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首页> 外文期刊>Electroanalysis >Protein-film Voltammetry of Two-step Electrode Enzymatic Reactions Coupled with an Irreversible Chemical Reaction of a Final Product - A Theoretical Study in Square-wave Voltammetry
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Protein-film Voltammetry of Two-step Electrode Enzymatic Reactions Coupled with an Irreversible Chemical Reaction of a Final Product - A Theoretical Study in Square-wave Voltammetry

机译：两步电极的蛋白质 - 膜伏安法与最终产品的不可逆化学反应相结合 - 方波伏安法中的理论研究

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摘要

Redox mechanisms in which a consecutive two-step electrode transformation occurs, and the product generated in the second electrochemical step at the electrode surface is coupled to a follow-up irreversible chemical reaction, is theoretically considered under conditions of square-wave voltammetry. The electrochemical description of considered systems is a "surface EECirr mechanism". With the methodology named "protein-film square-wave voltammetry" we provide theoretical information on kinetics and thermodynamics of many lipophilic enzymes containing quinones or polyvalent cations of transient metals as redox active sites. We address theoretically situations of energetically separated square-wave voltammetric peaks for at least -150 mV at potential scale. We also consider also a complex scenario of a single voltammetric peak, hiding in its shape both the features of electrode steps (occurring at same potential) and the chemical reaction. We pay a particular attention on how to distinguish the surface two-step EECirr mechanism from a simple one-step surface ECirr mechanism, but also from other two-step surface mechanisms. While presenting plenty of calculated square-wave voltammograms relevant to many enzymatic systems, we point out several simple features that allow kinetic characterization of studied mechanism from time-independent experiments at constant scan rate.
机译：在理论上考虑在方波伏安法的条件下理论上考虑了在电极表面的第二电化学步骤中产生的氧化还原机制，并且在电极表面的第二电化学步骤中产生的产物与随访的不可逆化学反应相连。考虑系统的电化学描述是“表面eecir机构”。通过命名为“蛋白质 - 薄膜方波伏安法”的方法，我们提供了有关许多亲脂性酶的动力学和热力学的理论信息，其含有Quinones或多价金属的多价阳离子作为氧化还原活性位点。我们以潜在的规模在理论上解决了高能量分离的方波伏安峰的情况，至少-150mV。我们还考虑了单个伏安峰的复杂场景，隐藏在其形状中的形状（在相同的电位时发生）和化学反应。我们特别注意如何从简单的一步表面ecirr机构区分表面两步电机机构，而且来自其他两步表面机构。在呈现与许多酶系统相关的大量计算的方波伏安图，我们指出了几种简单的特征，允许在恒定扫描速率下从时间独立实验中进行研究机制的动力学表征。

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