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超分子开关对囊泡的金属离子、光和氧化还原响应相互作用

Metal ion, light, and redox responsive interaction of vesicles by a supramolecular switch.

作者信息

Samanta Avik, Ravoo Bart Jan

机构信息

Organic Chemistry Institute and Graduate School of Chemistry, Westfälische Wilhelms-Universität Münster, Corrensstrasse 40, 48149 Münster (Germany).

出版信息

Chemistry. 2014 Apr 22;20(17):4966-73. doi: 10.1002/chem.201304658. Epub 2014 Mar 18.

Abstract

Chemical, photochemical and electrical stimuli are versatile possibilities to exert external control on self-assembled materials. Here, a trifunctional molecule that switches between an "adhesive" and a "non-adhesive" state in response to metal ions, or light, or oxidation is presented. To this end, an azobenzene-ferrocene conjugate with a flexible N,N'-bis(3-aminopropyl)ethylenediamine spacer was designed as a multistimuli-responsive guest molecule that can form inclusion complexes with β-cyclodextrin. In the absence of any stimulus the guest molecule induces reversible aggregation of host vesicles composed of amphiphilic β-cyclodextrin due to the formation of intervesicular inclusion complexes. In this case, the guest molecule operates as a noncovalent cross-linker for the host vesicles. In response to any of three external stimuli (metal ions, UV irradiation, or oxidation), the conformation of the guest molecule changes and its affinity for the host vesicles is strongly reduced, which results in the dissociation of intervesicular complexes. Upon elimination or reversal of the stimuli (sequestration of metal ion, visible irradiation, or reduction) the affinity of the guest molecules for the host vesicles is restored. The reversible cross-linking and aggregation of the cyclodextrin vesicles in dilute aqueous solution was confirmed by isothermal titration calorimetry (ITC), optical density measurements at 600 nm (OD600 ), dynamic light scattering (DLS), ζ-potential measurements and cyclic voltammetry (CV). To the best of our knowledge, a dynamic supramolecular system based on a molecular switch that responds orthogonally to three different stimuli is unprecedented.

摘要

化学、光化学和电刺激是对自组装材料施加外部控制的多种方式。本文介绍了一种三功能分子,它能响应金属离子、光或氧化作用,在“粘性”和“非粘性”状态之间切换。为此,设计了一种带有柔性N,N'-双(3-氨丙基)乙二胺间隔基的偶氮苯-二茂铁共轭物作为多刺激响应客体分子,它能与β-环糊精形成包合物。在没有任何刺激的情况下,由于形成了囊泡间包合物,客体分子会诱导由两亲性β-环糊精组成的主体囊泡发生可逆聚集。在这种情况下,客体分子作为主体囊泡的非共价交联剂。响应三种外部刺激(金属离子、紫外线照射或氧化)中的任何一种,客体分子的构象都会改变,其对主体囊泡的亲和力会大幅降低,从而导致囊泡间复合物的解离。当刺激消除或逆转(金属离子螯合、可见光照射或还原)时,客体分子对主体囊泡的亲和力会恢复。通过等温滴定量热法(ITC)、600 nm处的光密度测量(OD600)、动态光散射(DLS)、ζ电位测量和循环伏安法(CV),证实了环糊精囊泡在稀水溶液中的可逆交联和聚集。据我们所知,基于对三种不同刺激正交响应的分子开关的动态超分子体系是前所未有的。

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