Department of Pharmacy, The First Affiliated Hospital of USTC, Division of Life Sciences and Medicine, and CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, China.
Angew Chem Int Ed Engl. 2022 Jul 25;61(30):e202204526. doi: 10.1002/anie.202204526. Epub 2022 Jun 1.
Photoredox catalysis has emerged as a robust tool for chemical synthesis. However, it remains challenging to implement photoredox catalysis under physiological conditions due to the complex microenvironment and the quenching of photocatalyst by biologically relevant molecules such as oxygen. Here, we report that UV-absorbing N,N'-dinitroso-1,4-phenylenediamine derivatives can be selectively activated by fac-Ir(ppy) photocatalyst within micellar nanoparticles under visible light irradiation (e.g., 500 nm) through photoredox catalysis in aerated aqueous solutions to form quinonediimine (QDI) residues with concomitant release of NO. Notably, the formation of QDI derivatives can actively scavenge the reactive oxygen species generated by fac-Ir(ppy) , thus avoiding oxygen quenching of the photocatalyst. Further, we exemplify that the oxygen-tolerant photoredox catalysis-mediated NO release can not only kill planktonic bacteria in vitro but also efficiently treat MRSA infections in vivo.
光氧化还原催化已成为化学合成的有力工具。然而，由于复杂的微环境以及生物相关分子（如氧）对光催化剂的猝灭，在生理条件下实施光氧化还原催化仍然具有挑战性。在这里，我们报告说，在有氧水相溶液中，通过光氧化还原催化，在可见光照射下（例如 500nm），可将具有紫外吸收的 N,N'-二硝基-1,4-苯二胺衍生物选择性地激活为胶束纳米颗粒内的 fac-Ir(ppy) 光催化剂，以形成伴随有 NO 释放的醌二亚胺 (QDI) 残基。值得注意的是，QDI 衍生物的形成可以主动清除由 fac-Ir(ppy) 产生的活性氧物种，从而避免光催化剂的氧猝灭。此外，我们举例说明了耐氧的光氧化还原催化介导的 NO 释放不仅可以杀死体外浮游细菌，而且可以有效地治疗体内耐甲氧西林金黄色葡萄球菌感染。
