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2018 Fiscal Year Annual Research Report

N-Heterocyclic Carbene-modified Gold Nanoclusters: Novel Materials with Potential Biological Applications

Research Project

Project/Area Number 16K13962
Research InstitutionNagoya University

Principal Investigator

CRUDDEN Cathleen  名古屋大学, トランスフォーマティブ生命分子研究所, 客員教授 (10721029)

Project Period (FY) 2016-04-01 – 2019-03-31
KeywordsNano Materials / Nanocluster / N-Heterocyclic Carbene / Gold / Thiol / Biological Applications / Stability
Outline of Annual Research Achievements

金属ナノ粒子、ナノクラスターはバルク金属、金属錯体とも異なる物性を示すことから新規金属材料として注目を集めている。その中でも金ナノ物質は生体イメージングとしての応用が期待されてきたが、生体環境下での安定性が大きな課題であった。これまでにN-ヘテロサイクリックカルベン(NHC)を用いることで金表面、金ナノ粒子を極めて安定化させることを見出している。本研究では安定性に優れたNHCで修飾された新規金ナノクラスターの創製を目指した。本年度は二座NHC配位子を有する金錯体からのボトムアップ合成による金ナノクラスターの創製を行った。昨年度に二座NHC配位子を用いることで温度やチオールに対して非常に安定な金ナノ粒子を得ることに成功している。この知見を基に、アルキル基で架橋したイミダゾリウム塩を合成した。次に塩基存在下、塩化金ジメチルスルフィド錯体と反応させることで二座NHC-金錯体を得た。得られた金錯体を水素化ホウ素ナトリウムを用いて還元することで、金ナノクラスターを得ることに成功した。質量分析(ESI-TOF)によって、得られた金クラスターは金原子を14個、二座NHCは5つ有するものが主生成物であることがわかった。興味深いことに、得られた金クラスターはアセトニトリル中80Cで1日加熱してもクラスター構造が保たれており、温度に対して極めて高い安定性が示唆された。また金クラスターはオレンジ色の蛍光を示すことも明らかとなった。生体内での安定性評価には至っていないが、本研究の目標である安定な金ナノクラスターの創出に向けた非常に重要な研究成果が得られたと考えている。

  • Research Products

    (19 results)

All 2019 2018 Other

All Int'l Joint Research (3 results) Journal Article (5 results) (of which Int'l Joint Research: 5 results,  Peer Reviewed: 5 results) Presentation (11 results) (of which Int'l Joint Research: 5 results,  Invited: 7 results)

  • [Int'l Joint Research] Queen's University/McGill University/The University of Toronto(カナダ)

    • Country Name
      CANADA
    • Counterpart Institution
      Queen's University/McGill University/The University of Toronto
    • # of Other Institutions
      1
  • [Int'l Joint Research] China University of Political Science(中国)

    • Country Name
      CHINA
    • Counterpart Institution
      China University of Political Science
  • [Int'l Joint Research] University of Jyvaskyla(フィンランド)

    • Country Name
      FINLAND
    • Counterpart Institution
      University of Jyvaskyla
  • [Journal Article] N-Heterocyclic Carbene-functionalized Magic-number Gold Nanoclusters2019

    • Author(s)
      Mina R. Narouz, Hannu Hakkinen, Tatsuya Tsukuda, Cathleen M. Crudden, et al
    • Journal Title

      Nature Chemistry

      Volume: 印刷中 Pages: 印刷中

    • DOI

      10.1038/s41557-019-0246-5

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Cu‐Catalyzed Desulfonylative Amination of Benzhydryl Sulfones2019

    • Author(s)
      Masakazu Nambo Yasuyo Tahara Dr. Jacky C.‐H. Yim, Cathleen M. Crudden
    • Journal Title

      Chemistry A European Journal

      Volume: 25 Pages: 1923-1926

    • DOI

      10.1002/chem.201805638

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Generation and conversion of an N-heterocyclic carbene on Pt(111)2018

    • Author(s)
      Yang Zeng, Tianchi Zhang, Mina R. Narouz, Cathleen M. Crudden, Peter H. McBreen
    • Journal Title

