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Dynamics of molecular recognition

Research Project

Project/Area Number 04101003
Research Category

Grant-in-Aid for Specially Promoted Research

Allocation TypeSingle-year Grants
Research InstitutionKYOTO UNIVERSITY

Principal Investigator

OGOSHI Hisanobu  Kyoto University, Graduate School of Engineering, Professor, 工学研究科, 教授 (90026188)

Co-Investigator(Kenkyū-buntansha) SUZUKI Akihiro  Nagaoka National College of Technology, Department of Materials Engineering, Ass, 物質工学科, 助手 (60179190)
MASUDA Hideki  Nagoya Institute of Technology, Department of Applied Chemistry, Professor, 応用化学科, 助教授 (50209441)
AOYAGI Katsuhiro  Fukushima National College of Technology, Department of Industrial Chemistry, As, 工業化学科, 助教授 (40150940)
HAYASHI Takashi  Kyoto University, Graduate School of Engineering, Research Associate, 工学研究科, 助手 (20222226)
Project Period (FY) 1992 – 1995
Project Status Completed (Fiscal Year 1995)
Budget Amount *help
¥250,000,000 (Direct Cost: ¥250,000,000)
Fiscal Year 1995: ¥10,000,000 (Direct Cost: ¥10,000,000)
Fiscal Year 1994: ¥15,000,000 (Direct Cost: ¥15,000,000)
Fiscal Year 1993: ¥80,000,000 (Direct Cost: ¥80,000,000)
Fiscal Year 1992: ¥145,000,000 (Direct Cost: ¥145,000,000)
KeywordsMolecular Recognition / Porphyrin / Chiral Recognition / Electron Transfer / Thermodynamic Parameter / Conformation / Solvent Effects / 熱力学パラメーター / 円偏光ニ色性 / 電子移動反応 / 水素結合 / キノン / シクロデキストリン / ヌクレオチド / アミノ酸 / シクロデモストリン / ユビキノン
Research Abstract

We have studied four topics to elucidate the dynamics of molecular recognition : (1) Conformational changes induced by molecular recognition, (2) Thermodynamic and spectroscopic studies of multi-point molecular recognition, (3) Electron transfer process regulated by molecular recognition, and (4) Fluoroporphyrins and reconstituted myoglobin.
1.Induced-fit binding of quinones to tetrahydroxyporphyrin results in the atropisomerization in the porphyrin. Also preorganization of flexible nucleobase receptor before binding a target guest was demonstrated by determining thermodynamic parameters of the binding. Porphyrin dimer formation following atropisomerization was also studied kinetically.
2.Circular dichroism was used to investigate the interaction mode of porphyrin-amino acid system. Two-point recognition lead to split-type induced CD,through electrostatic coupling between the chromophores. Novel chiral porphyrins were prepared, which show moderate to high enantioselective binding of amino acid esters. Receptors for tartaric acid, aspartic acid and sugars were also prepared. These receptors showed high regioselectivity for the guest. Enthalpy and entropy changes upon complexation were used to estimate conformational changes during complex formation.
3.Fast electron transfer from singlet state of porphyrin to quinone or viologens driven photochemically was realized by designing a binding site for quenchers. Electron transfer from zinc porphyrin in myoglobin to quinone which is attached by a peptide spacer occurred from a singlet state with a rate one order of magnitude slower than in dichloromethane.
4.Reconstitution of myoglobin by artificial hemes showed that interactions between heme and apoprotein can be split into contributions from non-polar interactions of 1,2,3,4-alkyl groups and polar interactions of 6,7-propionate groups. The polar interactions between propionate groups and protein was found to stabilize oxyheme.

Report

(5 results)
  • 1995 Annual Research Report   Final Research Report Summary
  • 1994 Annual Research Report
  • 1993 Annual Research Report
  • 1992 Annual Research Report
  • Research Products

    (36 results)

All Other

All Publications (36 results)

  • [Publications] T.Hayashi: "Relationship between Electron Transfer and Structure of Quinone-Linked Zinc Porphyrin having Flexible Peptide Spacer" J.Chem.Soc.,Chem.Commun.545-546 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H.Ogoshi: "Molecular Rccognition: New Chiral Metalloporphyrins as Receptor Model" Supramolecular Chemistry. 6. 115-124 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T.Mizutani: "Molecular Recognition of Carbohydrates by Zinc Porphyrins." J.Chem.Soc.,Chem.Commun.1257-1258 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Kuroda: "Chiral Amino Acid Recognition on Artificial Receptor Based on Porphyrin" J.Am.Chem.Soc.117. 10950-10957 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T.Hayashi: "Photoinduced Singlet Electron Transfer in a Complex Formed from Zinc Myoglobin and Methyl Viologen: Artificial Recognition by a Chemically Modified Porphyrin" J.Am.Chem.Soc.117. 11606-11607 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T.Mizutani: "An Artificial Receptor for Dimethyl Aspartate" J.Qrg.Chem.61. 539-548 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T.Hayashi: "Relationship between Electron Transfer and Structure of Quinone-Linked Zinc Porphyrin having Flexible Peptide Spacer" J.Chem.Soc., Chem.Commun.545-546 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] H.Ogoshi, Molecular Recognition: "New Chiral Metalloporphyrins as Receptor Models" Supramol.Chem. 6. 115-124 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T.Mizutani: "Molecular Recognition of Carbohydrates by Zinc Porphyrins" J.Chem.Soc., Chem.Commun.1257-1258 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] Y.Kuroda, Chiral Amino Acid Recognition on Artificial Receptor Based on Porphyrin: "J.Am.Chem.Soc." 117. 10950-10957 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T.Hayashi: "Photoinduced Singlet Electron Transfer in a Complex Formed from Zinc Myoglobin and Methyl Viologen : Artificial Recognition by a Chemically Modified Porphyrin" J.Am.Chem.Soc. 117. 11606-11607 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T.Mizutani: "An artificial Receptor for Dimethyl Aspartate" J.Org.Chem. 61. 539-548 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1995 Final Research Report Summary
  • [Publications] T.Hayashi: "Relationship between Electron Transfer and Structure of Quinone-Linked Zinc Porphyrin having Flexible Peptide Spacer" J.Chem.Soc.,Chem.Commun. 545-546 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] H.Ogoshi: "Molecular Recognition:New Chiral Metalloporphyrins as Receptor Model" Supramolecular Chemistry. 6. 115-124 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] H.Ogoshi: "Molecular Recognition of Carbohydrates by Zinc Porphyrins." J.Chem.Soc.,Chem.Commun.1257-1258 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] H.Ogoshi: "Chiral Amino Acid Recongnition on Artificial Receptor Based on Porphyrin" J.Am.Chem.Soc.117. 10950-10957 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] T.Hayashi: "Photoinduced Singlet Electron Transfer in a Complex Formed from Zinc Myoglobin and Methyl Viologen:Artificial Recognition by a Chemically Modified Porphyrin" J.Am.Chem.Soc.117. 11606-11607 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] H.Ogoshi: "An Artificial Receptor for Dimethyl Aspartate" J.Org.Chem.61. 539-548 (1996)

