interface"Angew.Chem.Int.Ed. Vol.40. 1098-1101 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Shimakoshi, et al.: "Formation and Cleavage of a Dicobalt Complex Bridged with a Pentamethylene Group"Chem.Lett. 346-347 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Hayashi, et al.: "Cobaltporphycenes as Catalysts. The Oxidation of Vinyl Ethers via the Formation and Dissociation of Cobalt-Carbon Bonds"Organometallics. Vol.20. 3074-3078 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Shimakoshi, et al.: "Electroorganic Syntheses of Macrocyclic Lactones Mediated by Vitamin B12 Model Complexes"J.Electroanal.Chem. 507. 170-176 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Shimakoshi, et al.: "Reductive Coupling of benzyl Bromide Catalyzed by a Novel Dicobalt Complex Having Two Salen Units"J.Chem.Soc., Dalton Trans. 1971-1974 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Ariga, et al.: "Langmuir Monolayer of Organoalkoxysilane for vitamin B12-modified Electrode"Physical Chemistry Chemical Physics. Vol.3. 3442-3442 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Hayashi, et al.: "Chemical Properties of Reconstituted Myoglobins with Functionalized Hemin Derivatives"J.Inorg.Biochem. 86. 57-57 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Ando, et al.: "Photoinduced Electron Transfer within an Artificially Created Protein-protein Complex"J.Inorg.Biochem. 86. 124-124 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Dejima, et al.: "New Myoglobin Reconstituted with an Iron Porphycene as a Structural Isomer of Heme Moiety"J.Inorg.Biochem. 86. 200-200 (2001)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Hayashi, et al.: "New Functionalization of Myoglobin by Chemical Modification of Heme-Propionates"Acc.Chem.Res. 35. 35-43 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Hayashi, et al.: "Chemical Recognition and Chiral Induction by Use of Zinc Porphyrin Dimers"Tetrahedron. 58. 2803-2811 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Shimakoshi, et al.: "Synthesis, Characterization, and Redox Behavior of New Dicobalt Complexes Having Monoanionic Imine/Oxime-type Ligands"Bull.Chem.Soc.Jpn.. 75. 1553-1558 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Hayashi, et al.: "Contribution of Heme-Propionate Side Chains to Structure and Function of Myoglobin : Chemical Approach by Artificially Created Prosthetic Groups"J.Inorg.Biochem. 91. 94-100 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] I.Aritome, et al.: "3,6,13,19-Tetrabromo-2,7,12,17-tetrapropylporphycene"Acta Cryst. C58. 563-564 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] K.Sakurai, et al.: "Polysaccharide-Polynucleotide Complexes VIII. Cation-Induced Complex Formation between Polyuridylic Acid and Schizophyllan"Biopolymers. 65. 1-9 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Hayashi, et al.: "Blue Myoglobin Reconstituted with an Iron Porphycene Shows Extremely High Oxygen Affinity"J.Am.Chem.Soc. 124. 11226-11227 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Matsuo, et al.: "Reductive Activation of Dioxygen by a Myoglobin Reconstituted with a Flavohemin"J.Am.Chem.Soc. 124. 11234-11235 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Shimakoshi, et al.: "Syntheses of Large-membered Macrocycles Having multiple Hydrogen Bonding Moieties"Tetrahedron Lett. 43. 8261-8264 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] F.Tani, et al.: "Iron Twin-Coronet Porphyrins as Models of Myoglobin and Hemoglobin : Amphibious Electrostatic Effects of Overhanging Hydroxyl Groups for Successful CO/O_2 Discrimination"Chem.Eur.J.. 9. 862-870 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Maeda, et al.: "N-Confused Porphyrin-Bearing meso-Perfluorophenyl Groups : A Potential Agent That Forms Stable Square-Planar Complexes with Cu (II) and Ag (III)"Org.Lett. 5. 1293-1296 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Hayashi, et al.: "Enhancement of Peroxygenase Activity of Horse Heart Myoglobin by Modification of Heme-propionate Side Chains"Chem.Lett. 32. 496-497 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Shimakoshi, et al.: "Hydrophobic Vitamin B12. Part 18. Preparation of a sol-gel modified electrode immobilized with vitamin B12 derivative and its reductive dehalogenation activity"J.Chem.Soc., Dalton Trans. 2308-2312 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Shimakoshi, et al.: "Syntheses of new water-soluble dicobalt complexes having two cobalt-carbon bonds and their ability for DNA cleavage"Tetrahedron Lett. 44. 5197-5199 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Hayashi, et al.: "Role of Heme-Propionate Side Chains in Myoglobin Function"J.Inorg.Biochem. 96. 50-50 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Shimakoshi, et al.: "Solid-solid synthesis of a hydrophobic vitamin B12 having a benzo-18-crown-6 moiety at the C10 position of the corrin ring"Tetrahedron Lett. 44. 6421-6424 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Hayashi, et al.: "Synthesis, Structure and Unique Chemical Property of a First Fluorine-Containing Porphycene"Org.Lett. 5. 2845-2848 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] T.Hayashi, et al.: "Synthesis, Characterization and Autoreduction of a Highly Electron-Deficient Porphycenatoiron (III) with Trifluoromethyl Substituents"Inorg.Chem. 42. 7345-7347 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Hisaeda et al.: "Organic/Inorganic Hybrid Nanomaterials with Vitamin B_<12> Functions"Interface. 3. 73-78 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Shimakoshi, et al.: "Preparation and electrochemical behaviour of hydrophobic vitamin B12 covalently immobilized onto platinum electrode"Chem.Commun. 50-51 (2004)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Sato, et al.: "Hybridization of Modified-Heme Reconstitution and Distal Histidine Mutation to Functionalize Sperm Whale Myoglobin"J.Am.Chem.Soc. 126. 436-437 (2004)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Hisaeda, et al.: "Organic Electrochemistry"The Etectrochemical Society. 4 (2002)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] Y.Hisaeda, et al.: "Mechanistic and Synthetic Aspects of Organic and Biological Electrochemistry (Eds. by J.Simonet, D.Peters, H.Tanaka)"The Electrochemical Society. 4 (2003)

