In Situ Probe Supramolecular Self-Assembly Dynamics and Chirality Transfer Mechanism at Air–Water Interface
In Situ Probe Supramolecular Self-Assembly Dynamics and Chirality Transfer Mechanism at Air–Water Interface
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原位探针空水界面超分子自组装动力学和手性传递机制
DOI：
10.1021/acs.jpclett.2c00657
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发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Zhen Zhang
中科院分区：
文献类型：
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作者：
Yuening Zhang;Changhui Yu;Linyu Han;Minghua Liu;Yuan Guo;Zhen Zhang
研究超分子自组装动力学和手性转移机理对于合理设计具有潜在功能的手性超分子材料和理解生物体系中同手性的起源具有重要意义。本文利用和频光谱和二次谐波光谱研究了四（4-磺酸基苯基）卟啉（TPPS）分子与对映体手性两亲分子（l-/d-G_（12））的吸附作用所形成的超分子组装体。首先建立了涉及吸附和组装的动力学模型，并通过拟合该模型获得了动力学参数。提出了从thel-/d-G_（12）分子的手性中心到整个超分子组装体的手性转移机理。最后，我们提出了TPPS分子上的磺酸基和苯基表现出同手性，而卟啉环在thel-/d-G_（12）和TPPS自组装过程中形成J-聚集体并表现出镜像对称的结构手性的解释。
The study of supramolecular self-assembly dynamics and the chirality transfer mechanism is of importance to the rational design of potentially functional chiral supramolecular materials and an understanding of the origin of homochirality in biological systems. Herein, we study the supramolecular assemblies constructed by the tetrakis(4-sulfonatophenyl) porphyrin (TPPS) molecules’ adsorption on the enantiomer chiral amphiphilic molecules (l-/d-G12) using sum-frequency generation (SFG) and second harmonic generation (SHG) spectra. We first establish a dynamic model that involved adsorption and assembly and obtained the dynamic parameters by fitting this model. We then propose the chiral transfer mechanism from the chiral center of thel-/d-G12 molecule to the whole supramolecular assembly. Finally, we put forward an explanation that the sulfonic acid group and the phenyl group on the TPPS molecule show homochirality, but the porphyrin ring forms J-aggregation and shows mirror-symmetric structural chirality in thel-/d-G12 and TPPS self-assembly at these processes.