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Nanoscale Designing of Iron-Sulfur Active Center in Nitrogenase towards Nano-biomimetic Enzyme

Research Project

Project/Area Number 15550129
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Functional materials chemistry
Research InstitutionKEIO UNIVERSITY

Principal Investigator

NAKAJIMA Atsushi  Keio University, Faculty of Science and Technology, Professor, 理工学部, 教授 (30217715)

Project Period (FY) 2003 – 2005
Project Status Completed (Fiscal Year 2005)
Budget Amount *help
¥3,600,000 (Direct Cost: ¥3,600,000)
Fiscal Year 2005: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2004: ¥1,300,000 (Direct Cost: ¥1,300,000)
Fiscal Year 2003: ¥1,500,000 (Direct Cost: ¥1,500,000)
KeywordsFunctional Cluster / Enzyme / Soft-landing / Self-assembled Layer / Alkanethiol Molecules / Gold Substrate / Silicon Substrate / ニトロゲナーゼ / 生体模倣機能触媒 / 有機金属クラスター / 自己組織化単分子膜 / ソフトランディング法 / 鉄 / 硫黄 / ナノクラスター / レーザー蒸発法
Research Abstract

The aim of this research has focused on the creation of nanoscale biomimetic enzyme by unveiling the function and mechanism of an iron-sulfur active center in nitrogenase enzyme. To achieve this research target, two methodologies have been developed ; (1) The production technique of organometallic and molecular clusters has been refined by laser vaporization and molecular beam in order to generate functional cluster efficiently through gas phase reactions. (2) The soft-landing method using self-assembled monolayer on a gold substrate was broadened toward various substrates, and their characteristics were evaluated by infrared reflection absorption spectroscopy (IRAS) and temperature programmed desorption spectroscopy.
Functional clusters, such as organometallic cluster of vanadium-benzene, could be soft-landed efficiently onto the self-assembled monolayer on a gold substrate compared to a bare gold substrate. The adsorption state and thermal stability of V(benzene)_2 sandwich clusters soft-landed onto a self-assembled monolayer of different chain-length n-alkanethiols (C_n-SAM, n = 8, 12, 16, 18, and 22) were studied. The IRAS measurement confirmed that V(benzene)_2 clusters are molecularly adsorbed and maintain a sandwich structure on all of the SAM substrates. In addition, the clusters supported on the SAM substrates are oriented with their molecular axes tilted 70-80° off the surface normal. An Arrhenius analysis of the TPD spectra reveals that the activation energy for the desorption of the supported clusters increases linearly with the chain-length of the SAMs. For the longest chain C_<22>-SAM, the activation energy reaches around 150 kJ/mol, and the thermal desorption of the supported clusters can be considerably suppressed near room temperature, which is superior to a silicon substrate covered with hydrocarbon molecules.

Report

(4 results)
  • 2005 Annual Research Report   Final Research Report Summary
  • 2004 Annual Research Report
  • 2003 Annual Research Report
  • Research Products

    (28 results)

All 2006 2005 2004 Other

All Journal Article (23 results) Book (1 results) Publications (4 results)

  • [Journal Article] Soft-Landing Isolation of Vanadium-Benzene Sandwich Clusters on a Room-Temperature Substrate Using n-Alkanethiolare Self-Assembled Monolayer Matrixes2006

    • Author(s)
      Masaaki Mitsui, Shuhei Nagaoka, Takeshi Matsumoto, Atsushi Nakajima
    • Journal Title

      The Journal of Physical Chemistry B 110・7

      Pages: 2968-2971

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Annual Research Report 2005 Final Research Report Summary
  • [Journal Article] Electronic Properties of Cs-Atom Doped Aluminum and Silicon Clusters : Al_nCs_m and Si_nCs_m2006

    • Author(s)
      Kiichirou Koyasu, Minoru Akutsu, Junko Atobe, Masaki Mitsui, Atsushi Nakajima
    • Journal Title

