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

单层保护金属纳米团簇的合成后不对称转变及其手性光学响应

• 批准号: 22510104
• 负责人: YAO Hiroshi
• 金额: $ 2.41万
• 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 (C)
• 财政年份: 2010
• 资助国家: 日本
• 起止时间: 2010 至 2012
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-22510104/
• 关键词: 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

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.

我们深入研究了光学非活性单层保护金属纳米团簇的合成后不对称转化。我们发现：(1)成功合成了非手性巯基苯硼酸保护的金纳米团簇。添加 D- 或 L- 果糖在金属电子跃迁中产生了明显的圆二色性 (CD) 信号，其符号相反（镜像关系）。对原始纳米团簇的电子吸收和磁圆二色性（MCD）光谱进行同时去卷积分析，对复杂的 CD 响应进行了定量解释：（2）D-/L-青霉胺保护的金纳米团簇上最外层氨基与异氰酸乙酯修饰了手性表面结构。通过氨基甲酰化氨基的额外反应延长配体大小（长度）。它们的光学和手性光学响应总体上相似，但配体大小对手性光学响应有明显影响：（3）具有两个立体中心的手性二硫醇（L-二硫苏糖醇）对光学非活性金纳米团簇的交联化学被证明。大的手性光学活性可能是由于与二硫醇分子的环状交联引起的表面固有旋向性。

项目成果

ナノの本質 -ナノサイエンスからナノテクノロジーまで

纳米的本质——从纳米科学到纳米技术

• 发表时间: 2011
• 作者: Yuji Kunisada;Hirofumi Kishi;Fajarisandi Dimas;Melanie Yadao David;Hiroshi Nakanishi;Hideaki Kasai;Takuma Asari;Shigeo Hayashi;石山 博恒;木村啓作・八尾浩史・佐藤井一
• 通讯作者: 木村啓作・八尾浩史・佐藤井一

Functionalization of Carbon Graphite Surfaces with Two-Dimensional Arrays of Bio- molecular Ligand-Protected Gold Nanoparticles

用生物分子配体保护的金纳米粒子二维阵列对碳石墨表面进行功能化

• 发表时间: 2010
• 作者: 西川雄大;角南武志;松浦友亮;四方哲也;Hiroshi Yao;Hiroshi Yao
• 通讯作者: Hiroshi Yao

Electrical Properties of Surface-Modified Gold Nanoparticle Assemblies

表面改性金纳米颗粒组件的电性能

• 发表时间: 2011
• 作者: Tien Quang Nguyen;Mary Clare Escano;Hideaki Kasai;Hirofumi Yamauchi(発表)・Hiroshi Yao(代表)
• 通讯作者: Hirofumi Yamauchi(発表)・Hiroshi Yao(代表)

Organic Mediator-Induced Structural Transformation in Superlattices of Monolayer-Protected Gold Nanoparticles

有机介体诱导的单层保护金纳米颗粒超晶格结构转变

• DOI: 10.1016/j.jcis.2010.10.053
• 发表时间: 2011
• 期刊: J. Colloid Interface Sci
• 作者: Hiroshi Yao;Ai Kuriyama;Keisaku Kimura
• 通讯作者: Keisaku Kimura

Organic Porphyrin Nanoparticles with Induced Optical Activity: Ion-Based Synthesis from Achiral Chromophore and Chiral Counterions

具有诱导光学活性的有机卟啉纳米粒子：非手性发色团和手性抗衡离子的离子合成

• DOI: 10.1021/cm102736d
• 发表时间: 2011
• 期刊: Chem. Mater
• 作者: Hiroshi Yao;Hisamu Sasahara;Keisaku Kimura
• 通讯作者: Keisaku Kimura