    • Description
      「研究成果報告書概要(和文)」より
  • [Publications] H.Shimakoshi et al.: "Synthesis and Redox Behavior of Dialkylated Dicobalt Complexes Having Two Discrete Salen Units"Tetrahedron Letters. Vol.42. 1949-1951 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Hitomi et al.: "Interprotein Electron Transfer Reaction Regulated by an Artificial Interface"Angew.Chem.Int.Ed.Engl.. Vol.40. 1098-1101 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Shimakoshi et al.: "Formation and Cleavage of a Dicobalt Complex Bridged with a Pentamethylene Group"Chem.Lett.. 346-347 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Hayashi et al.: "Cobaltporphycenes as Catalysts. The Oxidation of Vinyl Ethers via the Formation and Dissociation of Cobalt-Carbon Bonds"Organometallics. Vol.20, No.14. 3074-3078 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Shimakoshi et al.: "Electroorganic Syntheses of Macrocyclic Lactones Mediated by Vitamin B_<12> Model Complexes"J.Electroanal.Chem.. Vol.507, No.1-2. 170-176 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Shimakoshi et al.: "Reductive Coupling of benzyl Bromide Catalyzed by a Novel Dicobalt Complex Having Two Salen Units"J.Chem.Soc.(Dalton Trans.). No.13. 1971-1974 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Ariga et al.: "Langmuir Monolayer of Organoalkoxysilane vitamin B12-modified Electrode"Physical Chemistry Chemical Physics. Vol.3. 3442-3446 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Hayashi et al.: "Chemical Properties of Reconstituted Myoglobins with Functionalized Hemin Derivatives"J.Inorg.Biochem.. Vol.86, No.1. 57 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Ando et al.: "Photoinduced Electron Transfer within an Artificially Created Protein-protein Complex"J.Inorg.Biochem.. Vol.86, No.1. 124 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Dejima et al.: "New Myoglobin Reconstituted with an Iron Porphycene as a Structural Isomer of Heme Moiety"J.Inorg.Biochem.. Vol.86, No.1. 200 (2001)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Hayashi et al.: "New Functionalization of Myoglobin by Chemical Modification of Heme-Propionates"Acc.Chem.Res.. Vol.35. 35-43 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Hayashi et al.: "Chemical Recognition and Chiral Induction by Use of Zinc Porphyrin Dimers"Tetrahedron. Vol.58,. 2803-2811 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Shimakoshi et al.: "Synthesis, Characterization, and Redox Behavior of New Dicobalt Complexes Having Monoanionic Imine/Oxime-type Ligands"Bull.Chem.Soc.jpn.. Vol.75, No.7. 1553-1558 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Hayashi et al.: "Contribution of Heme-Propionate Side Chains to Structure and Function of Myoglobin : Chemical Approach by Artificially Created Prosthetic Groups"J.Inorg.Biochem.. Vol.91. 94-100 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] I.Aritome et al.: "3,6,13,19-Tetrabromo-2,7,12,17-tetrapropylporphycene"Acta Cryst.. Vol.C58. 563-564 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] K.Sakurai et al.: "Polysaccharide-Polynucleotide Complexes VIII. Cation-Induced Complex Formation between Polyuridylic Acid and Schizophyllan"Biopolymers. Vol.65. 1-9 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Hayashi et al.: "Blue Myoglobin Reconstituted with an Iron Porphycene Shows Extremely High Oxygen Affinity"J.Am.Chem.Soc.. Vol.124, No.38. 11226-11227 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Matub et al.: "Reductive Activation of Dioxygen by a Myoglobin Reconstituted with a Flavohemin"J.Am.Chem.Soc.. Vol.124, No.38. 