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2016 年度 実績報告書

N-heterocyclic carbene-modified gold nanoparticles for biosensing

研究課題

研究課題/領域番号 26288023
研究機関名古屋大学

研究代表者

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)

研究期間 (年度) 2014-04-01 – 2018-03-31
キーワードNano Material / Gold Nanoparticles / N-Heterocyclic Carbene / Bio-imaging / Stability / Photoacoustic Properties
研究実績の概要

This year we have made substantial progress in the area of NHC-stabilized nanoparticles. Our first publication appeared in Angewandte Chemie International Edition. This paper detailed our study of carboxylated NHCs as ligands for the preparation of water soluble gold nanoparticles. These nanoparticles were extensively studied and could be analyzed by polyacrylamide gel electrophoresis due to their charged nature. In basic pHs, the nanoparticles were exceptionally stable, however they aggregated under acidic pH. This aggregation was shown to be reversible. The NHC-stabilized nanoparticles were stable under a variety of biologically-relevant conditions, except thiol stability was still sub optimal. In addition to the synthetic and stability studies, in collaboration with the Yamaguchi group, we were able to test the photoacoustic properties of these nanoparticles. The nanoparticles were shown to have a linear response and even the smallest nanoparticles had a reasonable photoacoustic response.
In more recent work, we have prepared a new type of bidentate NHC, one that has a single NHC ligand and a thiol ligand on the same molecule. This compound was shown to make Au(1) nanoclusters when exposed to molecular gold, and to make highly stable nanoparticles when exposed to auric acid and reducing agents. In this work, we have prepared the first NHC-based nanoparticle that is stable to exogenous thiol. This work is very preliminary and will continue in the next funding year.

現在までの達成度 (区分)
現在までの達成度 (区分)

1: 当初の計画以上に進展している

理由

The use of bidentate NHCs to stabilize nanoparticles has proven to be an excellent strategy and we believe will be the key to employing these nanoparticles in vivo. Synthetic issues in the previous year were overcome this year, permitting us to make two of the important structures that we needed to make, namely bidentate alkylated NHCs and bidentate NHC/thiol ligands. Both of these ligands turned out to be excellent supporting ligands for gold nanoparticles.
In addition to solving synthetic issues with regards to the preparation of the ligands, we were also able to analyze the water soluble nanoparticles with the assistance of the Itami and Higashiyama group at the Institute of Transformative Bio-Molecules.

今後の研究の推進方策

Future work will focus on three areas:
(1) Completion of work on mixed thiol/NHC ligands and nanoparticles. The stability of these nanoparticles will be studied in more depth and the use of various linker lengths and nanoparticle sizes will be studied.
(2) The preparation of larger nanoparticles for a variety of applications will be a focus of this year. In collaboration with the Higashiyama group we will examine micron sized nanostructures for gene delivery and we will also examine more typical 40-50 nm structures for in vivo applications.
(3) Biological applications will also be addressed head on in this year since we now have a variety of sizes and types of water soluble nanoparticles and have the ability to prepare many types of NHC ligands. This will require bioconjugation studies.

次年度使用額が生じた理由

新規金属ナノ粒子の合成を遂行する予定であった博士研究員の博士号取得が遅れたことにより雇用が遅れ、研究計画に大幅な遅延が生じたため

次年度使用額の使用計画

研究遂行の為の物品費、また研究発表のために使用する。

  • 研究成果

    (20件)

すべて 2017 2016 その他

すべて 国際共同研究 (3件) 雑誌論文 (8件) (うち国際共著 4件、 査読あり 8件、 謝辞記載あり 1件、 オープンアクセス 1件) 学会発表 (9件) (うち国際学会 3件、 招待講演 6件)

  • [国際共同研究] クイーンズ大学(カナダ)

    • 国名
      カナダ
    • 外国機関名
      クイーンズ大学
  • [国際共同研究] セント・アンドルーズ大学(英国)

