Diazaborines oxidize slowly with H2O2 but rapidly with peroxynitrite in aqueous buffer

Abstract

Reactive oxygen species (ROS) such as hydrogen peroxide (H₂O₂) and peroxynitrite (ONOO^-) oxidize arylboronic acids to their corresponding phenols. When used in molecular imaging probes and in ROS-responsive molecules, however, simple arylboronic acids struggle to discriminate between H₂O₂ and ONOO^- because of their fast rate of reaction with both ROS. Here, we show that diazaborines (DABs) react slowly with H₂O₂ but rapidly with peroxynitrite in an aqueous buffer. In addition to their slow reaction with H₂O₂, the immediate product of DAB oxidation with H₂O₂ and ONOO^- can yield a kinetically trapped CN Z-isomer that slowly equilibrates with its E-isomer. Taken together, our work shows that diazaborines exhibit enhanced kinetic discrimination between H₂O₂ and ONOO^- compared to arylboronic acids, opening up new opportunities for diazaborine-based tools in chemical biology.