Zhang Guiping, Liu Qingyuan, Xu Chunli, Li Baoxin
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education; Key Laboratory of Analytical Chemistry for Life Science of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an 710062, China.
Anal Chem. 2023 Apr 11;95(14):6107-6114. doi: 10.1021/acs.analchem.3c00396. Epub 2023 Mar 30.
Chiral nanoparticles are one of the research hotspots in the field of materials science, chemistry, and biology. Understanding and controlling the chirality of nanoparticles is one key step toward their use, but the origin of nanoparticles' chirality and its determinative factor are not well understood. In this work, we studied the chirality of gold nanoparticles (AuNPs) prepared through the conventional citrate reduction method. Unexpectedly, it was found that small AuNPs (∼13 nm) exhibited opposite chirality to the large AuNPs (>30 nm). The origin of the AuNPs chirality was revealed by comparing the crystal structure between small AuNPs and large AuNPs. It was proposed that the lattice orientation of fivefold-twinned AuNPs may be responsible for the intrinsic chirality of AuNPs. This work provides a deep mechanistic understanding of the intrinsic chirality of the AuNPs and will boost the development of the structure-controlled synthesis and application of chiral AuNPs and other chiral nanomaterials. Furthermore, based on the unexpected size effect, chiral AuNP probes were rationally constructed to improve the precision of chiral recognition.
手性纳米粒子是材料科学、化学和生物学领域的研究热点之一。理解和控制纳米粒子的手性是其应用的关键一步,但纳米粒子手性的起源及其决定性因素尚未得到很好的理解。在这项工作中,我们研究了通过传统柠檬酸盐还原法制备的金纳米粒子(AuNPs)的手性。出乎意料的是,发现小的AuNPs(约13纳米)与大的AuNPs(>30纳米)表现出相反的手性。通过比较小AuNPs和大AuNPs之间的晶体结构,揭示了AuNPs手性的起源。有人提出,五次孪晶AuNPs的晶格取向可能是AuNPs固有手性的原因。这项工作为AuNPs的固有手性提供了深入的机理理解,并将推动手性AuNPs和其他手性纳米材料的结构控制合成及应用的发展。此外,基于意外的尺寸效应,合理构建了手性AuNP探针以提高手性识别的精度。