Postsynthetic asymmetric transformation of monolayer-protected metal nanoclusters and their chiroptical responses

• Project/Area Number: 22510104
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Nanostructural science
• Research Institution: University of Hyogo
• Principal Investigator: YAO Hiroshi 兵庫県立大学, 大学院・物質理学研究科, 准教授 (20261282)
• Research Collaborator: SASAKI Akito (株)リガク, X線研究所
• Project Period (FY): 2010 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥3,770,000 (Direct Cost: ¥2,900,000、Indirect Cost: ¥870,000); Fiscal Year 2012: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000); Fiscal Year 2011: ¥650,000 (Direct Cost: ¥500,000、Indirect Cost: ¥150,000); Fiscal Year 2010: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
• Keywords: ナノ多機能材料 / 光学活性 / クラフター / 金属ナノクラスター / ポストキラル変換 / 不斉誘導 / 円偏光二色性 / ジチオール連結 / 磁気円二色性 / スペクトル分割 / 不斉場効果 / 配位子変換 / ポストキラル / ボロン酸

Research Abstract

We have intensively studied on postsynthetic asymmetric transformation of optically inactive monolayer-protected metal nanoclusters. We found that;
(1) Gold nanoclusters protected by achiral mercaptophenylboronic acid were successfully synthesized. Addition of D- or L-fructose brought about appreciable circular dichroism (CD) signals with an opposite sign (mirror-image relationship) in metal-based electronic transitions. Simultaneous deconvolution analysis of electronic absorption and magnetic circular dichroism (MCD) spectra of the pristine nanoclusters gave quantitative inter- pretation on the complicated CD responses:
(2) Reaction of the outermost amino groups on D-/L-penicillamine-protected gold nanoclusters with ethyl isocyanate modified the chiral surface structure. Ligand size (length) was extended through additional reactions of the carbamoylated amino groups. Their optical and chiroptical responses were overall similar to each other, but the ligand size had a distinct influence on the chiroptical response:
(3) Cross-linking chemistry of optically-inactive gold nanoclusters by chiral dithiol with two stereogenic centers (L-dithiothreitol) was demonstrated. The large chiroptical activity can be due to surface intrinsic handedness caused by a cyclic cross-linking with dithiol molecules.

Research Products

• [Journal Article] On the Surface Structure of 1,3-Dithiol- Protected Gold Nanoparticles interpreted by the Size Effect of IR Absorption Properties (2013)
  • Author(s): Ryota Ueno, Hiroshi Yao
  • Journal Title: Colloid Surf. A: Physicochem. Eng. Aspects Volume: 426 Pages: 39-46
  • DOI: 10.1016/j.colsurfa.2013.03.013
  • Peer Reviewed
• [Journal Article] Chemical Transformation of Chiral Monolayer-Protected Gold Clusters: Observation of Ligand Size Effects on Optical and hiroptical Responses (2012)
  • Author(s): Hiroshi Yao, Noriyuki Kitaoka, Akito Sasaki
  • Journal Title: Nanoscale Volume: 4 Issue: 3 Pages: 955-963
  • DOI: 10.1039/c2nr11544a
  • Peer Reviewed
• [Journal Article] Boronic-Acid-Protected Gold Clusters capable of Asymmetric Induction: Spectral Deconvolution Analysis of Their Electronic Absorption and Magnetic Circular Dichroism (2012)
