Reactive oxygen and nitrogen species have been implicated in many biological processes and diseases, including immune responses, cardiovascular dysfunction, neurodegeneration, and cancer. These chemical species are short-lived in biological settings, and detecting them in these conditions and diseases requires the use of molecular probes that form stable, easily detectable, products. The chemical mechanisms and limitations of many of the currently used probes are not well-understood, hampering their effective applications. Boronates have emerged as a class of probes for the detection of nucleophilic two-electron oxidants. Here, we report the results of an oxygen-18-labeling MS study to identify the origin of oxygen atoms in the oxidation products of phenylboronate targeted to mitochondria. We demonstrate that boronate oxidation by hydrogen peroxide, peroxymonocarbonate, hypochlorite, or peroxynitrite involves the incorporation of oxygen atoms from these oxidants. We therefore conclude that boronates can be used as probes to track isotopically labeled oxidants. This suggests that the detection of specific products formed from these redox probes could enable precise identification of oxidants formed in biological systems. We discuss the implications of these results for understanding the mechanism of conversion of the boronate-based redox probes to oxidant-specific products.

中文翻译：

---

使用基于硼酸酯的氧化还原探针跟踪同位素标记的氧化剂。

活性氧和氮物质与许多生物过程和疾病有关，包括免疫反应，心血管功能障碍，神经变性和癌症。这些化学物质在生物环境中寿命很短，要在这些条件和疾病中检测它们，就需要使用形成稳定，易于检测的产品的分子探针。许多当前使用的探针的化学机理和局限性尚未得到很好的理解，从而妨碍了它们的有效应用。硼酸盐已成为一类用于检测亲核两电子氧化剂的探针。在这里，我们报告氧18标记MS研究的结果，以鉴定针对线粒体的苯基硼酸酯氧化产物中氧原子的起源。我们证明过氧化氢，过氧化一碳酸氢盐，次氯酸盐或过氧化亚硝酸盐的硼酸盐氧化反应涉及从这些氧化剂中引入氧原子。因此，我们得出结论，硼酸盐可以用作探针来跟踪同位素标记的氧化剂。这表明检测由这些氧化还原探针形成的特定产物可以准确鉴定生物系统中形成的氧化剂。我们讨论这些结果的含义，以了解基于硼酸酯的氧化还原探针向氧化剂特异性产物转化的机理。这表明检测由这些氧化还原探针形成的特定产物可以准确鉴定生物系统中形成的氧化剂。我们讨论这些结果的含义，以了解基于硼酸酯的氧化还原探针向氧化剂特异性产物转化的机理。这表明检测由这些氧化还原探针形成的特定产物可以准确鉴定生物系统中形成的氧化剂。我们讨论这些结果的含义，以了解基于硼酸酯的氧化还原探针向氧化剂特异性产物转化的机理。