    • 国名
      英国
    • 外国機関名
      セント・アンドルーズ大学
  • [国際共同研究]

    • 他の国数
      2
  • [雑誌論文] Water-Soluble N-Heterocyclic Carbene-Protected Gold Nanoparticles: Size-Controlled Synthesis, Stability, and Optical Properties2017

    • 著者名/発表者名
      Kirsi Salorinne, Renee W. Y. Man, Chien-Hung Li, Masayasu Taki, Masakazu Nambo, Cathleen M. Crudden
    • 雑誌名

      Angewandte Chemie International Edition

      巻: 印刷中 ページ: 印刷中

    • DOI

      10.1002/anie.201701605

    • 査読あり / 国際共著 / 謝辞記載あり
  • [雑誌論文] Borocation catalysis2017

    • 著者名/発表者名
      Patrick Eisenberger, Cathyleen M. Crudden
    • 雑誌名

      Dalton Transactions

      巻: 46 ページ: 4874-4887

    • DOI

      10.1039/C6DT04232E

    • 査読あり
  • [雑誌論文] 2. Development of Versatile Sulfone Electrophiles for Suzuki-Miyaura Cross-Coupling Reactions2017

    • 著者名/発表者名
      Masakazu Nambo, Eric C. Keske, Jason P. G. Rygus, Jacky, C.-H. Yim, Cathleen M. Crudden
    • 雑誌名

      ACS Catalysis

      巻: 7 ページ: 1108-1112

    • DOI

      10.1021/acscatal.6b03434

    • 査読あり / 国際共著
  • [雑誌論文] Installing Stable Molecular Chirality within the Walls of Periodic Mesoporous Organosilicas via Self-Assembly2016

    • 著者名/発表者名
      Lacey M. Reid, Cathleen M. Crudden
    • 雑誌名

      Chemistry of Materials

      巻: 28 ページ: 7605-7612

    • DOI

      10.1021/acs.chemmater.6b02153

    • 査読あり
  • [雑誌論文] Simple direct formation of self-assembled N-heterocyclic carbene monolayers on gold and their application in biosensing2016

    • 著者名/発表者名
      C. M. Crudden, J. H. Horton, M. R. Narouz, Z. Li, C. A. Smith, K. Munro, C. J. Baddeley, C. R. Larrea, B. Drevniok, B. Thanabalasingam, A. B. McLean, O. V. Zenkina, I. I. Ebralidze, Z. She, H.-B. Kraatz, N. J. Mosey, L. N. Saunders, A. Yagi
    • 雑誌名

      Nature Communications

      巻: 7 ページ: 12654

    • DOI

      10.1038/ncomms12654

    • 査読あり / オープンアクセス / 国際共著
  • [雑誌論文] Chiral carbene-borane adducts: precursors for borenium catalysts for asymmetric FLP hydrogenations2016

    • 著者名/発表者名
      Jolie Lam, Benjamin A. R. Gunther, Jeffrey M. Farrell, Patrick Eisenberger, Brian P. Bestvater, Paul D. Newman, Rebecca L. Melen, Cathleen M. Crudden, Douglas W. Stephan
    • 雑誌名

      Dalton Transactions

      巻: 45 ページ: 15303-15316

    • DOI

      10.1039/C6DT02202B

    • 査読あり
  • [雑誌論文] Accessible bidentate diol functionality within highly ordered composite periodic mesoporous organosilicas2016

    • 著者名/発表者名
      Lacey M. Reid, Gang Wu, Cathleen M. Crudden
    • 雑誌名

      New journal of Chemistry

      巻: 40 ページ: 6487-6497

    • DOI

      10.1039/C6NJ00401F

    • 査読あり
  • [雑誌論文] 4. Arylative Desulfonation of Diarylmethyl Phenyl Sulfones with Arenes Catalyzed by Scandium Triflate2016

    • 著者名/発表者名
      Masakazu Nambo, Zachary T. Ariki, Daniel Canseco-Gonzalez, D. Dawson Beattie, Cathleen M. Crudden
    • 雑誌名