  • Author(s): Hiroshi Yao, Masanori Saeki, Akito Sasaki
  • Journal Title: Langmuir Volume: 28 Issue: 8 Pages: 3995-4002
  • DOI: 10.1021/la204731a
  • Peer Reviewed
• [Journal Article] Efficient Excitation-Energy Transfer in Ion-Based Organic Nanoparticles with Versatile Tunability of the Fluorescence Colours (2012)
  • Author(s): Hiroshi Yao, Koji Ashiba
  • Journal Title: ChemPhysChem Volume: 13 Issue: 11 Pages: 2703-2710
  • DOI: 10.1002/cphc.201200191
  • Peer Reviewed
• [Journal Article] On the Electronic Structures of Au_25(SR)_18 Clusters Studied by Magnetic Circular Dichroism Spectroscopy (2012)
  • Author(s): Hiroshi Yao
  • Journal Title: J. Phys. Chem. Lett Volume: 3 Issue: 12 Pages: 1701-1706
  • DOI: 10.1021/jz300396u
  • Peer Reviewed
• [Journal Article] Controlled Formation of Fluorescent Organic Nanoparticles of Carbocyanine Dye via Ion-Association Approach (2012)
  • Author(s): Tomoki Enseki, Hiroshi Yao
  • Journal Title: Chem. Lett Volume: 41 Issue: 10 Pages: 1119-1121
  • DOI: 10.1246/cl.2012.1119
  • NAID: 130004426353
  • Peer Reviewed
• [Journal Article] Organic Mediator-Induced Structural Transformation in Superlattices of Monolayer-Protected Gold Nanoparticles (2011)
  • Author(s): Hiroshi Yao, Ai Kuriyama, Keisaku Kimura
  • Journal Title: J. Colloid Interface Sci Volume: 354 Issue: 1 Pages: 55-60
  • DOI: 10.1016/j.jcis.2010.10.053
  • Peer Reviewed
• [Journal Article] Organic Porphyrin Nanoparticles with Induced Optical Activity: Ion-Based Synthesis from Achiral Chromophore and Chiral Counterions (2011)
  • Author(s): Hiroshi Yao, Hisamu Sasahara, Keisaku Kimura
  • Journal Title: Chem. Mater Volume: 23 Issue: 3 Pages: 913-922
  • DOI: 10.1021/cm102736d
  • Peer Reviewed
• [Journal Article] Highly Fluorescent Organic Nanoparticles of Thiacyanine Dye: A Synergetic Effect of Intermolecular H-Aggregation and Restricted Intramolecular Rotation (2011)
  • Author(s): Hiroshi Yao, Koji Ashiba
  • Journal Title: RSC Advances Volume: 1 Issue: 5 Pages: 834-838
  • DOI: 10.1039/c1ra00497b
  • Peer Reviewed
• [Journal Article] Conformational Study of Chiral Penicillamine Ligand on Optically Active Silver Nanoclusters with IR and VCD Spectroscopy (2010)
  • Author(s): Hiroshi Yao, Naoki Nishida, Keisaku Kimura
  • Journal Title: Chem. Phys Volume: 368 Issue: 1-2 Pages: 28-37
  • DOI: 10.1016/j.chemphys.2009.12.006
  • Peer Reviewed
• [Journal Article] Induced Optical Activity in Boronic-Acid-Protected Silver Nanoclusters by Complexation with Chiral Fructose (2010)
  • Author(s): Hiroshi Yao, Masanori Saeki, Keisaku Kimura
  • Journal Title: J. Phys. Chem. C Volume: 114 Issue: 38 Pages: 15909-15915
  • DOI: 10.1021/jp910875s
  • Peer Reviewed
• [Journal Article] Carbon Graphite Surfaces Modified with Two-dimensional Arrays of N-Acetyltripeptide-Protected Gold Nanoparticles (2010)
  • Author(s): Hiroshi Yao, Motoi Kurokami, Keisaku Kimura
  • Journal Title: Colloid Surf. A: Physicochem. Eng. Aspects Volume: 361 Issue: 1-3 Pages: 174-179
  • DOI: 10.1016/j.colsurfa.2010.03.033
  • Peer Reviewed
