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基于四苯乙烯的多假轮烷的制备及串联活化聚集诱导发光

Polypseudorotaxanes Derived from Tetraphenylethylene: Preparation and Tandem-Activated Aggregation-Induced Emission.

机构信息

School of Chemical Engineering and Light Industry, Guangdong University of Technology, Guangzhou 510006, China.

School of Materials Science and Engineering, South China University of Technology, Guangzhou 510641, China.

出版信息

Biomacromolecules. 2021 May 10;22(5):2248-2255. doi: 10.1021/acs.biomac.1c00328. Epub 2021 Apr 18.

Abstract

Tuning the fluorescence of aggregation-induced emission (AIE)-based materials in a reversible way is essential and a requisite for their applications. The multiple host-guest interactions of polypseudorotaxanes (PPRs) could alter the aggregation state of hydrophobic AIE-based polymeric materials and consequently switch the fluorescence. Herein, tetraphenylethylene (TPE) as a typical AIE molecule has been incorporated into the main chains of the guest polyurethane a step condensation between poly(ethylene glycol) (PEG)-based dicarbonate and TPE-diamine along with the cleavable disulfide bonds. γ-Cyclodextrins (γ-CDs) can selectively recognize the TPE units at the polyurethane chains to afford a PPR. Hydrophilic PEG segments and γ-CD molecules in the PPR could promote the disaggregation of TPE units, suppressing the fluorescence emission of TPE. To restore the aggregated state and fluorescence of TPE units, tris(2-carboxyethyl)phosphine (TCEP) and α-amylase are sequentially introduced to cleave the disulfide bonds and cut α-1,4 glycosidic bonds of γ-CD, reactivating the AIE behavior of PPR tandemly and accomplishing the reversible cycle of tuning the fluorescence of TPE. The present study provides a tandem way to switch the AIE behavior of polymeric materials reversibly.

摘要

以可逆的方式调谐聚集诱导发光(AIE)基材料的荧光对于它们的应用是至关重要的。聚轮烷(PPR)的多重主客体相互作用可以改变疏水性 AIE 基聚合材料的聚集状态,并因此切换荧光。在此,四苯乙烯(TPE)作为一种典型的 AIE 分子已被掺入到客体聚氨酯的主链中,这是通过聚(乙二醇)(PEG)-基碳酸酯和 TPE-二胺之间的缩合反应以及可断裂的二硫键来完成的。γ-环糊精(γ-CDs)可以选择性地识别聚氨酯链上的 TPE 单元,从而形成 PPR。PPR 中的亲水性 PEG 段和 γ-CD 分子可以促进 TPE 单元的解聚集,抑制 TPE 的荧光发射。为了恢复 TPE 单元的聚集状态和荧光,顺序引入三(2-羧乙基)膦(TCEP)和α-淀粉酶来断裂二硫键并切割 γ-CD 的α-1,4 糖苷键,使 PPR 的 AIE 行为重新激活,并完成 TPE 荧光调谐的可逆循环。本研究提供了一种串联的方式来可逆地切换聚合材料的 AIE 行为。

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