Department of Chemistry, Ralph N. Adams Institute for Bioanalytical Chemistry, University of Kansas, Lawrence, KS 66047, USA.
Electrophoresis. 2012 Sep;33(17):2725-32. doi: 10.1002/elps.201200113.
An approach to on-capillary dual-electrode detection for CE using a parallel electrode configuration has been developed. The parallel configuration provides two operating modes. In the first mode, one working electrode is held at an oxidizing potential and the second working electrode is held at a reducing potential. This results in redox cycling of analytes between the oxidized and reduced forms, enhancing sensitivity compared to single-electrode detection. In the second mode, both working electrodes are held at different oxidizing potentials. This mode provides electrochemical characterization of electrophoretic peaks. In the redox cyclying mode, signal enhancement of up to twofold was observed for the dual-electrode detection of phenolic acid standards compared to single-electrode detection. Variation in response of less than 10% from electrode to electrode was determined (at a concentration of 60 nM) indicating reproducible fabrication. LODs were determined to be as low as 5.0 nM for dual-electrode configuration. Using the dual-potential mode peak identification of targeted phenolic acids in whiskey samples were confirmed based on both migration time and current ratios.
已经开发出一种用于 CE 的毛细管内双电极检测方法,采用平行电极配置。平行配置提供两种操作模式。在第一种模式下,一个工作电极保持在氧化电位,第二个工作电极保持在还原电位。这导致分析物在氧化和还原形式之间进行氧化还原循环,与单电极检测相比提高了灵敏度。在第二种模式下,两个工作电极都保持在不同的氧化电位。这种模式提供电泳峰的电化学特性。在氧化还原循环模式下,与单电极检测相比,双电极检测酚酸标准品的信号增强了两倍。从一个电极到另一个电极的响应变化小于 10%(在 60 nM 浓度下),表明可重复制造。LOD 低至 5.0 nM 对于双电极配置。使用双电位模式,可以根据迁移时间和电流比确认威士忌样品中目标酚酸的峰识别。