• [Journal Article] Synthesis, Characterization and Optical Properties of Organic Nanoparticles of Piroxicam Anti-Inflammatory Drug, J. Photochem. Photobiol. A (2010)
  • Author(s): Maged El-Kemary, Hiroshi Yao
  • Journal Title: Chem. Volume: 212 Issue: 2-3 Pages: 170-175
  • DOI: 10.1016/j.jphotochem.2010.04.012
  • Peer Reviewed
• [Journal Article] Induced Optical Activity in Boronic-Acid-Protected Silver Nanoclusters by Complexation with Chiral Fructose (2010)
  • Author(s): Hiroshi Yao
  • Journal Title: J.Phys.Chem.C Volume: 114 Pages: 15909-15915
  • Peer Reviewed
• [Journal Article] Carbon Graphite Surfaces modified with Two-dimensional Arrays of N-Acetyltripeptide-Protected Gold Nanoparticles (2010)
  • Author(s): Hiroshi Yao
  • Journal Title: Colloid Surf.A : Physicochem.Eng.Aspects Volume: 361 Pages: 174-179
  • Peer Reviewed
• [Journal Article] Synthesis, Characterization and Optical Properties of Organic Nanoparticles of Piroxicam Anti-Inflammatory Drug (2010)
  • Author(s): Maged El-Kemary, Hiroshi Yao
  • Journal Title: J.Photochem.Photobiol.A : Chem Volume: 212 Pages: 170-175
  • Peer Reviewed
• [Presentation] ジチオール配位子保護金ナノクラスターの作製と評価 (2012)
  • Author(s): 上野竜太・八尾浩史
  • Organizer: Cat-on-cat 新規表面反応研究センターシンポジウム2012
  • Place of Presentation: 先端科学技術支援センター(兵庫県)
  • Year and Date: 2012-12-08
• [Presentation] ESIPT反応型有機ナノ粒子の作製とその発光特性 (2012)
  • Author(s): 船田智仁・八尾浩史
  • Organizer: Cat-on-cat 新規表面反応研究センターシンポジウム 2012
  • Place of Presentation: 先端科学技術支援センター(兵庫県)
  • Year and Date: 2012-12-08
• [Presentation] Ligand-Protected Metal Nanoparticles with Chirality (2012)
  • Author(s): Hiroshi Yao
  • Organizer: Postsynthetic Asymmetric Trans- formation via the Boronic Acid- Saccharides Chemistry, 012 EMN (Energy Materials Nanotechnology) Fall Meeting
  • Place of Presentation: ラスベガス(アメリカ合衆国)
  • Year and Date: 2012-11-30
• [Presentation] Postsynthetic Asymmetric Transformation of Boronic-Acid- Protected Gold Nano- clusters Studied by Magnetic Circular Dichroism (MCD) and Electronic Circular Dichroism (ECD) (2012)
  • Author(s): Hiroshi Yao
  • Organizer: The 13th edition of Trends in Nanotechnology International Conference (TNT2012)
  • Place of Presentation: マドリード(スペイン)
  • Year and Date: 2012-09-14
• [Presentation] Synthesis of Chiral Dithiol-Protected Gold Nanoclusters: Do Chiroptical Responses Recognize the Ligand Structures including Dithiol Bonding Motif? (2012)
  • Author(s): Ryota Ueno, Hiroshi Yao
  • Organizer: Gold 2012: The 6th International Conference
  • Place of Presentation: 京王プラザホテル(東京都)
  • Year and Date: 2012-09-06
• [Presentation] Ion-Based Organic Dye Nanoparticles with Versatile Fluorescence Colour Tunability: Efficient Antenna Effect (2012)
  • Author(s): Hiroshi Yao
  • Organizer: 26th Conference of the European Colloid and Interface Society (ECIS 2012)
  • Place of Presentation: マルメ(スウェーデン)
  • Year and Date: 2012-09-04
• [Presentation] Organic Nanoparticles of Carbocyanine Dye: Synthesis and Interesting Spectroscopic Properties (2012)
  • Author(s): Tomoki Enseki, Hiroshi Yao
  • Organizer: IACIS (International Association of Colloid and Interface Scientists) 2012
  • Place of Presentation: 仙台国際センター(宮城県)
