Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China.
Anal Chem. 2015 Dec 1;87(23):11819-25. doi: 10.1021/acs.analchem.5b03280. Epub 2015 Nov 9.
In a hydrophilic droplet three-electrode system, electroactive species within the droplet play very important roles in the electron-transfer (ET) process on the solid/electrolyte interface, which can then induce an ion-transfer (IT) reaction at the liquid/liquid interface. In this work, several redox couples and electroactive species are chosen to study ET-IT coupling processes at the water/1,2-dichloroethane (W/DCE) interface by cyclic voltammetry (CV) and Osteryoung square wave voltammetry (OSWV). Among them, the redox couple Ru(NH3)6(3+/2+) has been found to have the widest useful potential window of about 1.2 V. A hydrophilic droplet three-electrode system using a single electroactive molecule instead of a redox couple has been confirmed to be stable and has similar functionality to a redox couple. In addition, the lipophilicity of antiplatelet drug clopidogrel at the W/DCE interface is investigated and its ionic partition diagram has been constructed. Protonated clopidogrel is detected in a linear concentration range of 5.0-50 μM and the limit of detection (LOD) is calculated to be 3.0 μM by using the hydrophilic droplet system Ru(NH3)6(3+/2+) and OSWV.
在亲水液滴三电极体系中，液滴内的电活性物质在固/电解质界面上的电子转移（ET）过程中起着非常重要的作用，这可以在液/液界面诱导离子转移（IT）反应。在这项工作中，选择了几种氧化还原对和电活性物质，通过循环伏安法（CV）和Osteryoung 方波伏安法（OSWV）研究了水/1,2-二氯乙烷（W/DCE）界面处的 ET-IT 偶联过程。其中，Ru(NH3)6(3+/2+)氧化还原对具有约 1.2 V 的最宽有用电位窗口。已证实使用单个电活性分子而不是氧化还原对的亲水液滴三电极系统稳定且具有与氧化还原对相似的功能。此外，还研究了抗血小板药物氯吡格雷在 W/DCE 界面的亲脂性，并构建了其离子分配图。通过使用亲水液滴系统 Ru(NH3)6(3+/2+)和 OSWV，在 5.0-50 μM 的线性浓度范围内检测到了质子化的氯吡格雷，检测限（LOD）计算为 3.0 μM。
