Diazaborines oxidize slowly with H2O2 but rapidly with peroxynitrite in aqueous buffer. Issue 5 (14th January 2022)

• Record Type: Journal Article
• Authors: Haggett, Jack G.; Han, Gun Su; Moser, Angela R.; Golzwarden, Julian V. A.; Vyas, Shubham; Domaille, Dylan W.
• Is Part Of: Organic & biomolecular chemistry. Volume 20:Issue 5(2022)
• Page Start: 995
• Page End: 999
• Publication Date: 2022-01-14
• Subjects: Chemistry, Organic -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1039/d1ob01668g
• Languages: English
• ISSNs: 1477-0520

Abstract

Abstract : Diazaborines react slowly with H2 O2 but rapidly with ONOO −, offering a new platform for discriminating between these two cellular ROS. Abstract : Reactive oxygen species (ROS) such as hydrogen peroxide (H2 O2 ) 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 H2 O2 and ONOO − because of their fast rate of reaction with both ROS. Here, we show that diazaborines (DABs) react slowly with H2 O2 but rapidly with peroxynitrite in an aqueous buffer. In addition to their slow reaction with H2 O2, the immediate product of DAB oxidation with H2 O2 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 H2 O2 and ONOO − compared to arylboronic acids, opening up new opportunities for diazaborine-based tools in chemical biology.