  • Year and Date: 2012-05-15
• [Presentation] Synthesis and Optical Properties of Organic Carbocyanine Dye Nanoparticles (2011)
  • Author(s): Tomoki Enseki, Hiroshi Yao
  • Organizer: International Meeting on Novel Catalyst Design and Surface Science
  • Place of Presentation: イーグレ姫路(兵庫県)
  • Year and Date: 2011-12-09
• [Presentation] Creation of Functional Hybrids of Avidin Protein and Gold Nanoparticles (2011)
  • Author(s): Tatsuya Sugimoto, Keisaku Kimura, Hiroshi Yao
  • Organizer: International Meeting on Novel Catalyst Design and Surface Science
  • Place of Presentation: イーグレ姫路(兵庫県)
  • Year and Date: 2011-12-09
• [Presentation] Electrical Properties of Surface- Modified Gold Nanoparticle Assemblies (2011)
  • Author(s): Hirofumi Yamauchi, Tetsuaki Dobashi, Seiichi Sato, Hiroshi Yao
  • Organizer: International Meeting on Novel Catalyst Design and Surface Science
  • Place of Presentation: イーグレ姫路(兵庫県)
  • Year and Date: 2011-12-09
• [Presentation] Electrical Properties of Surface-Modified Gold Nanoparticle Assemblies (2011)
  • Author(s): Hirofumi Yamauchi(発表)・Hiroshi Yao(代表)
  • Organizer: International Meeting on Novel Catalyst Design and Surface Science
  • Place of Presentation: イーグレ姫路(兵庫県)
  • Year and Date: 2011-12-09
• [Presentation] Organic Dye Nanoparticles with Intense Fluorescence caused by a Combined Effect of Intermolecular H-aggregation and Restricted Intramolecular Rotation (2011)
  • Author(s): Hiroshi Yao, Koji Ashiba
  • Organizer: 12th Conference on Methods and Applications of Fluorescence (MAF12)
  • Place of Presentation: ストラスブール(フランス共和国)
  • Year and Date: 2011-09-12
• [Presentation] Organic dye nanoparticles with intense fluorescence caused by a combined effect of intermolecular H-aggregation and restricted intramolecular rotation (2011)
  • Author(s): Hiroshi Yao
  • Organizer: 12th Conference on Methods and Applications of Fluorescence (MAF12)
  • Place of Presentation: ストラスブール(フランス共和国)
  • Year and Date: 2011-09-12
• [Presentation] 金ナノ粒子の表面構造制御とアビジンタンパク質との結合 (2011)
  • Author(s): 杉元達哉・木村啓作・八尾 浩史
  • Organizer: 第63回コロイドおよび界面化学討論会
  • Place of Presentation: 京都大学(京都府)
  • Year and Date: 2011-09-09
• [Presentation] Porphyrin Nanoparticles with Induced Optical Activity (2011)
  • Author(s): Hiroshi Yao
  • Organizer: 25th ECIS (European Colloid and Interface Society) Conference
  • Place of Presentation: ベルリン(ドイツ連邦共和国)
  • Year and Date: 2011-09-05
• [Presentation] Porphyrin nanoparticles with induced optical activity (2011)
  • Author(s): Hiroshi Yao
  • Organizer: 25th ECIS (European Colloid and Interface Society) Conference
  • Place of Presentation: ベルリン(ドイツ連邦共和国)
  • Year and Date: 2011-09-05
• [Presentation] Optical Activity and Asymmetric Transformation of Monolayer-Protected Gold Clusters (2011)
  • Author(s): Hiroshi Yao
  • Organizer: BIT 2nd Annual World Congress of Catalytic Asymmetric Synthesis 2011(招待講演)
  • Place of Presentation: 北京(中華人民共和国)
  • Year and Date: 2011-08-09
• [Presentation] Optical Activity and Asymmetric Transformation of Monolayer-Protected Gold Clusters (2011)
  • Author(s): Hiroshi Yao
