Güell Mireia, Luis Josep M, Siegbahn Per E M, Solà Miquel
Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus de Montilivi, 17071, Gerona, Spain.
J Biol Inorg Chem. 2009 Feb;14(2):273-85. doi: 10.1007/s00775-008-0447-7. Epub 2008 Nov 18.
Peptidylglycine alpha-amidating monooxygenase and dopamine beta-monooxygenase are copper-containing proteins which catalyze essential hydroxylation reactions in biological systems. There are several possible mechanisms for the reductive O(2)-activation at their mononuclear copper active site. Recently, Karlin and coworkers reported on the reactivity of a copper(II)-superoxo complex which is capable of inducing the hydroxylation of phenols with incorporated oxygen atoms derived from the Cu(II)-O(2) (.-) moiety. In the present work the reaction mechanism for the abovementioned superoxo complex with phenols is studied. The pathways found are analyzed with the aim of providing some insight into the nature of the chemical and biological copper-promoted oxidative processes with 1:1 Cu(I)/O(2)-derived species.
肽基甘氨酸α-酰胺化单加氧酶和多巴胺β-单加氧酶是含铜蛋白质，它们在生物系统中催化重要的羟基化反应。在其单核铜活性位点上，存在几种可能的还原O₂活化机制。最近，卡林及其同事报道了一种铜（II）-超氧配合物的反应活性，该配合物能够诱导酚类的羟基化反应，其中掺入的氧原子来自Cu（II）-O₂⁻部分。在本工作中，研究了上述超氧配合物与酚类的反应机理。对所发现的反应途径进行了分析，目的是深入了解化学和生物体系中由1:1 Cu（I）/O₂衍生物种促进的铜氧化过程的本质。
