Expanding the repertoire of reactions available to enzymes is an enduring challenge in biocatalysis. Owing to the synthetic versatility of transition metals, metalloenzymes have been favored targets for achieving new catalytic functions. Although less well explored, enzymes lacking metal centers can also be effective catalysts for non-natural reactions, providing access to reaction modalities that compliment those available to metals. By understanding how these activation modes can reveal new functions, strategies can be developed to access novel biocatalytic reactions. This review will cover discoveries in the last two years which access catalytic reactions that go beyond the native repertoire of metal-free biocatalysts.

中文翻译：

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扩大生物催化酶工具箱的新兴策略。


扩大酶可用的反应范围是生物催化领域的一个持久挑战。由于过渡金属的合成多功能性，金属酶已成为实现新催化功能的热门靶标。尽管探索较少，但缺乏金属中心的酶也可以成为非自然反应的有效催化剂，提供与金属可用的反应方式相辅相成的途径。通过了解这些激活模式如何揭示新功能，可以制定策略来实现新的生物催化反应。这篇综述将涵盖过去两年中的发现，这些发现超出了无金属生物催化剂的固有范围。