  • Organizer: BIT 2nd Annual World Congress of Catalytic Asymmetric Synthesis 2011
  • Place of Presentation: 北京(中華人民共和国)(招待講演)
  • Year and Date: 2011-08-09
• [Presentation] Induced Optical Activity in Boronic-Acid-Protected Silver Clusters by Complexation with Chiral Fructose (2010)
  • Author(s): Hiroshi Yao
  • Organizer: Pacifichem 2010
  • Place of Presentation: ホノルル(アメリカ)
  • Year and Date: 2010-12-17
• [Presentation] Synthesis of Monodisperse Boronic-Acid Protected Gold Nano- clusters and Their Chiral Sensing Applications for Sugar (2010)
  • Author(s): Masanori Saeki, Hiroshi Yao, Keisaku Kimura
  • Organizer: International Conference on Nanoscopic Colloid and Surface Science (NCSS 2010)
  • Place of Presentation: 幕張メッセ(千葉県)
  • Year and Date: 2010-09-21
• [Presentation] Synthesis of Monodisperse Boronic-Acid Protected Gold Nanoclusters and Their Chiral Sensing Applications for Sugar (2010)
  • Author(s): Masanori Saeki, Hiroshi Yao, Keisaku Kimura
  • Organizer: International Conference on Nanoscopic Colloid and Surface Science (NCSS 2010)
  • Place of Presentation: 幕張メッセ(千葉)
  • Year and Date: 2010-09-21
• [Presentation] Induced Optical Activity in Boronic-Acid-Protected Silver Clusters by Complexation with Chiral Fructose (2010)
  • Author(s): Hiroshi Yao
  • Organizer: Pacifichem 2010
  • Place of Presentation: ホノルル(アメリカ合衆国)
  • Year and Date: 2010-09-17
• [Presentation] Boronic-acid-protected Silver Nanoclusters: High Affinity for Chiral Saccharides and Induced Optical Activity (2010)
  • Author(s): Hiroshi Yao
  • Organizer: International Conference on Nanostructured Materials - NANO 2010
  • Place of Presentation: ローマ(イタリア)
  • Year and Date: 2010-09-17
• [Presentation] Boronic-acid-protected silver nanoclusters : High affinity for chiral saccharides and induced optical activity (2010)
  • Author(s): Hiroshi Yao
  • Organizer: International Conference on Nanostructured Materials-NANO 2010
  • Place of Presentation: ローマ(イタリア)
  • Year and Date: 2010-09-17
• [Presentation] Functionalization of Carbon Graphite Surfaces with Two-Dimensional Arrays of Bio- molecular Ligand-Protected Gold Nanoparticles (2010)
  • Author(s): Hiroshi Yao
  • Organizer: 24th Conference of the European Colloid and Interface Society (ECIS 2010)
  • Place of Presentation: プラハ(チェコ共和国)
  • Year and Date: 2010-09-06
• [Presentation] Functionalization of carbon graphite surfaces with two-dimensional arrays of biomolecular ligand-protected gold nanoparticles (2010)
  • Author(s): Hiroshi Yao
  • Organizer: 24th Conference of the Enropean Colloid and Interface Society(ECIS 2010)
  • Place of Presentation: プラハ(チェコ共和国)
  • Year and Date: 2010-09-06
• [Presentation] Organic Nanoparticles of Carbocyanine Dye: Synthesis and Interesting Spectroscopic Properties
  • Author(s): Tomoki Enseki ( 発表 ) , Hiroshi Yao ( 代表 )
  • Organizer: IACIS (International Association of Colloid and Interface Scientists) 2012
  • Place of Presentation: 仙台国際センター ( 宮城県 )
• [Presentation] Synthesis of Chiral Dithiol-Protected Gold Nanoclusters: Do Chiroptical Responses Recognize the Ligand Structures including Dithiol Bonding Motif?
