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电子圆二色性在超分子体系研究中的应用。

Application of electronic circular dichroism in the study of supramolecular systems.

机构信息

Dipartimento di Chimica e Chimica Industriale, Università di Pisa, via Risorgimento 35, I-56126 Pisa, Italy.

出版信息

Chem Soc Rev. 2014 Aug 7;43(15):5211-33. doi: 10.1039/c4cs00104d.

DOI:10.1039/c4cs00104d
PMID:24825540
Abstract

Chiral supramolecular architectures constitute crucial structural and functional elements in living systems and have been long mimicked by chemists to synthesize new artificial systems endowed with desired properties and functions. Among several techniques to study noncovalent chiral assemblies or aggregates, electronic circular dichroism (ECD) plays a key role because many mechanisms responsible for the appearance of ECD bands occur through space, and therefore are intrinsically sensitive to intermolecular interactions, from short to long-range. The aim of this tutorial review is to emphasize the different kinds of information which can be obtained specifically when chiral supramolecular species are characterized by means of ECD spectroscopy. We will survey several typical applications of ECD in the context of supramolecular chemistry, ranging from the simple detection of chiral aggregates or complexes, to the definition of stoichiometric ratios between the partners, the derivation of thermodynamic and kinetic parameters such as binding and rate constants, and ultimately to the refinement of the most plausible structure of the supramolecular species.

摘要

手性超分子结构是生命系统中至关重要的结构和功能单元,长期以来一直被化学家模仿,以合成具有所需性质和功能的新型人工系统。在研究非共价手性组装体或聚集体的几种技术中,电子圆二色性(ECD)起着关键作用,因为许多导致 ECD 带出现的机制是通过空间发生的,因此本质上对手性超分子物种通过 ECD 光谱进行表征时,可以获得不同种类的信息。我们将综述 ECD 在超分子化学中的几个典型应用,范围从简单检测手性聚集体或配合物,到确定配体之间的化学计量比,推导热力学和动力学参数,如结合和速率常数,最终完善手性超分子物种最合理的结构。

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