Department of Biology, University of Naples Federico II, Naples, Italy.
National Research Council - Institute of Biomolecular Chemistry - CNR-ICB, Pozzuoli, Italy.
Essays Biochem. 2023 Aug 11;67(4):653-670. doi: 10.1042/EBC20230012.
Life sustains itself using energy generated by thermodynamic disequilibria, commonly existing as redox disequilibria. Metals are significant players in controlling redox reactions, as they are essential components of the engine that life uses to tap into the thermodynamic disequilibria necessary for metabolism. The number of proteins that evolved to catalyze redox reactions is extraordinary, as is the diversification level of metal cofactors and catalytic domain structures involved. Notwithstanding the importance of the topic, the relationship between metals and the redox reactions they are involved in has been poorly explored. This work reviews the structure and function of different prokaryotic organometallic-protein complexes, highlighting their pivotal role in controlling biogeochemistry. We focus on a specific subset of metal-containing oxidoreductases (EC1 or EC7.1), which are directly involved in biogeochemical cycles, i.e., at least one substrate or product is a small inorganic molecule that is or can be exchanged with the environment. Based on these inclusion criteria, we select and report 59 metalloenzymes, describing the organometallic structure of their active sites, the redox reactions in which they are involved, and their biogeochemical roles.
生命利用热力学不平衡产生的能量维持自身，这种不平衡通常表现为氧化还原不平衡。金属在控制氧化还原反应中起着重要作用，因为它们是生命用来利用代谢所需热力学不平衡的引擎的重要组成部分。进化来催化氧化还原反应的蛋白质数量非常多，涉及的金属辅因子和催化结构域的多样化程度也非常高。尽管这一主题非常重要，但金属与它们所参与的氧化还原反应之间的关系尚未得到充分探索。这项工作回顾了不同原核有机金属蛋白复合物的结构和功能，强调了它们在控制生物地球化学中的关键作用。我们专注于直接参与生物地球化学循环的一类含金属氧化还原酶（EC1 或 EC7.1），即至少有一种底物或产物是一种与环境可交换的小分子无机物。基于这些纳入标准，我们选择并报告了 59 种金属酶，描述了它们活性位点的有机金属结构、它们所参与的氧化还原反应以及它们的生物地球化学作用。