  • Author(s): Ryota Ueno ( 発表 ) , Hiroshi Yao ( 代表 )
  • Organizer: Gold 2012: The 6th International Conference
  • Place of Presentation: 京王プラザホテル ( 東京都 )
• [Presentation] Ion-Based Organic Dye Nanoparticles with Versatile Fluorescence Colour Tunability: Efficient Antenna Effect
  • Author(s): Hiroshi Yao
  • Organizer: 26th Conference of the European Colloid and Interface Society (ECIS 2012)
  • Place of Presentation: マルメ ( スウェーデン )
• [Presentation] Postsynthetic Asymmetric Transformation of Boronic-Acid-Protected Gold Nanoclusters Studied by Magnetic Circular Dichroism (MCD) and Electronic Circular Dichroism (ECD)
  • Author(s): Hiroshi Yao
  • Organizer: The 13th edition of Trends in Nanotechnology International Conference (TNT2012)
  • Place of Presentation: マドリード ( スペイン )
• [Presentation] Ligand-Protected Metal Nanoparticles with Chirality: Postsynthetic Asymmetric Transformation via the Boronic Acid–Saccharides Chemistry
  • Author(s): Hiroshi Yao
  • Organizer: 2012 EMN (Energy Materials Nanotechnology) Fall Meeting
  • Place of Presentation: ラスベガス ( アメリカ合衆国 )
  • Invited
• [Presentation] ジチオール配位子保護金ナノクラスターの作製と評価
  • Author(s): 上野竜太 ( 発表 ) , 八尾浩史 ( 代表 )
  • Organizer: Cat-on-cat 新規表面反応研究センターシンポジウム2012
  • Place of Presentation: 兵庫県立先端科学技術支援センター ( 兵庫県 )
• [Presentation] ESIPT反応型有機ナノ粒子の作製とその発光特性
  • Author(s): 船田智仁 ( 発表 ) , 八尾浩史 ( 代表 )
  • Organizer: Cat-on-cat 新規表面反応研究センターシンポジウム2012
  • Place of Presentation: 兵庫県立先端科学技術支援センター ( 兵庫県 )
• [Book] Mesoscopic Morphology, Optical Anisotropy and Spectroscopic Properties of Cyanine J-Aggregates; in J-Aggregates (2012)
  • Author(s): Hiroshi Yao
  • Total Pages: 520
  • Publisher: World Scientific (Singapore)
• [Book] Mesoscopic Morphology, Optical Anisotropy and Spectroscopic Properties of Cyanine J-Aggregates; in "J-Aggregates, Volume 2" (2012)
  • Author(s): Hiroshi Yao
  • Publisher: World Scientific (Singapore)
• [Book] Mesoscopic Self-Assembly of Trimethine Cyanine Dye in Solution: Electrolyte- Induced Conversion in Their Supramolecular Structures: in Molecular Self-Assembly: Advances in Chemistry (2011)
  • Author(s): Hiroshi Yao
  • Total Pages: 268
  • Publisher: Nova Science Publishers
• [Book] ナノの本質 -ナノサイエンスからナノテクノロジーまで (2011)
  • Author(s): 木村啓作・八尾浩史・佐藤井一
  • Total Pages: 536
  • Publisher: 共立出版
• [Book] ナノの本質-ナノサイエンスからナノテクノロジーまで (2011)
  • Author(s): 木村啓作・八尾浩史・佐藤井一
  • Total Pages: 536
  • Publisher: 共立出版
• [Book] Mesoscopic Self-Assembly of Trimethine Cyanine Dye in Solution : Electrolyte-Induced Conversion in Their Supramolecular Structures : In Molecular Self-Assembly : Advances in Chemistry, Biology and Nanotechnology (2011)
  • Author(s): Hiroshi Yao
  • Publisher: Nova Science Publishers
• [Book] Prospects for Organic Dye Nanoparticles: in Advanced Fluorescence Reporters in Chemistry and Biology. II (2010)
  • Author(s): Hiroshi Yao
  • Total Pages: 459
  • Publisher: Springer
• [Book] Prospects for Organic Dye Nanoparticles : In Advanced Fluorescence Reporters in Chemistry and Biology.II.Molecular Constructions, Polymers and Nanoparticles (2010)
  • Author(s): Hiroshi Yao
  • Total Pages: 20
  • Publisher: Springer
• [Remarks] 産学交流 八尾浩史:強発光性有機ナノ粒子の創製,はりま産学交流会, 2012年10月17日姫路商工会議所(兵庫県)
• [Remarks]
  • URL: http://lib.laic.u-hyogo.ac.jp/laic/2/archive/annual/a-vol-22/22060063.pdf
• [Remarks]
  • URL: http://lib.laic.u-hyogo.ac.jp/laic/2/archive/annual/a-vol-21/21054057.pdf