文献类型：期刊文献

英文题名：Fluorescence umpolung enables light-up sensing of N-acetyltransferases and nerve agents

作者：Yan, Chenxu[1];Guo, Zhiqian[1];Chi, Weijie[2];Fu, Wei[1];Abedi, Syed Ali Abbas[2];Liu, Xiaogang[2];Tian, He[1];Zhu, Wei-Hong[1]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat & Joint Int Res Lab Precis Chem &, Frontiers Sci Ctr Mat & Dynam Chem,Sch Chem & Mol, Shanghai Key Lab Funct Mat Chem,Inst Fine Chem, Shanghai, Peoples R China;[2]Singapore Univ Technol & Design, Fluorescence Res Grp, Singapore, Singapore

年份：2021

卷号：12

期号：1

外文期刊名：NATURE COMMUNICATIONS

收录：;WOS:【SCI-EXPANDED(收录号:WOS:000668762000011)】；

基金：This work was supported by NSFC/China (21788102, 21636002, 21622602, and 21908060), the National Key Research and Development Program (2017YFC0906902 and 2016YFA0200300), Shanghai Municipal Science and Technology Major Project (Grant 2018SHZDZX03), the Innovation Program of Shanghai Municipal Education Commission, Scientific Committee of Shanghai (15XD1501400), Programme of Introducing Talents of Discipline to Universities (B16017), the Shuguang Program (18SG27), the China Postdoctoral Science Foundation (2019M651417), and A*STAR under its Advanced Manufacturing and Engineering Program (A2083c0051). The authors would like to acknowledge the use of the computing service of SUTD-MIT IDC and the National Supercomputing Centre, Singapore.

语种：英文

摘要：Intramolecular charge transfer (ICT) is a fundamental mechanism that enables the development of numerous fluorophores and probes for bioimaging and sensing. However, the electron-withdrawing targets (EWTs)-induced fluorescence quenching is a long-standing and unsolved issue in ICT fluorophores, and significantly limits the widespread applicability. Here we report a simple and generalizable structural-modification for completely overturning the intramolecular rotation driving energy, and thus fully reversing the ICT fluorophores' quenching mode into light-up mode. Specifically, the insertion of an indazole unit into ICT scaffold can fully amplify the intramolecular rotation in donor-indazole--acceptor fluorophores (fluorescence OFF), whereas efficiently suppressing the rotation in their EWT-substituted system (fluorescence ON). This molecular strategy is generalizable, yielding a palette of chromophores with fluorescence umpolung that spans visible and near-infrared range. This strategy expands the bio-analytical toolboxes and allows exploiting ICT fluorophores for light-up sensing of EWTs including N-acetyltransferases and nerve agents. The electron-withdrawing target (EWT)-induced fluorescence quenching is an unsolved issue in intramolecular charge transfer (ICT) fluorophores that limits their applicability. Here, the authors report a simple and generalizable strategy to reverse the EWT-induced quenching mode into light-up mode, by introducing an indazole building block between the pi -bridge and the donor in the ICT scaffold.