文献类型：期刊文献

英文题名：Dual-emissive self-reporting photosensitizers characterized by Kasha/anti-Kasha behaviors engineered via a gradient donor-acceptor strategy

作者：Gu, Xixin[1,2];Zhang, Xinyi[1,2];Han, Yujie[3];Mei, Ju[1,2];Zhang, Qi-Wei[3];Hua, Jianli[1,2]

机构：[1]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Key Lab Adv Mat, 130 Meilong Rd, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Feringa Nobel Prize Scientist Joint Res Ctr, Frontiers Sci Ctr Materiobiol & Dynam Chem, Sch Chem & Mol Engn,Joint Int Res Lab Precis Chem, 130 Meilong Rd, Shanghai 200237, Peoples R China;[3]East China Normal Univ, Sch Chem & Mol Engn, Shanghai Key Lab Green Chem & Chem Proc, Dept Chem, Shanghai 200241, Peoples R China

年份：2025

卷号：16

期号：35

起止页码：16168

外文期刊名：CHEMICAL SCIENCE

收录：;EI(收录号：20253819173401);WOS:【SCI-EXPANDED(收录号:WOS:001546728600001)】；

基金：For financial support of this research, the authors thank the projects supported by the National Natural Science Foundation of China (21788102, 22271093, 21971064 and 22322405), the Science and Technology Commission of Shanghai Municipality (24DX1400200), the Programme of Introducing Talents of Discipline to Universities (B16017) and the Fundamental Research Funds for the Central Universities. The authors thank the Research Center of Analysis and Test of East China University of Science and Technology for the help on the characterization.

语种：英文

外文关键词：Isomers - Photodynamic therapy - Photosensitizers - Plants (botany) - Transient absorption spectroscopy

摘要：Real-time monitoring of photodynamic therapy (PDT) is essential for precision medicine, yet remains hindered by microenvironmental interference and photobleaching of conventional mono-emissive photosensitizers (PSs). Herein, inspired by the energy level gradients depicted in the Jablonski diagram, we report a gradient donor-acceptor molecular design strategy to overcome Kasha's rule, achieving intrinsic dual-emissive PSs. Combining femtosecond transient absorption spectroscopy with theoretical calculations, we have verified the Kasha/anti-Kasha properties of the compounds: near-infrared (NIR) emission peaking at 710 nm, exhibiting viscosity dependence stems, from the S1-to-S0 excited-state decay of the primary acceptor-donor framework, whereas visible emission at 530-590 nm, significantly enhanced upon DNA binding, originates from the S2-to-S0 excited-state decay of the additional acceptor-donor segment. A systematic comparison of the effects of additional acceptors on anti-Kasha behaviors and photogenerated reactive oxygen species (ROS) performance has been conducted by constructing two diketopyrrolopyrrole (DPP)-based isomers, namely DPP-F32 and DPP-F34. Both PSs target the Golgi apparatus to activate NIR signals, but only DPP-F32 exhibits visible emission in the nucleus of apoptotic cells, enabling ratiometric tracking of the PDT process at two-/three-dimensional cellular models via dual-channel imaging. This study provides a new paradigm for self-reporting PSs with Kasha/anti-Kasha behaviors that combine precise targeting, efficient ROS generation, and real-time dynamic monitoring.