Shimada K, Oe T
Faculty of Pharmaceutical Sciences, Kanazawa University, Japan.
Yakugaku Zasshi. 1991 Apr-May;111(4-5):225-33. doi: 10.1248/yakushi1947.111.4-5_225.
High-performance liquid chromatography (HPLC) with electrochemical detection has been developed for the trace analysis of electrochemically active substances in biological fluids such as catecholamines. The recent development of this system, both instruments and application, has been reviewed. The principle of instrument and newly developed electrode for electrochemical detector have been described at the first section. Series electrodes, especially with coulometric detection, gave much higher selectivity to the analysis of biological substances. The application of HPLC with electrochemical detection to the determination of estrogens in biological fluids clarified the metabolic pathway of catechol estrogens. The applicability to the determination of vitamin D3 and related compounds has been also suggested. For the purpose of extending the applicability of HPLC with electrochemical detection to electro-inactive compounds, pre- and post-column labeling methods have been developed. Pre-column derivatization reagents possessing ferrocene as an electrophore provided a selective and sensitive response to the detector, because of their high-reversibility and low applied potential in the redox reaction. Post-column reaction by using immobilized enzyme reactor has been widely used for the determination of acetylcholine and choline in biological fluids.
已开发出带电化学检测的高效液相色谱法（HPLC）用于生物流体（如儿茶酚胺）中电化学活性物质的痕量分析。本文综述了该系统（包括仪器和应用）的最新进展。第一节介绍了仪器原理和新开发的电化学检测器电极。串联电极，特别是采用库仑检测时，对生物物质的分析具有更高的选择性。HPLC结合电化学检测在生物流体中雌激素测定中的应用阐明了儿茶酚雌激素的代谢途径。还提出了其在维生素D3及相关化合物测定中的适用性。为了将HPLC结合电化学检测的适用性扩展到电惰性化合物，已开发了柱前和柱后标记方法。以二茂铁为电基团的柱前衍生试剂对检测器具有选择性和灵敏的响应，这是因为它们在氧化还原反应中具有高可逆性和低施加电位。使用固定化酶反应器的柱后反应已广泛用于生物流体中乙酰胆碱和胆碱的测定。
