Chiral chemistry in metal nanoclusters : Fundamentals and applications

金属纳米团簇中的手性化学：基础和应用

• 批准号: 19310076
• 负责人: YAO Hiroshi
• 金额: $ 12.98万
• 依托单位: University of Hyogo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2007
• 资助国家: 日本
• 起止时间: 2007 至 2009
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-19310076/
• 关键词: ナノ多機能材料; 光学活性; クラスター; 金属ナノクラスター; キール; エナンチオマー; 不斉変換; 円二色性スペクトル; 振動円偏光二色性; 不斉場モデル; キラル; 円偏光二色性; 不斉場効果; ナノ粒子

We found large optical activity in gold nanoclusters (<2nm) protected by a pair of penicillamine enantiomers. The observed optical activity was attributed to a dissymmetric field induced by the chiral ligands. We have also succeeded in synthesizing a pair of optical isomers of silver nanoclusters. Their chiroptical response was several-fold larger than that of the analogous gold nanoclusters with comparable core size. The dissymmetric field effect from chiral ligands should be a universal origin for their optical activity, but its enhancement observed in a small size region of silver might be attributed to additional contributions from a chiral silver core. Next, the VCD spectra of penicillamine-protected silver nanoclusters have been studied experimentally, and analyzed theoretically. The spectral assignment suggested that the solvent effect was necessary to account for an agreement between the experimental and theoretical VCD spectra, resulting in the P_N-type conformation as the most probable isomer. Furthermore, we have achieved asymmetric transformation or symmetry breaking of the optically inactive gold and silver nanoclusters using chiral phase-transfer or boronic-acid chemistry.

我们发现在一对青霉素对映异构体保护的金纳米簇（<2nm）中，光学活性很大。观察到的光活性归因于手性配体诱导的非对称场。我们还成功地合成了一对银纳米簇的光学异构体。它们的手势响应比具有可比核心大小的类似金纳米群的类似金纳米群的响应大几倍。手性配体的不对称场作用应成为其光学活性的普遍起源，但是在微型银色区域中观察到的增强可能归因于手性银核的其他贡献。接下来，已经对受青霉素保护的银纳米簇的VCD光谱进行了实验研究，并从理论上进行了分析。光谱分配表明，溶剂效应是必要的，以说明实验和理论VCD光谱之间的一致性，从而导致P_N型构象是最可能的异构体。此外，我们使用手性相位转移或硼酸化学的化学实现了光学非活性金和银纳米簇的不对称转化或对称破坏。

项目成果

Three-Dimensional Superlattices of N-Acetylglutathione-Protected Gold Nanoparticles:Emergence of Fivefold Symmetry

N-乙酰谷胱甘肽保护的金纳米粒子的三维超晶格：五重对称性的出现

• 发表时间: 2007
• 作者: Hiroshi Yao;Takayuki Minami;Keisaku Kimura
• 通讯作者: Keisaku Kimura

Chiral Functionalization of Monolayer- Protected Silver Nanoclusters by Chiral- Exchange Reactions

通过手性交换反应对单层保护的银纳米团簇进行手性功能化

• 发表时间: 2008
• 作者: Naoki;Nishida;Hiroshi Yao;Keisaku Kimura
• 通讯作者: Keisaku Kimura

Chemometric and Microscopic Analyses for the Size Growth of Monolayer-Protected Gold Nanoparticles during their Superlattice Formation

单层保护的金纳米颗粒在超晶格形成过程中尺寸增长的化学计量学和显微分析

• 发表时间: 2007
• 期刊: Langmuir 23
• 作者: Hiroshi Yao;K. Moriyama;K. Kimura
• 通讯作者: K. Kimura

Proof of Partial Flattening of Meso Substituents in Tetracationic Porphyrin at a Mica/Solution Interface

云母/溶液界面四阳离子卟啉中内消旋取代基部分扁平化的证明

• 发表时间: 2008
• 期刊: Chem. Lett 37
• 作者: Hiroshi Yao;Shogo Kobayashi;Keisaku Kimura
• 通讯作者: Keisaku Kimura

Chiroptical Responses of d-/l-Penicillamine-Capped Gold Clusters under Perturbations of Temperature Change and Phase Transfer

• DOI: 10.1021/jp074830b
• 发表时间: 2007-09
• 期刊: Journal of Physical Chemistry C
• 影响因子: 3.7
• 作者: H. Yao;Toshiyuki Fukui;K. Kimura