      Chemistry Physics Letters 421・4-6

      Pages: 534-539

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Photoelectron Spectroscopy of Binary Au Cluster Anions with A Doped Metal Atom : Au_nM^- (n =2-7), M = pd, Ni, Zn, Cu, and Mg2006

    • Author(s)
      Kiichirou Koyasu, Minoru Akutsu, Junko Atobe, Masaaki Mitsui, Atsushi Nakajima
    • Journal Title

      Chemistry Physics Letters 422・1,2

      Pages: 62-66

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Classification and characterization of gold and nickel nanoparticles with a differential mobility analyzer2006

    • Author(s)
      Yasutomo Naono, Sayuri Kawabata, Seung H. Huh, Atsushi Nakajima
    • Journal Title

      Science and Technology of Advanced Materials 7・2

      Pages: 209-215

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Laser Synthesis of Amorphous Iron and Cobalt Carbide Nanoparticles with Carbon Onion : Magnetic Core Shells2006

    • Author(s)
      Seung H.Huh, Atsushi Nakajima
    • Journal Title

      Journal of Applied Physics 99・6

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Soft-Landing Isolation of Vanadium-Benzene Sandwich Clusters on a Room-Temperature Substrate Using n-Alkanethiolate Self-Assembled Monolayer Matrices2006

    • Author(s)
      M.Mitsui, S.Nagaoka, T.Matsumoto, A.Nakajima
    • Journal Title

      J.Phys.Chem.B 110(7)

      Pages: 2968-2971

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electronic properties of Cs-atom doped aluminum and silicon clusters : Al_nCs_m and Si_nCs_m2006

    • Author(s)
      K.Koyasu, M.Akutsu, J.Atobe, M.Mitsui, A.Nakajima
    • Journal Title

      Chem.Phys.Lett. 421(4-6)

      Pages: 534-539

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Photoelectron spectroscopy of binary Au cluster anions with doped metal of M = Pd, Ni, Zn, Cu, and Mg : Au_nM- (n = 2-7)2006

    • Author(s)
      K.Koyasu, Y.Naono, M.Akutsu, M.Mitsui, A.Nakajima
    • Journal Title

      Chem.Phys.Lett. 422(1,2)

      Pages: 62-66

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Classification and characterization of gold and nickel nanoparticles with a differential mobility analyzer2006

    • Author(s)
      Y.Naono, S.Kawabata, S.H.Huh, A.Nakajima
    • Journal Title

      Science and Technology of Advanced Materials 7(2)

      Pages: 209-215

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Laser synthesis and magnetism of amorphous iron and cobalt carbide nanoparticles with carbon onion2006

    • Author(s)
      S.H.Huh, A.Nakajima
    • Journal Title

      J.Appl.Phys. 99(6)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Electronic Properties of Cs-Atom Doped Aluminum and Silicon Clusters : Al_nCs_m and Si_nCs_m2006

    • Author(s)
      Kiichirou Koyasu, Minoru Akutsu, Junko Atobe, Masaaki Mitsui, Atsushi Nakajima
    • Journal Title

      Chemistry Physics Letters 421

      Pages: 534-539

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Photoelectron Spectroscopy of Binary Au Cluster Anions with A Doped Metal Atom : Au_nM^-(n=2-7),M=Pd,Ni,Zn,Cu,and Mg2006

    • Author(s)
      Kiichirou Koyasu, Minoru Akutsu, Junko Atobe, Masaaki Mitsui, Atsushi Nakajima
    • Journal Title

      Chemistry Physics Letters 422

      Pages: 62-66

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Classification and characterization of gold and nickel nanoparticles with a differential mobility analyzer2006

    • Author(s)
      Yasutomo Naono, Sayuri Kawabata, Seung H.Huh, Atsushi Nakajima
    • Journal Title

      Science and Technology of Advanced Materials in press

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Laser Synthesis of Amorphous Iron and Cobalt Carbide Nanoparticles with Carbon Onion : Magnetic Core Shells2006

