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无有机成分的手性无机纳米结构引发的分子对称性破缺

Symmetry Breaking of Molecules Triggered by Chiral Inorganic Nanostructures Without Organic Components.

作者信息

Yao Tao, Chen Xiao, Fang Yating, Huang Zhifeng

机构信息

Department of Chemistry, The Chinese University of Hong Kong, Shatin, New Territories, Hong Kong, SAR, 999077, P. R. China.

Shenzhen Research Institute, The Chinese University of Hong Kong, No.10, 2nd Yuexing Road, Nanshan, Shenzhen, Guangdong Province, 518057, P. R. China.

出版信息

Adv Sci (Weinh). 2025 Aug;12(32):e04269. doi: 10.1002/advs.202504269. Epub 2025 Jun 20.

Abstract

Chirality transfer has garnered significant attention due to its potential to revolutionize asymmetric synthesis of enantiopure compounds and to provide fundamental insights into molecular symmetry breaking, which is widely believed to underlie the pervasive phenomenon of homochirality in biological systems. While organic-to-organic and organic-to-inorganic chirality transfers have been extensively studied, the inorganic-to-organic counterpart remains challenging due to the dimensional mismatch between the nanoscale of inorganic materials and the molecular scale of organic compounds, the thermodynamic instability of chiral inorganic lattices, and the uncontrollable influence of defects on chirality transfer. This review summarizes the synthesis of organic-free chiral nano-inorganic materials and explores the concept of inorganic-to-organic chirality transfer via symmetry breaking induced by these materials through three proposed pathways: enantiospecific inorganic-organic interactions, chirality transfer from circularly polarized light to molecules, electron spin-determined enantiopreferential reactions governed by chiral-induced spin selectivity. Inorganic-to-organic chirality transfer via symmetry breaking offers a novel framework for investigating spin chemistry, advancing asymmetric synthesis, enabling enantioselective production of single-enantiomer pharmaceuticals, and elucidating the origin of homochirality on prebiotic Earth.

摘要

手性转移因其有可能彻底改变对映体纯化合物的不对称合成,并为分子对称性破缺提供基本见解而备受关注,人们普遍认为分子对称性破缺是生物系统中普遍存在的同手性现象的基础。虽然有机-有机和有机-无机手性转移已得到广泛研究,但无机-有机手性转移由于无机材料的纳米尺度与有机化合物的分子尺度之间的维度不匹配、手性无机晶格的热力学不稳定性以及缺陷对手性转移的不可控影响而仍然具有挑战性。本文综述了无有机配体的手性纳米无机材料的合成,并通过三种提出的途径探讨了通过这些材料诱导的对称性破缺实现无机-有机手性转移的概念:对映体特异性无机-有机相互作用、从圆偏振光到手性分子的手性转移、由手性诱导自旋选择性控制的电子自旋决定的对映体优先反应。通过对称性破缺实现无机-有机手性转移为研究自旋化学、推进不对称合成、实现单一对映体药物的对映选择性生产以及阐明前生物地球上同手性的起源提供了一个新的框架。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b882/12407384/7dba56bd0003/ADVS-12-e04269-g004.jpg

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