Department of Chemistry, The University of Texas at Austin, Austin, TX 78712, United States of America.
Department of Chemistry, The University of Texas at Austin, Austin, TX 78712, United States of America.
J Inorg Biochem. 2024 Oct;259:112669. doi: 10.1016/j.jinorgbio.2024.112669. Epub 2024 Jul 19.
The continuously increasing level of atmospheric CO in the atmosphere has led to global warming. Converting CO into other carbon compounds could mitigate its atmospheric levels and produce valuable products, as CO also serves as a plentiful and inexpensive carbon feedstock. However, the inert nature of CO poses a major challenge for its reduction. To meet the challenge, nature has evolved metalloenzymes using transition metal ions like Fe, Ni, Mo, and W, as well as electron-transfer partners for their functions. Mimicking these enzymes, artificial metalloenzymes (ArMs) have been designed using alternative protein scaffolds and various metallocofactors like Ni, Co, Re, Rh, and FeS clusters. Both the catalytic efficiency and the scope of CO-reduction product of these ArMs have been improved over the past decade. This review first focuses on the natural metalloenzymes that directly reduce CO by discussing their structures and active sites, as well as the proposed reaction mechanisms. It then introduces the common strategies for electrochemical, photochemical, or photoelectrochemical utilization of these native enzymes for CO reduction and highlights the most recent advancements from the past five years. We also summarize principles of protein design for bio-inspired ArMs, comparing them with native enzymatic systems and outlining challenges and opportunities in enzymatic CO reduction.
大气中不断增加的 CO 水平导致了全球变暖。将 CO 转化为其他碳化合物可以降低其大气水平，并产生有价值的产品，因为 CO 也是一种丰富且廉价的碳原料。然而，CO 的惰性对其还原构成了重大挑战。为了应对这一挑战，自然界已经进化出了使用过渡金属离子（如 Fe、Ni、Mo 和 W）以及电子转移伙伴来发挥功能的金属酶。为了模仿这些酶，人们使用替代的蛋白质支架和各种金属辅因子（如 Ni、Co、Re、Rh 和 FeS 簇）设计了人工金属酶（ArMs）。在过去的十年中，这些 ArMs 的催化效率和 CO 还原产物的范围都得到了提高。这篇综述首先关注直接还原 CO 的天然金属酶，讨论它们的结构和活性位点，以及提出的反应机制。然后介绍了电化学、光化学或光电化学利用这些天然酶进行 CO 还原的常见策略，并重点介绍了过去五年的最新进展。我们还总结了仿生 ArMs 的蛋白质设计原则，将其与天然酶系统进行比较，并概述了酶促 CO 还原中的挑战和机遇。