      Chemical Communications

      Volume: 54 Pages: 12527-12530

    • DOI

      10.1039/C8CC06894A

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Self-Assembled N-Heterocyclic Carbene-Based Carboxymethylated Dextran Monolayers on Gold as a Tunable Platform for Designing Affinity-Capture Biosensor Surfaces2018

    • Author(s)
      Zhijun Li, Kim Munro, Mina R. Narouz, Andrew Lau, Hongxia Hao, Cathleen M. Crudden, J. Hugh Horton
    • Journal Title

      ACS Applied Materials and Interfaces

      Volume: 10 Pages: 17560-17570

    • DOI

      10.1021/acsami.8b02595

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] The Structural and Electrochemical Effects of N-Heterocyclic Carbene Monolayers on Magnesium2018

    • Author(s)
      Lisa Stephens, J. Daniel Padmos, Mina R. Narouz, Abrar Al-Rashed, Chien-Hung Li, Nicholas Payne, Matthew Zamora, Cathleen M. Crudden, Janine Mauzeroll, J. Hugh Horton
    • Journal Title

      Journal of The Electrochemical Society

      Volume: 165 Pages: G139-G145

    • DOI

      10.1149/2.0501811jes

    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Toward game-changing molecular materials2019

    • Author(s)
      Cathleen Crudden
    • Organizer
      International ERATO Itami Molecular Nanocarbon Symposium 2019
    • Invited
  • [Presentation] Metal catalysts, clusters and surfaces: Catalytic preparation of chiral bio-molecules and carbon-based self-assembled monolayers2018

    • Author(s)
      Cathleen Crudden
    • Organizer
      Southwestern Ontario Undergraduate Chemistry Conference
    • Invited
  • [Presentation] N-heterocyclic carbenes as ligands for metal surfaces2018

    • Author(s)
      Cathleen Crudden
    • Organizer
      255th ACS National Meeting
    • Int'l Joint Research
  • [Presentation] Organoboron compounds in cross coupling chemistry and as catalysts for FLP reductions2018

    • Author(s)
      Cathleen Crudden
    • Organizer
      255th ACS National Meeting
    • Int'l Joint Research
  • [Presentation] Metal catalysts, clusters and surfaces from carbon-based self assembled monolayers2018

    • Author(s)
      Cathleen Crudden
    • Organizer
      25th Canadian Symposium on Catalysis
    • Invited
  • [Presentation] N-Heterocyclic Carbenes as Ligands for Surfaces, Nanoparticles and Clusters2018

    • Author(s)
      Cathleen Crudden
    • Organizer
      CIC Catalysis Award Lecture, 101st Canadian Society for Chemistry annual conference
    • Invited
  • [Presentation] Main Group Catalysis in the Reduction of Organic Compounds2018

    • Author(s)
      Cathleen Crudden
    • Organizer
      Si Symposium for Bob West, 101st Canadian Society for Chemistry annual conference
    • Invited
  • [Presentation] Borenium Ions and Cross-Coupling Transformations of Multiply Borylated Molecules2018

    • Author(s)
      Cathleen Crudden
    • Organizer
      Boron in the Americas XVI “Boron in Catalysis
    • Int'l Joint Research
  • [Presentation] The Many Dimensions of Stereochemistry: Catalysis, Chemical Biology, Macromolecules, and Synthesis, “Sulfur in the Suzuki- Miyaura Reaction"2018

    • Author(s)
      Cathleen Crudden
    • Organizer
      Gordon Research Conference
    • Invited
  • [Presentation] N-heterocyclic Carbenes on Au and Cu Surfaces: Opportunities in ALD and ALE2018

    • Author(s)
      Cathleen Crudden
    • Organizer
      American Vacuum Society, 65th International symposium
    • Int'l Joint Research
  • [Presentation] Advances in the Suzuki-Miyaura Reaction and Catalysis with NHC-modified materials2018

    • Author(s)
      Cathleen Crudden
    • Organizer
      International Kyoto Conference on Organic Chemistry
    • Int'l Joint Research / Invited

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Published: 2019-12-27  

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