    • Author(s)
      Seung H.Huh, Atsushi Nakajima
    • Journal Title

      Journal of Applied Physics in press

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Formation and Photoelectron Spectroscopy of Nanoscale Cluster Anions of Biphenyl, (BP)_n (n = 2-100)2005

    • Author(s)
      Masaaki Mitsui, Yukino Matsumoto, Naoto Ando, Atsushi Nakajima
    • Journal Title

      Chemistry Letters 34・9

      Pages: 1244-1245

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Formation and Photoelectron Spectroscopy of Nanoscale Cluster Anions of Biphenyl, (BP)_n-(n = 2-100)2005

    • Author(s)
      M.Mitsui, Y.Matsumoto, N.Ando, A.Nakajima
    • Journal Title

      Chemistry Letters 34(9)

      Pages: 1244-1245

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2005 Final Research Report Summary
  • [Journal Article] Formation and Photoelectron Spectroscopy of Nanoscale Cluster Anions of Biphenyl,(BP)_n(n=2-100)2005

    • Author(s)
      Masaki Mitsui, Yukino Matsumoto, Naoto Ando, Atsushi Nakajima
    • Journal Title

      Chemistry Letters 34・9

      Pages: 1244-1245

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Lanthanide Organometallic Sandwich Nanowires : Formation Mechanism2005

    • Author(s)
      N.Hosoya, A.Nakajima 他
    • Journal Title

      Journal of Physical Chemistry A 109・1

      Pages: 9-12

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Electronic Structures of Exohedral Lanthanide-C_<60> Clusters2004

    • Author(s)
      J.Suzumura, A.Nakajima 他
    • Journal Title

      Journal of Chemical Physics 121・6

      Pages: 2649-2654

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Ferromagnetism in One-Dimensional Vanadium-Benzene Sandwich Clusters2004

    • Author(s)
      K.Miyajima, A.Nakajima 他
    • Journal Title

      Journal of American Chemical Society 126・41

      Pages: 13202-13203

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Photoelectron spectroscopy of pyrene cluster anions, (pyrene)_n^-, (n=1-20)2004

    • Author(s)
      N.Ando, A.Nakajima 他
    • Journal Title

      Chemical Physics Letters 389・3,4

      Pages: 279-283

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Coexistence of two different anion states in polyacene nanocluster anions2004

    • Author(s)
      M.Mitsui, A.Nakajima 他
    • Journal Title

      Journal of Chemical Physics 121・16

      Pages: 7553-7556

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Negative ion photoelectron spectroscopy of acridine molecular anion and its monohydrate2004

    • Author(s)
      S.Kokubo, A.Nakajima 他
    • Journal Title

      Journal of Chemical Physics 121・22

      Pages: 11112-11117

    • Related Report
      2004 Annual Research Report
  • [Book] 触媒活用大事典2004

    • Author(s)
      中嶋 敦(分担執筆)
    • Total Pages
      1134
    • Publisher
      工業調査会
    • Related Report
      2004 Annual Research Report
  • [Publications] A.Pramann: "Band gap shifting in Co-doped Nbn(n=3-15) clusters"Int.J.of Mass Spectrometry. 229. 77-82 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] M.Mitsui: "Coexistence of solvated electrons and solvent valence anions in negatively charged acetonitrile clusters"Phys.Rev.Lett.. 91・15. 153002 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] S.H.Huh: "Magnetic trapping of Co_<core>CO_<shell> Nanoparticles produced by gas phase reaction"Chem.Lett.. 印刷中.

    • Related Report
      2003 Annual Research Report
  • [Publications] 三井 正明, 中嶋 敦: "気相ナノクラスターの材料化を目指したソフトランディング技術とナノデザイン"化学工業. 55巻. 7-12 (2004)

    • Related Report
      2003 Annual Research Report

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Published: 2003-04-01   Modified: 2016-04-21  

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