四川大学杨成团队报道了超分子手性诱导、记忆、擦除和反转中的自我抑制特征。相关研究成果于2022年1月14日发表于国际顶尖学术期刊《美国化学会杂志》。

自抑制在分级生化过程中已被广泛观察到，但尚未在纯分子物理过程而不是化学或生物过程中得到证实。

该文中，研究人员报道了柱[5]芳烃（P[5]）衍生物在超分子手性诱导、记忆、擦除和反转过程中的一个前所未有的自我抑制例子。将手性丙氨酸乙酯添加到大量取代基修饰的P[5]s中，由于SP和RP构象P[5]的平衡移动，导致了依赖时间的手性诱导。有趣的是，更多的手性诱导剂导致更强烈的最终手性光学性质，但较低的手性诱导率。因此，手性诱导剂起着激活剂和抑制剂的双重作用。该自我抑制本质上源于三个串联平衡的动力学操纵。

此外，用非手性竞争性粘合剂取代手性诱导剂可以记忆手性性质，用反足手性诱导剂可以擦除和反转手性信号，也表现出自抑制特性。

附：英文原文

Title: The More the Slower: Self-Inhibition in Supramolecular Chirality Induction, Memory, Erasure, and Reversion

Author: Jiecheng Ji, Xueqin Wei, Wanhua Wu, Chunying Fan, Dayang Zhou, Kuppusamy Kanagaraj, Guo Cheng, Kui Luo, Xiang-Guang Meng, Cheng Yang

Issue&Volume: January 14, 2022

Abstract: Self-inhibition has been observed widely in hierarchical biochemical processes but has yet to be demonstrated in pure molecular physical rather than chemical or biological processes. Herein, we report an unprecedented example of self-inhibition during the supramolecular chirality induction, memory, erasure, and inversion processes of pillar[5]arene (P[5]) derivatives. The addition of chiral alanine ethyl ester to bulky substituent-modified P[5]s led to time-dependent chirality induction due to the shift in the equilibrium of the SP and RP conformers P[5]. Intriguingly, more chiral inducers led to more intensive final chiroptical properties but lower chiral induction rates. Thus, the chiral inducer plays the role of both activator and inhibitor. Such self-inhibition essentially arises from kinetics manipulation of three tandem equilibria. Moreover, the chiroptical properties could be memorized by replacing the chiral inducer with an achiral competitive binder, and the chiroptical signal could be erased and reversed by an antipodal chiral inducer, which also showed the self-inhibition property.

DOI: 10.1021/jacs.1c13210

Source: https://pubs.acs.org/doi/10.1021/jacs.1c13210