Laboratory of Molecular Modeling & Drug Discovery , Istituto Italiano di Tecnologia , Via Morego 30 , 16163 Genova , Italy.
Dipartimento di Scienze Chimiche , Università di Padova , Via Marzolo 1 , 35131 Padova , Italy.
ACS Nano. 2019 Jun 25;13(6):7127-7134. doi: 10.1021/acsnano.9b02552. Epub 2019 Jun 14.
The transfer of chirality between nanomolecules is at the core of several applications in chiral technology such as sensing and catalysis. However, the origin of this phenomenon and how exactly nanoscale objects transfer chirality to molecules in their vicinity remain largely obscure. Here, we show that the transfer of chirality for the intrinsically chiral gold cluster Au(SR) is site dependent; that is, it differs depending on the ligand-binding sites. This is closely related to the dynamic nature of the ligands on the cluster surface. Using a combination of NMR techniques and molecular dynamics simulations, we could assign the four symmetry-unique ligands on the cluster. The study reveals largely different conformational dynamics of the bound ligands, explaining the diverse diastereotopicities observed for the CH protons of the ligands. Although chirality is a structural property, our study reveals the importance of dynamics for the transfer of chirality.
手性在纳米分子间的传递是手性技术中传感和催化等几个应用的核心。然而，这种现象的起源以及纳米尺度的物体究竟如何将手性传递给附近的分子，在很大程度上仍然不清楚。在这里，我们表明，对于固有手性的金簇 Au(SR)，手性的传递具有位依赖性；也就是说，它取决于配体结合的位置。这与簇表面配体的动态性质密切相关。通过使用 NMR 技术和分子动力学模拟的组合，我们可以对簇上的四个对称独特的配体进行分配。该研究揭示了结合配体的构象动力学存在很大差异，这解释了配体的 CH 质子观察到的不同非对映选择性。尽管手性是一种结构特性，但我们的研究揭示了动力学在手性传递中的重要性。