      Organic Letters

      巻: 18 ページ: 2339-2342

    • DOI

      10.1021/acs.orglett.6b00744

    • 査読あり / 国際共著
  • [学会発表] Water-soluble N-heterocyclic carbene protected gold nanoparticles for biological applications2017

    • 著者名/発表者名
      Kirsi Salorinne, Renee Man, Henry Li, Masayasu Taki, Masakazu Nambo, Cathleen M. Crudden
    • 学会等名
      96th CSJ meeting
    • 発表場所
      Keio Univeristy
    • 年月日
      2017-03-17 – 2017-03-17
  • [学会発表] Enhanced stability: Synthesis and characterizations of N-heterocyclic carbene-stabilized gold nanoparticles2017

    • 著者名/発表者名
      Renee Man, Henry Li, Masakazu Nambo, Cathleen M. Crudden
    • 学会等名
      96th CSJ meeting
    • 発表場所
      Keio Univeristy
    • 年月日
      2017-03-17 – 2017-03-17
  • [学会発表] Organometallic chemistry at the interfaces: Preparation of biologically active molecules using enantiospecific cross coupling and the design of novel carbon-based monolayers on gold2016

    • 著者名/発表者名
      Cathleen M. Crudden
    • 学会等名
      4th International Symposium on New Frontiers in Materials Science
    • 発表場所
      Hokkaido, Japan
    • 年月日
      2016-11-08 – 2016-11-08
    • 国際学会 / 招待講演
  • [学会発表] Catalysis from Molecules to Materials2016

    • 著者名/発表者名
      Cathleen M. Crudden
    • 学会等名
      Connaught Industry Alliance Symposium
    • 発表場所
      Toronto, Canada
    • 年月日
      2016-10-11 – 2016-10-11
    • 招待講演
  • [学会発表] New Trends in Organometallic Chemistry leading to Organic Synthesis2016

    • 著者名/発表者名
      Cathleen M. Crudden
    • 学会等名
      American Chemical Society Conference
    • 発表場所
      Philidelphia, United States
    • 年月日
      2016-08-21 – 2016-08-21
    • 国際学会 / 招待講演
  • [学会発表] Pd-Catalyzed Sequential Arylation of Methyl Sulfone Derivatives toward Straightforward Synthesis of Multiply-arylated Methanes2016

    • 著者名/発表者名
      Masakazu Nambo, Eric, C. Keske, Jason, P. G. Ryugus, Jacky C.-H. Yim, Cathleen M. Crudden
    • 学会等名
      Gordon Research Conference, Stereochemistry
    • 発表場所
      Boston, United States
    • 年月日
      2016-07-27 – 2016-07-28
    • 国際学会
  • [学会発表] Organometallic chemistry for the preparation of biologically important molecules and for the design of novel self assembled monolayers on gold2016

    • 著者名/発表者名
      Cathleen M. Crudden
    • 学会等名
      Centre in Green Chemistry and Catalysis annual meeting
    • 発表場所
      Montreal, Canada
    • 年月日
      2016-06-03 – 2016-06-03
    • 招待講演
  • [学会発表] Organometallic chemistry: Surfaces and Catalysts2016

    • 著者名/発表者名
      Cathleen M. Crudden
    • 学会等名
      IRTG Symposium
    • 発表場所
      Muenster, Germany
    • 年月日
      2016-05-23 – 2016-05-23
    • 招待講演
  • [学会発表] N-Heterocyclic carbenes as valuable supporting ligands in catalysis: From cross-coupling to borenium catalysis to materials chemistry2016

    • 著者名/発表者名
      Cathleen M. Crudden
    • 学会等名
      Catalysis Division Conference
    • 発表場所
      Ottawa, Canada
    • 年月日
      2016-05-10 – 2016-05-10
    • 招待講演

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公開日: 2018-01-16  

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