Meng Dejing, Li Xu, Gao Xinshuang, Zhang Chenqi, Ji Yinglu, Hu Zhijian, Ren Lingling, Wu Xiaochun
CAS Key Laboratory of Standardization and Measurement for Nanotechnology, CAS Center for Excellence in Nanoscience, National Center for Nanoscience and Technology (NCNST), Beijing 100190, P. R. China.
Nanoscale. 2021 Jun 3;13(21):9678-9685. doi: 10.1039/d1nr01458g.
A sergeants-and-soldiers (S&S) effect is very useful to the fabrication of supramolecular chirality. This strategy has not yet been explored in the construction of chiral plasmonic superstructures. Herein, we demonstrate a spatially separated S&S effect in fabricating plasmonic superstructures and modulating their chiroptical responses. Specifically, chiral cysteine (Cys) molecules, acting as sergeants, are sandwiched between a gold nanorod (AuNR) core and a Au shell via AuNR-templated Au overgrowth. Cationic surfactants, CTAB (cetyltrimethylammonium bromide) or CPC (cetylpyridinium chloride), are modified on the AuNR@Cys@Au shell surface, thus spatially separating from the chiral sergeants. During the assembly process, the surfactants act as soldiers which could transfer and amplify the local chirality induced by the adsorbed chiral molecules from the plasmonic monomers to the oligomers. Huge PCD signals could be achieved in the plasmonic oligomers by finely tuning chiral sergeants and achiral soldiers, indicating the feasibility of the S&S effect in fabricating chiral plasmonic superstructures.
军士-士兵（S&S）效应对于超分子手性的构建非常有用。这种策略在构建手性等离子体超结构方面尚未得到探索。在此，我们展示了在制造等离子体超结构及其调控圆二色响应方面的空间分离S&S效应。具体而言，作为军士的手性半胱氨酸（Cys）分子通过金纳米棒（AuNR）模板化的金过度生长夹在金纳米棒（AuNR）核心和金壳之间。阳离子表面活性剂十六烷基三甲基溴化铵（CTAB）或十六烷基吡啶氯化物（CPC）修饰在AuNR@Cys@Au壳表面，从而与手性军士在空间上分离。在组装过程中，表面活性剂充当士兵，可将由吸附的手性分子诱导的局部手性从等离子体单体转移并放大到低聚物。通过精细调节手性军士和非手性士兵，在等离子体低聚物中可实现巨大的圆二色性（PCD）信号，这表明S&S效应在制造手性等离子体超结构方面的可行性。