11234-11235 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Shimakoshi et al.: "Syntheses of Large-membered Macrocycles Having multiple Hydrogen Bonding Moieties"Tetrahedron Lett.. Vol.43, No.46. 8261-8264 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] F.Tani ef al.: "Iron Twin-Coronet Porphyrins as Models of Myoglobin and Hemoglobin : Amphibious Electrostatic Effects of Overhanging Hydroxyl Groups for Successful CO/O_2 Discrimination"Chem.Eur.J.. Vol.9, No.4. 862-870 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Maeda et al.: "N-Confused Porphyrin-Bearing meso-Perfluorophenyl Groups : A Potential Agent That Forms Stable Square-Planar Complexes with Cu(II) and Ag(III)"Org.Lett.. Vol.5, No.8. 1293-1296 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Hayashi et al.: "Enhancement of Peroxygenase Activity of Horse Heart Myoglobin by Modification of Heme-propionate Side Chains"Chem.Lett.. Vol.32, No.6. 496-497 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Shimakoshi et al.: "Hydrophobia Vitamin B_<12>. Part 18. Preparation of a sol-gel modified electrode immobilized with vitamin B_<12> derivative and its reductive dehalogenation activity"J.Chem.Soc.(Dalton Trans.). 2308-2312 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Shimakoshi et al.: "Syntheses of new water-soluble dicobalt complexes having two cobalt-carbon bonds and their ability for DNA cleavage"Tetrahedron Lett.. Vol.44, No.28. 5197-5199 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Hayashi et al.: "Role of Heme-Propionate Side Chains in Myoglobin Function"J.Inorg.Biochem.. Vol.96. 50 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Shimakoshi et al.: "Solid-solid synthesis of a hydrophobic vitamin B_<12> having a benzo-18-crown-6 moiety at the C10 position of the corrin ring"Tetrahedron Lett.. Vol.44, No.34. 6421-6424 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Hayashi et al.: "Synthesis, Structure and Unique Chemical Property of a First Fluorine-Containing Porphycene"Org.Lett.. Vol.5, No.16. 2845-2848 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] T.Hayashi et al.: "Synthesis, Characterization and Autoreduction of a Highly Electron-Deficient Porphycenatoiron(III) with Trifluoromethyl Substituents"Inorg.Chem.. Vol.42, No.23. 7345-7347 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Shimakoshi et al.: "Preparation and electrochemical behaviour of hydrophobic vitamin B_<12> covalently immobilized onto platinum electrode."Chem.Commun.. 50-51 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] H.Sato et al.: "Hybridization of Modified-Heme Reconstitution and Distal Histidine Mutation to Functionalize Sperm Whale Myoglobin"J.Am.Chem.Soc.. Vol.126, No.2. 436-437 (2004)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Hisaeda et al.: "Electrochemical Molecular Transformations Catalyzed by Vitamin B_<12> Derivatives"Organic Electrochemistry. Vol.10. 48-51 (2002)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Hisaeda et al.: "Reductive Molecular Transformations on Vitamin B_<12> Modified Electrodes"Mechanistic and Synthetic Aspects of Organic and Biological Electrochemistry. 109-112 (2003)

    • Description
      「研究成果報告書概要(欧文)」より
  • [Publications] Y.Hisaeda et al.: "Organic/Inorganic Hybrid Nanomaterials with Vitamin B_<12> Functions"Interface. No.3. 73-78 (2003)

    • Description
      「研究成果報告書概要(欧文)」より

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Published: 2005-04-19  

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