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Molecular Recognition and Catalytic Functions of Novel Macrocyclic Compounds

Research Project

Project/Area Number 01470097
Research Category

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

Allocation TypeSingle-year Grants
Research Field Synthetic chemistry
Research InstitutionKyushu University

Principal Investigator

MURAKAMI Yukito  Kyushu University, Department of Organic Synthesis, Professor, 工学部, 教授 (30037717)

Co-Investigator(Kenkyū-buntansha) OHNO Teruhisa  Kyushu University, Department of Organic Synthesis, Associate Professor, 工学部, 助教授 (10203887)
HISAEDA Yoshio  Kyushu University, Department of Organic Synthesis, Associate Professor, 工学部, 助教授 (70150498)
Project Period (FY) 1989 – 1990
Project Status Completed (Fiscal Year 1990)
Budget Amount *help
¥7,400,000 (Direct Cost: ¥7,400,000)
Fiscal Year 1990: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 1989: ¥6,100,000 (Direct Cost: ¥6,100,000)
KeywordsHydrophobic vitamin B_<12> / Holoenzyme model / Octopus cyclophane / Cage-type cyclophane / Molecular discrimination / Isomerization reaction / Lock-and-key mechanism / Induced-fit mechanism / Schiff塩基生 / ビタミンB_6 / 疎水性相互作用 / 不斉認識 / ビタミンB_<12> / 触媒官能基 / 分子認識 / 静電相互作用
Research Abstract

We prepared an octopus cyclophanes having L-aspartate residues as connector units interposed between a macrocyclic ring and four double-chain hydrocarbon segments. This cationic host strongly binds anionic and nonionic hydrophobic guests and exercises the induced-fit guest-binding behavior originating from both hydrophobic and electrostatic interactions. We also prepared a hexapus cyclophane having three catechol moieties and six hydrocarbon chains, the former acting as the metal binding sites. The inclusion behavior of a Fe-complex of the hexapus cyclophane was examined in water. When the catechol segments of the cyclophane are coordinated to Fe^<3+>, the binding constant for hydrophobic guests becomes larger than that of the hexapus cyclophane without metal coordination. The present metal-bound hexapus cyclopahne exhibits marked inclusion capability toward organic guests, as arising from hydrophobic, electrostatic, and coordination effects. Vitamin B_<12>-dependent enzymes catalyze v … More arious isomerization reactions accompanied with carbon-skeleton rearrangements. In order to simulate catalytic functions of vitamin B_<12>-dependent enzymes, we have been dealing with hydrophobic vitamin B_<12> derivatives. We succeeded in constructing an artificial vitamin B_<12>-dependent holoenzyme composed of an octopus cyclophane as an apoenzyme model and hydrophobic vitamin B_<12> as a coenzyme model. The octopus cyclophane acts as an effective apoenzyme model for constitution of an artificial vitamin B_6-dependent holoenzyme by simultaneous incorporation of pyridoxal-5'-phosphate and a hydrophobic alkylammonium substrate into the host cavity to give the Schiff-base species, showing the substrate selectivity.
We prepared cyclophanes of another structural feature ; a cage-type cubical molecule with six faces each consisting of a 2, 11, 20, 29-tetraaza[3.3.3.3] paracyclophane ring. This host possesses eight tertiary aminomoieties and acts as a polycationic host in acidic media. The host shows size-sensitive and regioselective molecular discrimination. The second cage-type cyclophane is composed of two macrocyclicskeletons, 1, 6, 20, 25-tetraaza[6.1.6.1.] paracyclophane 2, 11, 20, 29-tetraaza[3.3.3.3] paracyclophane segments. This cationic host incorporates anionic and nonionic hydrophobic fluorescent guests into its in ternal cavityand exercises marked chiral discrimination toward selected amino acids in aqueous media. Less

Report

(3 results)
  • 1990 Annual Research Report   Final Research Report Summary
  • 1989 Annual Research Report
  • Research Products

    (29 results)

All Other

All Publications (29 results)

