美国威斯康星大学麦迪逊分校Shannon S. Stahl团队报道了成对电化学氧还原和水氧化合成双加氧酶的反应性。相关研究成果于2024年1月12日发表于国际顶尖学术期刊《科学》。

分子氧的反应性对清洁能源技术和绿色化学合成至关重要，但动力学障碍使这两种应用复杂化。在合成中，双氧应该能够以完美的原子经济性将氧原子转移到两个有机分子上，但这种反应性是罕见的。单加氧酶通常通过牺牲一个氧原子来产生更具反应性的氧化剂，从而还原性地激活双氧。

该文中，研究人员使用四苯基卟啉锰催化剂将电化学氧还原和水氧化配对，在两个电极上产生活性氧氧化锰。这个过程将氧原子转移到两个硫醚底物分子上，用一当量的氧产生两当量的亚砜。这种净双加氧酶反应性不消耗电子，但使用电化学能量来克服动力学障碍。

附：英文原文

Title: Synthetic dioxygenase reactivity by pairing electrochemical oxygen reduction and water oxidation

Author: Md. Asmaul Hoque, James B. Gerken, Shannon S. Stahl

Issue&Volume: 2024-01-12

Abstract: The reactivity of molecular oxygen is crucial to clean energy technologies and green chemical synthesis, but kinetic barriers complicate both applications. In synthesis, dioxygen should be able to undergo oxygen atom transfer to two organic molecules with perfect atom economy, but such reactivity is rare. Monooxygenase enzymes commonly reductively activate dioxygen by sacrificing one of the oxygen atoms to generate a more reactive oxidant. Here, we used a manganese-tetraphenylporphyrin catalyst to pair electrochemical oxygen reduction and water oxidation, generating a reactive manganese-oxo at both electrodes. This process supports dioxygen atom transfer to two thioether substrate molecules, generating two equivalents of sulfoxide with a single equivalent of dioxygen. This net dioxygenase reactivity consumes no electrons but uses electrochemical energy to overcome kinetic barriers.

DOI: adk5097

Source: https://www.science.org/doi/10.1126/science.adk5097