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构型阶梯限域实现了可调谐手性近红外发光超分子吩噻嗪有机框架。

Configurationally Stepping Confinement Achieved Tunable Chiral Near-Infrared Luminescence Supramolecular Phenothiazine Organic Framework.

作者信息

Yu Jie, Niu Jie, Xu Xiufang, Liu Yu

机构信息

College of Chemistry, State Key Laboratory of Elemento-Organic Chemistry, Nankai University, Tianjin, 300071, P. R. China.

出版信息

Adv Sci (Weinh). 2024 Nov;11(42):e2408107. doi: 10.1002/advs.202408107. Epub 2024 Sep 20.

Abstract

Herein, thermally responsive reversible chiral supramolecules are reported, constructed by the chirality transfer from tripeptides to achiral network supramolecular organic frameworks (SOF) based on configurationally stepping confinement, which displayed not only highly selective reversible chirality transfer but also efficient enhanced near-infrared (NIR) luminescence. Taking advantage of macrocyclic confinement, CB[8] separately encapsulated two kinds of tetracationic bis(phenothiazines) derivatives (G1, G2) at 2:1 stoichiometric to form organic 2D SOFs, efficiently enhancing 12.6 fold NIR luminescence and blueshifted from 705 to 680 nm for G1, and redshifted from 695 to 710 nm for G2, respectively. Uncommonly, the tripeptide coassembled with two kinds of achiral noncovalent frameworks (G1/CB[8] or G2/CB[8]) displayed different opposite circular dichroism signals based on different binding modes and affinity, achieving chirality transfer from tripeptide to organic supramolecular assemblies with further enhanced NIR fluorescence up to 46.2 times and the quantum yield (QY) increased from 0.71% to 10.29% for G2/CB[8], showing reversible chirality transfer and tunable NIR fluorescence under thermal stimulus. Therefore, the current research has achieved controllable chirality transfer from tripeptide to the SOFs and the enhancement of tunable NIR fluorescence, which is successfully applied in thermal responsive chiral logic gates, information encryption, and cell imaging.

摘要

在此,我们报道了基于构型逐步限制实现从三肽到手性网络超分子有机框架(SOF)的手性转移构建的热响应可逆手性超分子,其不仅显示出高度选择性的可逆手性转移,还具有高效增强的近红外(NIR)发光。利用大环限制,杯[8]以2:1的化学计量比分别封装两种四价双(吩噻嗪)衍生物(G1、G2)以形成有机二维SOF,有效增强了G1的近红外发光12.6倍,且从705纳米蓝移至680纳米,G2则从695纳米红移至710纳米。不同寻常的是,三肽与两种非手性非共价框架(G1/杯[8]或G2/杯[8])共组装时,基于不同的结合模式和亲和力显示出不同的相反圆二色性信号,实现了从三肽到手性超分子组装体的手性转移,G2/杯[8]的近红外荧光进一步增强至46.2倍,量子产率(QY)从0.71%提高到10.29%,在热刺激下显示出可逆的手性转移和可调谐的近红外荧光。因此,当前的研究实现了从三肽到SOF的可控手性转移以及可调谐近红外荧光的增强,并成功应用于热响应手性逻辑门、信息加密和细胞成像。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/0d18/11558156/d57219c5c792/ADVS-11-2408107-g001.jpg

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