Artificial metalloenzymes (ArMs) comprise a synthetic metal complex in a protein scaffold. ArMs display performances combining those of both homogeneous catalysts and biocatalysts. Specifically, ArMs selectively catalyze non-natural reactions and reactions inspired by nature in water under mild conditions. In the past few years, the construction of ArMs that possess a genetically incorporated unnatural amino acid and the directed evolution of ArMs have become of great interest in the field. Additionally, biochemical applications of ArMs have steadily increased, owing to the fact that compartmentalization within a protein scaffold allows the synthetic metal complex to remain functional in a sea of inactivating biomolecules. In this review, we present updates on: (1) the newly reported ArMs, according to their type of reaction, and (2) the unique biochemical applications of ArMs, including chemoenzymatic cascades and intracellular/in vivo catalysis. We believe that ArMs have great potential as catalysts for organic synthesis and as chemical biology tools for pharmaceutical applications.

中文翻译：

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人工金属酶：从选择性化学转化到生化应用

人工金属酶 (ArMs) 包含蛋白质支架中的合成金属复合物。ArMs 表现出结合均相催化剂和生物催化剂的性能。具体而言，ArMs 在温和条件下选择性地催化非天然反应和受自然界启发的反应。在过去的几年里，具有基因整合的非天然氨基酸的ArMs的构建和ArMs的定向进化已成为该领域的极大兴趣。此外，由于蛋白质支架内的区室化允许合成金属络合物在失活的生物分子海洋中保持功能，因此 Arms 的生化应用稳步增加。在这篇综述中，我们介绍了以下方面的更新：（1）新报告的 Arms，根据它们的反应类型，(2) ArMs 独特的生化应用，包括化学酶级联反应和细胞内/体内催化。我们相信，ArMs 作为有机合成的催化剂和制药应用的化学生物学工具具有巨大的潜力。