Faculty of Chemistry of Functional Molecules, Konan University, Higashinada-ku, Kobe, 658-8501, Japan.
Graduate School of Science and Engineering, Ibaraki University, Bunkyo, Mito, 310-8512, Japan.
Chemistry. 2020 Jul 8;26(38):8324-8340. doi: 10.1002/chem.201905877. Epub 2020 May 11.
The phenoxyl radical plays important roles in biological systems as cofactors in some metalloenzymes, such as galactose oxidase (GO) catalyzing oxidation of primary alcohols to give the corresponding aldehydes. Many metal(II)-phenoxyl radical complexes have hitherto been studied for understanding the detailed properties and reactivities of GO, and thus the nature of GO has gradually become clearer. However, the effects of the subtle geometric and electronic structural changes at the active site of GO, especially the structural change in the catalytic cycle and the effect of the second coordination sphere, have not been fully discussed yet. In this Review, we focus on further details of the model studies of GO and discuss the importance of the structural change at the active site of GO.
苯氧自由基在生物系统中起着重要作用，作为某些金属酶的辅助因子，如半乳糖氧化酶 (GO) 催化伯醇氧化生成相应的醛。迄今为止，已经研究了许多金属 (II)-苯氧自由基配合物，以了解 GO 的详细性质和反应性，因此 GO 的性质逐渐变得清晰。然而，GO 活性位点的细微几何和电子结构变化的影响，特别是催化循环中的结构变化和第二配位球的影响，尚未得到充分讨论。在这篇综述中，我们重点讨论 GO 的模型研究的进一步细节，并讨论 GO 活性位点结构变化的重要性。
