Molybdenum- and tungsten-dependent proteins catalyze essential processes in living organisms and biogeochemical cycles. Among these enzymes, members of the dimethyl sulfoxide (DMSO) reductase superfamily are considered the most diverse, facilitating a wide range of chemical transformations that can be categorized as oxygen atom installation, removal, and transfer. Importantly, DMSO reductase enzymes provide high efficiency and excellent selectivity while operating under mild conditions without conventional oxidants such as oxygen or peroxides. Despite the potential utility of these enzymes as biocatalysts, such applications have not been fully explored. In addition, the vast majority of DMSO reductase enzymes still remain uncharacterized. In this review, we describe the reactivities, proposed mechanisms, and potential synthetic applications of selected enzymes in the DMSO reductase superfamily. We also highlight emerging opportunities to discover new chemical activity and current challenges in studying and engineering proteins in the DMSO reductase superfamily.

中文翻译：

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DMSO 还原酶超家族中酶的新兴化学多样性和潜在应用

钼和钨依赖性蛋白质催化生物体和生物地球化学循环中的重要过程。在这些酶中，二甲亚砜 (DMSO) 还原酶超家族的成员被认为是最多样化的，可促进广泛的化学转化，可分为氧原子安装、去除和转移。重要的是，DMSO 还原酶可提供高效率和出色的选择性，同时在温和条件下运行，无需使用氧气或过氧化物等常规氧化剂。尽管这些酶作为生物催化剂具有潜在的用途，但此类应用尚未得到充分探索。此外，绝大多数 DMSO 还原酶仍未得到表征。在这篇综述中，我们描述了 DMSO 还原酶超家族中选定酶的反应活性、提出的机制和潜在的合成应用。我们还强调了发现新化学活性的新机遇以及当前在 DMSO 还原酶超家族中研究和工程蛋白质方面面临的挑战。