Novel bioconjugation reactions have been heavily pursued for the past two decades. A myriad of conjugation reactions have been developed for labeling molecules of interest in their native context as well as for constructing multifunctional molecular entities or stimuli-responsive materials. A growing cluster of bioconjugation reactions were realized by tapping into the unique properties of boron. As a rare element in human biology, boronic acids and esters exhibit remarkable biocompatibility. A number of organoboron reagents have been evaluated for bioconjugation, targeting the reactivity of either native biomolecules or those incorporating bioorthogonal functional groups. Owing to the dynamic nature of B–O and B–N bond formation, a significant portion of the boron-enabled bioconjugations exhibit rapid reversibility and accordingly have found applications in the development of reversible covalent inhibitors. On the other hand, stable bioconjugations have been developed that display fast kinetics and significantly expand the repertoire of bioorthogonal chemistry. This contribution presents a summary and comparative analysis of the recently developed boron-mediated bioconjugations. Importantly, this article seeks to provide an in-depth discussion of the thermodynamic and kinetic profiles of these boron-enabled bioconjugations, which reveals structure–reactivity relationships and provides guidelines for bioapplications.

中文翻译：

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基于硼的生物偶联填料


在过去的二十年里，新型生物偶联反应一直受到广泛研究。已经开发了无数的偶联反应，用于在其天然环境中标记目标分子，以及用于构建多功能分子实体或刺激响应材料。通过利用硼的独特特性，实现了越来越多的生物偶联反应。作为人类生物学中的稀有元素，硼酸和酯表现出显著的生物相容性。许多有机硼试剂已经进行了生物偶联评估，靶向天然生物分子或掺入生物正交官能团的生物分子的反应性。由于 B-O 和 B-N 键形成的动态性质，很大一部分硼使生物偶联物表现出快速可逆性，因此在可逆共价抑制剂的开发中得到了应用。另一方面，已经开发了稳定的生物偶联物，它们显示出快速动力学并显着扩展了生物正交化学的库。本贡献对最近开发的硼介导的生物共轭进行了总结和比较分析。重要的是，本文旨在深入讨论这些硼生物偶联物的热力学和动力学曲线，从而揭示结构-反应性关系并为生物应用提供指南。