Unraveling proton-coupled electron transfer in cofactor-free oxidase- and oxygenase-catalyzed oxygen activation: a...

Oxygen plays a crucial role in the metabolic processes of non-anaerobic organisms. However, a detailed understanding of how triplet oxygen participates in the enzymatic oxidation of organic compounds involved in life processes is still lacking. It is noteworthy that recent studies have found that cofactor-free oxidase- and oxygenase-catalyzed oxygen activation occurs through proton-coupled electron transfer (PCET), which is significantly different from the previously proposed single electron transfer (SET) mechanism. Herein, we summarize the recent advances in the general mechanism of catalytic activation reactions of triplet oxygen by these enzymes. We believe that this review not only helps in providing a deep understanding of the processes involved in oxygen metabolism in organisms but also provides valuable theoretical reference data for designing more efficient enzyme mutants for treating diseases and handling environmental pollution in the future.