Huang Meijia, Cui Jie, Wu Qi, Liu Shengnan, Zhu Dongxia, Li Guangzhe, Bryce Martin R, Wang Dong, Tang Ben Zhong
Key Laboratory of Nanobiosensing and Nanobioanalysis at Universities of Jilin Province, Department of Chemistry, Northeast Normal University, 5268 Renmin Street, Changchun, Jilin Province 130024, P. R. China.
Center for AIE Research, College of Materials Science and Engineering, Shenzhen University, Shenzhen 518060, China.
Inorg Chem. 2024 Dec 16;63(50):24030-24040. doi: 10.1021/acs.inorgchem.4c04571. Epub 2024 Dec 2.
The ability of photosensitizers (PSs) to generate reactive oxygen species (ROS) is crucial for photodynamic therapy (PDT). However, many traditional PSs face the drawbacks that aggregation-caused quenching (ACQ) and highly expressed glutathione (GSH) in the tumor microenvironment seriously limit their ROS generation ability. Herein, we report two cationic dinuclear iridium complexes, and , which possess aggregation-induced emission (AIE). was constructed for GSH consumption by introducing a disulfide linkage between the two auxiliary ligands with imine units. Quantum chemical calculations revealed that and possess many degenerate states, which provide more channels for singlet-to-triplet exciton transitions, and then the intersystem crossing rate is increased due to the heavy atom effect of the iridium and sulfur atoms. The ROS production experiments indicated that the singlet oxygen yield of was 33 times more than that of the ACQ mononuclear iridium complex . Most importantly, consumed GSH through a thiol-disulfide exchange reaction, as demonstrated by mass spectrometry and high-performance liquid chromatography. Cell experiments testified that consumes GSH in tumor cells, possesses good ROS production capacity, and exhibits an extraordinary PDT effect. This is the first report of an AIE dinuclear iridium complex with a GSH-consuming function.
光敏剂（PSs）产生活性氧（ROS）的能力对于光动力疗法（PDT）至关重要。然而，许多传统光敏剂面临着聚集诱导猝灭（ACQ）以及肿瘤微环境中高表达的谷胱甘肽（GSH）严重限制其ROS生成能力的缺点。在此，我们报道了两种具有聚集诱导发光（AIE）特性的阳离子双核铱配合物 和 。 通过在两个带有亚胺单元的辅助配体之间引入二硫键构建而成，用于消耗GSH。量子化学计算表明 和 具有许多简并态，这为单重态到三重态激子跃迁提供了更多通道，然后由于铱和硫原子的重原子效应，系间窜越速率增加。ROS产生实验表明， 的单线态氧产率比ACQ单核铱配合物 高33倍。最重要的是，如质谱和高效液相色谱所证明的， 通过硫醇 - 二硫键交换反应消耗GSH。细胞实验证明 在肿瘤细胞中消耗GSH，具有良好的ROS产生能力，并表现出非凡的PDT效果。这是关于具有消耗GSH功能的AIE双核铱配合物的首次报道。