    • Related Report
      1995 Annual Research Report
  • [Publications] Tadashi MiZutani: " Design and Synthesis of a Trifunctional Chiral Porphyrin with C2 Symmetry as a ChiraI Recognition hos for Amino Acid Esters" J.Am.Chen.Soc.116. 4240-4250 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Tadashi Mizutani: "Mechanism of lnduced Circular Dichroism of Amino Acid Ester-Pophyrin Supramolecular Systems." 1norg.Chem.33. 3558-3566 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Takashi Hayashi: "Imetermolecular lnteraction between MuItifunctional Porphyrin and Ubiquinone Analogues" Pure Appl.Chem.66. 797-802 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Takashi Hayashi: "Preparation and Binding Affinity of New Porphyrin Host Molecule for Ubiquinone" Chem.Lett.1749-1752 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Yasuhisa Kuroda: "Flexible Nucleobase Receptor-Effect of Self-preorganization of Artificial Receptor." Tetrahedron Lett.35. 3729-3733 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Yasuhisa Kuroda: "Molecular Trench:Highly Complementary Binding Sites for Tsrtaric Acid DialkyI Ester" J.Am.Chem.Soc.106. 10338-10339 (1994)

    • Related Report
      1994 Annual Research Report
  • [Publications] Yasuhisa Kuroda: "Controlled Electron Transfer between Cyclodextrin Sandwiched Porphyrin and Quinones" J.Am.Chem.Soc.115. 7003-7004 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Takashi Hayashi: "Dynamic Molecular Recognition in a Multifunctional Porphyrin and a Ubiquinone Analogue" J.Am.Chem.Soc.115. 12210-12211 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Yasuhisa Kuroda: "Nucleotide Recognition in Aqueous Media with Artificial Receptor Based on Porphyrin" Tetrahedron Lett.34. 8285-8288 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Yasuhisa Kuroda: "Selective Transport of Nucleotides Mediated by Functionalized Porphyrin" Supramolecular Chem.3(印刷中). (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Yasuhisa Kuroda: "New Chiral Porphyrins-Syntheses and Molecular Recognition" Anger.Chem.105. 774-776 (1993)

    • Related Report
      1993 Annual Research Report
  • [Publications] Koichiro Jitsukawa: "Induced Assembly of Aromatic Rings Caused by a CH…π Interaction" Chem.Lett.303-306 (1994)

    • Related Report
      1993 Annual Research Report
  • [Publications] Takashi Hayashi: "Specific Molecular Recognition via Multipoint Hydrogen Bonding Ubiquinone Analogues-Porphyrin Having Four Convergent Hydoxyl Groups Pairing" J.Am.Chem.Soc.115. (1193)

    • Related Report
      1992 Annual Research Report
  • [Publications] Tadashi Mizutani: "Recognition of a-Amino Acid Esters by Zinc Porphyrin Derivatives via Coordination and Hydrogen Bonding Interactions.Evidence foe Two-point Fixation from Thermodynamic and Induced Circular Dichroism Spectroscopic Studies" Inorg.Chem. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Tadashi Mizutani: "Recognition of Chirality and Residual Groups of Amino Acid Esters using New Trifunctional Chiral Porphyrins C_2 Symmetry" J.Chem.Soc.,Chem Commun.(1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Takashi Hayashi: "Synthesis and Structure of a New cis-1,3-Dihydroxycyclohexane Derivative having Four Convergent Hydroxy Groups" J.Chem.Soc.,Chem.Commun.364-365 (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Yasuhisa Kuroda: "Liquid Chromatography with Aminopropylsilica Gel Modified by Heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin Derivative" Bull.Chem.Soc.Jpn.66. (1993)

    • Related Report
      1992 Annual Research Report
  • [Publications] Hideki Masuda: "Structures and Stabilities of Ternary Copper(II) Complexes Containing an Acidic and a Basic Amino Acid Evidence for Arginine Side Chain Involvement in Intermolecular Interactions and Its Biological Implication" Inorg.Chem.(1993)

    • Related Report
      1992 Annual Research Report

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Published: 1992-04-01   Modified: 2016-04-21  

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