Nitric Oxide Generation on Demand for Biomedical Applications via Electrocatalytic Nitrite Reduction by Copper BMPA- and BEPA-Carboxylate Complexes

作者：Andrew P. Hunt, Allison E. Batka, Marjan Hosseinzadeh, Jordan D. Gregory, Halima K. Haque, Hang Ren, Mark E. Meyerhoff, Nicolai Lehnert · 发表于：ACS Catalysis · 年份：2019 · DOI：10.1021/acscatal.9b01520 · 被引用次数：54 · 研究领域：CO2 Reduction Techniques and Catalysts、Electrochemical Analysis and Applications、Electrocatalysts for Energy Conversion

Intravascular (IV) catheters are essential devices in the hospital that are used to monitor a patient's blood and for administering drugs or nutrients. However, IV catheters are also prone to blood clotting at the point of insertion and infection by formation of robust bacterial biofilms on their surface. Nitric oxide (NO) is ideally suited to counteract both of these problems, due to its antimicrobial properties and its ability to inhibit platelet activation/aggregation. One way to equip catheters with NO releasing properties is by electrocatalytic nitrite reduction to NO by copper complexes in a multi-lumen configuration. In this work, we systematically investigate six closely related Cu(II) BMPA- and BEPA-carboxylate complexes (BMPA = bis-(2-methylpyridyl)amine); BEPA = bis-(2-ethylpyridyl)amine), using carboxylate groups of different chain lengths. The corresponding Cu(II) complexes were characterized using UV-Vis, EPR spectroscopy, and X-ray crystallography. Using detailed cyclic voltammetry (CV) and bulk electrocatalyic studies (with real-time NO quantification), in aqueous buffer, pH 7.4, we are able to derive clear reactivity relations between the ligand structures of the complexes, their Faradaic efficiencies for NO generation, their turnover frequencies (TOFs), and their redox potentials. Our results show that the complex [Cu(BEPA-Bu)](OAc) is the best catalyst with a high Faradaic efficiency over large nitrite concentration ranges and the expected best tolerance to...