State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Zhang Dayu School of Chemistry, Dalian University of Technology, 116024, Dalian, P. R. China.
Key Laboratory of Design and Assembly of Functional Nanostructures, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, 350002, Fuzhou, P. R. China.
Angew Chem Int Ed Engl. 2023 May 8;62(20):e202219172. doi: 10.1002/anie.202219172. Epub 2023 Mar 6.
Redox logic materials offer new avenues to modulate intracellular pathologic redox environment area-specifically, but the unambiguity of redox logic states and their unidirectional and repetitive switchability are challenging to realize. By merging a bistable diisophthalic phenazine dye ligand with Cu salt, a multistable coordination polymer (CP) was constructed, of which the dye-Cu anisotropic junction achieved the diode-like unidirectional electron transfer and logic state ratchet for the first time. Radical cationic CP maintained OFF status with low toxicity in healthy tissues, but was reduced to the neutral SERVO state by the overexpressed glutathione (GSH) in hypoxic tumors. After photoirradiation, the stabilized charge-separated ON status promoted photo-Fenton reaction for reactive oxygen species (ROS) signal transduction, and simultaneously recovered the initial state for catalytic signal amplification of ROS, furnishing intratumor redox photomodulation for therapy.
氧化还原逻辑材料为调节细胞内病理氧化还原环境提供了新途径，具有区域特异性，但氧化还原逻辑状态的明确性及其单向和可重复的开关性难以实现。通过将双稳态二异苯并嗪染料配体与铜盐结合，构建了一种多稳态配位聚合物 (CP)，其中染料-Cu 各向异性结首次实现了类似二极管的单向电子转移和逻辑状态棘轮。自由基阳离子 CP 在健康组织中保持低毒性的关闭状态，但在缺氧肿瘤中过表达的谷胱甘肽 (GSH) 还原为中性 SERVO 状态。光照射后，稳定的电荷分离开启状态促进了用于活性氧 (ROS) 信号转导的光芬顿反应，同时为 ROS 的催化信号放大恢复初始状态，为治疗提供肿瘤内氧化还原光调节。
