Kalimuthu Palraj, Heider Johann, Knack Daniel, Bernhardt Paul V
School of Chemistry and Molecular Biosciences, University of Queensland , Brisbane 4072, Australia.
J Phys Chem B. 2015 Feb 26;119(8):3456-63. doi: 10.1021/jp512562k. Epub 2015 Feb 12.
We report the electrocatalytic activity of ethylbenzene dehydrogenase (EBDH) from the β-proteobacterium Aromatoleum aromaticum. EBDH is a complex 155 kDa heterotrimeric molybdenum/iron-sulfur/heme protein which catalyzes the enantioselective hydroxylation of nonactivated ethylbenzene to (S)-1-phenylethanol without molecular oxygen as cosubstrate. Furthermore, it oxidizes a wide range of other alkyl-substituted aromatic and heterocyclic compounds to their secondary alcohols. Hydroxymethylferrocenium (FM) is used as an artificial electron acceptor for EBDH in an electrochemically driven catalytic system. Electrocatalytic activity of EBDH is demonstrated with both its native substrate ethylbenzene and the related substrate p-ethylphenol. The catalytic system has been modeled by electrochemical simulation across a range of sweep rates and concentrations of each substrate, which provides new insights into the kinetics of the EBDH catalytic mechanism.
我们报道了β-变形菌芳香油嗜芳烃菌中乙苯脱氢酶（EBDH）的电催化活性。EBDH是一种155 kDa的复杂异源三聚体钼/铁硫/血红素蛋白，它能在没有分子氧作为共底物的情况下，将未活化的乙苯对映选择性羟基化为（S）-1-苯乙醇。此外，它还能将多种其他烷基取代的芳香族和杂环化合物氧化为仲醇。在电化学驱动的催化体系中，羟甲基二茂铁鎓（FM）被用作EBDH的人工电子受体。EBDH对其天然底物乙苯和相关底物对乙基苯酚均表现出电催化活性。通过在一系列扫描速率和每种底物浓度下进行电化学模拟，对该催化体系进行了建模，这为EBDH催化机制的动力学提供了新的见解。
