Interpreting the catalytic voltammetry of electroactive enzymes adsorbed on electrodes
Interpreting the catalytic voltammetry of electroactive enzymes adsorbed on electrodes
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DOI：
10.1021/jp981023r
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发表时间：
1998-08-27
影响因子：
3.3
通讯作者：
Armstrong, FA
中科院分区：
文献类型：
--
作者：
Heering, HA;Hirst, J;Armstrong, FA
吸附在电极上的氧化还原酶所显示的稳态电催化波形进行分析，以揭示和量化参与催化的活性位点的重要机械特性，并阐明不同因素在确定整体电子传输速率的贡献。伏安波的形状、高度、陡度和电势是质量传递、界面电子转移速率以及酶的内在动力学和热力学性质的函数。首先构建一个模型，最简单的现实情况下，一个酶含有一个单一的两电子活性位点，然后这是扩展到包括额外的电子转移中心，作为分子内继电器。方程推导出预测的稳态行为预期不同的条件下，和模型被用来评估最近的实验结果。因此，酶催化电子传递的另一种观点，其中动力学和能量被认为是在潜在的域和分析。
Steady-state electrocatalytic waveforms displayed by redox enzymes adsorbed on electrodes are analyzed to reveal and quantify important mechanistic characteristics of the active sites involved in catalysis and to elucidate the contributions of different factors in determining the overall electron-transport rates. The shape, height, steepness, and potential of the voltammetric waves are functions of mass transport, interfacial electron-transfer rates, and the intrinsic kinetic and thermodynamic properties of the enzyme. A model is constructed first for the most simple realistic case, an enzyme containing a single two-electron active site, and then this is extended to include additional electron-transfer centers that serve as intramolecular relays. Equations are derived that predict the steady-state behavior expected for different conditions, and the models are used to assess recent experimental results. An alternative perspective on enzyme catalytic electron-transport is thus presented, in which kinetics and energetics are viewed and analyzed in the potential domain.