Otsuka Koji, Matsumura Mieko, Kim Jong-Bok, Terabe Shigeru
Faculty of Science, Himeji Institute of Technology, Kamigori, Hyogo 678-1297, Japan.
J Pharm Biomed Anal. 2003 Jan 15;30(6):1861-7. doi: 10.1016/s0731-7085(02)00529-0.
Enantioselective separation of triadimenol, a component of systemic agricultural fungicide, by electrokinetic chromatography (EKC) using cyclodextrins (CDs) as chiral selectors was investigated. Both a neutral CD derivative, hydroxypropyl-gamma-CD (HP-gamma-CD), and an ionic one, heptakis-6-sulfato-beta-CD (HS-beta-CD), were employed as an additive in cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) and as a chiral pseudostationary phase in CDEKC, respectively. In each system, four stereoisomeric peaks were completely or partially separated from each other. To enhance the detectability or the concentration sensitivity, on-line preconcentration techniques were applied to both EKC systems. Sweeping was used in the CD-MEKC system under an acidic condition, whereas stacking with a reverse migrating pseudostationary phase (SRMP) in the CDEKC system. Around 10-fold increase in the detection sensitivity for each peak was attained with both sweeping and SRMP systems. Good repeatabilities in the migration time, corrected peak area, and peak height were recognized in terms of the relative standard deviation. The limit of detection for each peak in the SRMP-CDEKC system, calculated from the calibration curve, was found to be 0.8-3.8 ppm.
研究了以环糊精(CDs)作为手性选择剂,通过电动色谱(EKC)对农用内吸性杀菌剂的成分三唑醇进行对映体拆分。分别使用中性CD衍生物羟丙基-γ-环糊精(HP-γ-CD)和离子型七(6-硫酸根)-β-环糊精(HS-β-CD)作为环糊精修饰的胶束电动色谱(CD-MEKC)中的添加剂以及CDEKC中的手性假固定相。在每个体系中,四个立体异构体峰彼此完全或部分分离。为提高检测能力或浓度灵敏度,对两个EKC体系均应用了在线预富集技术。在酸性条件下,CD-MEKC体系中使用了推扫技术,而CDEKC体系中使用了反向迁移假固定相(SRMP)进行堆积。推扫和SRMP体系均使每个峰的检测灵敏度提高了约10倍。从相对标准偏差来看,迁移时间、校正峰面积和峰高具有良好的重复性。根据校准曲线计算,SRMP-CDEKC体系中每个峰的检测限为0.8 - 3.8 ppm。