  • [Publications] Yukito Murakami: "Molecular Recognition of Hydrophobic Ammonium Substrates by a Cationic Octopus Cyclophane Bearing Noncovalently Bound Pyridoxalー5'ーPhosphate: A Vitamin B_6ーdependent Holoenzyme Model" Journal of Inclusion Phenomena. 7. 91-97 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Molecular Discrimination by Waterーsoluble Cubic Azaparacyclophane" Chemistry Letters. 881-884 (1989)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Hydrophobic Vitamin B_<12>. VII. Ringーexpansion Reactions Catalyzed by Hydrophobic Vitamin B_<12> in Octopus Azaparacyclophane" Journal of Coordination Chemistry. 21. 13-22 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yoshio Hisaeda: "Preparation and Molecular Recognition Behavior of a Hexapus Azaparacyclophane" Tetrahedron Letters. 31. 1027-1030 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Hydrophobic Vitamin B_<12>. 8. Carbonーskeleton Rearrangement Reactions Catalyzed by Hydrophobic Vitamin B_<12> in Octopus Azaparacyclophane" Bioorganic Chemistry. 18. 49-62 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Syntheses of Macrocyclic Enzyme Models.7.Octopus Cyclophanes Having LーAspartate residues as Novel Waterーsoluble Hosts;Aggregation Behavior and Inducedーfit Molecular Recognition" Journal of the American Chemical Society. 112. 7672-7681 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Inclusion Phenomena and Molecular Recognition" J.Atwood編,Plenum Press (New York), 11 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Advances in Supramolecular Chemistry" G.W.Gokel編,JAI Press (Greenwich,Connecticut), 36 (1990)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Molecular Recognition of Hydrophobic Ammonium Substrates by a Cationic Octopus Cyclophane Bearing Noncovalently BoundPyridoxal-5'-phosphate : A Vitamin B_6-dependent Holoenzyme Model" Journal of Inclusion Phenomena. 7. 91-97 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Molecular Discrimination by Water-soluble Cubic Azaparacyclophane" Chemistry Letters. 881-884 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Cyclophane-Molecular Recognition Behavior as Artificial Receptors and Enzymes" Journal of Synthetic Organic Chemistry, Japan. 47. 484-492 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "pH-Dependent Molecular Recognition Performed by a Polycationic Cibic Azaparacyclophane" Chemistry Letters. 1199-1202 (1989)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Hydrophobic Vitamin B_<12>. VII. Ring-expansion Reactions Catalyzed by Hydrophobic Vitamin B_<12> in Octopus Azaparacyclophane" Journal of Coordination Chemistry. 21. 13-22 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yoshio Hisaeda: "Preparation and Molecular Recognition Behavior of a Hexapus Azaparacyclophane" Tetrahedron Letters. 31. 1027-1030 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Hydrophobic Vitamin B_<12>.8. Carbon-skeleton Rearrangement Reactions Catalyzed by Hydrophobic Vitamin B_<12> in Octopus Azaparacyclophane" Bioorganic Chemistry. 18. 49-62 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Syntheses of Macrocyclic Enzyme Models. 7. Octopus Cyclophanes Having L-Aspartate Residues as Novel Water-soluble Hosts ; Aggregation Behavior and Induced-fit Molecular Recognition" Journal of the American Chemical Society. 112. 7672-7681 (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Catalytic Functions of Paracyclophanes Based on Molecular Recognition" Inclusion Phenomena and Molecular Recognition J. Atwood ed, Plenum Press. (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Molecular Recognition by Macrocycles Having a Three-dimensionally Extended Hydrophobic Cavity" Advances in Supramolecular Chemistry. vol. 1. (1990)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1990 Final Research Report Summary
  • [Publications] Yukito Murakami: "Hydrophobic Vitamin B_<12>.VII.Ringーexpansion Reactions Catalyzed by Hydrophobic Vitamin B_<12> in Octopus Azaparacyclophane" Journal of Coordination Chemistry. 21. 13-22 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Yoshio Hisaeda: "Preparation and Molecular Recognition Behavior of a Hexapus Azaparacyclophane" Tetrahedron Letters. 31. 1027-1030 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Yukito Murakami: "Hydrophobic Vitamin B_<12>.8.Carbonーskeleton Rearrangement Reactions Catalyzed by Hydrophobic Vitamin B_<12> in Octopus Azaparacyclophane" Bioorganic Chemistry. 18. 49-62 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Yukito Murakami: "Syntheses of Macrocyclic Enzyme Models.7.Octopus Cyclophanes Having LーAspartate Residues as Novel Waterーsoluble Hosts;Aggregation Behavior and Inducedーfit Molecular Recognition" Journal of the American Chemical Society. 112. 7672-7681 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Yukito Murakami: "Inclusion Phenomena and Molecular Recognition" J.Atwood 編,Plenum Press (New York), 11 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Yukito Murakami: "Advances in Supramolecular Chemistry" G.W.Gokel 編,JAI Press (Greenwich,Connecticut), 36 (1990)

    • Related Report
      1990 Annual Research Report
  • [Publications] Yukito Murakami: "Molecular Recognition of Hydrophobic Ammonium Substrates by a Cationic Octopus Cyclophane Bearing Noncovalently Bound Pyridoxal-5'-Phosphate:A Vitamin B_6ーdependent Holoenzyme model" Journal of Inclusion Phenomena. 7. 91-97 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Yukito Murakami: "Molecular Descrimination by Water-soluble Cubic Azaparacyclophane" Chemistry Letters. 5. 881-884 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] 村上幸人: "シクロファンー人工レセプタ-・人工酵素としての分子認識" 有機合成化学協会誌. 47. 484-492 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] Yukito Murakami: "pH-Dependent Molecular Recognition Performed by a Polycationic Cubic Azaparacyclophane" Chemistry Letters. 7. 1199-1202 (1989)

    • Related Report
      1989 Annual Research Report
  • [Publications] 村上幸人: "包接化合物の基礎と応用" (株)エヌ・テェ-・エス, 25 (1989)

    • Related Report
      1989 Annual Research Report

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Published: 1989-04-01   Modified: 2016-04-21  

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