De Meulder Marc, Remmerie Bart M M, de Vries Ronald, Sips Luc L A, Boom Sandra, Hooijschuur Edwin W J, van de Merbel Nico C, Timmerman Philip M M B L
Department of Bioanalysis, Johnson & Johnson Pharmaceutical Research and Development, a Division of Janssen Pharmaceutica N.V., Turnhoutseweg 30, B-2340 Beerse, Belgium.
J Chromatogr B Analyt Technol Biomed Life Sci. 2008 Jul 1;870(1):8-16. doi: 10.1016/j.jchromb.2008.04.041. Epub 2008 May 8.
Two liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) methods are described, one for the quantitative determination of risperidone and the enantiomers of its active metabolite 9-hydroxyrisperidone (paliperidone) in human plasma and the other for the determination of the enantiomers of 9-hydroxyrisperidone in human urine. The plasma method is based on solid-phase extraction of 200 microl of sample on a mixed-mode sorbent, followed by separation on a cellulose-based LC column with a 13.5-min mobile phase gradient of hexane, isopropanol and ethanol. After post-column addition of 10 mM ammonium acetate in ethanol/water, detection takes place by ion-spray tandem mass spectrometry in the positive ion mode. Method validation results show that the method is sufficiently selective towards the enantiomers of 7-hydroxyrisperidone and capable of quantifying the analytes with good precision and accuracy in the concentration range of 0.2-100 ng/ml. An accelerated (run time of 4.3 min) and equally valid method for the enantiomers of 9-hydroxyrisperidone alone in plasma is obtained by increasing the mobile phase flow-rate from 1.0 to 2.0 ml/min and slightly adapting the gradient conditions. The urine method is based on the same solid-phase extraction and chromatographic approach as the accelerated plasma method. Using 100 microl of sample, (+)- and (-)-9-hydroxyrisperidone can be quantified in the concentration range 1-2000 ng/ml. The accelerated method for plasma and the method for urine can be used only when paliperidone is administered instead of risperidone, as there is insufficient separation of the 9-hydroxy enantiomers from the 7-hydroxy enantiomers, the latter ones being present only after risperidone administration.
本文描述了两种液相色谱-串联质谱(LC-MS/MS)方法,一种用于定量测定人血浆中利培酮及其活性代谢物9-羟基利培酮(帕利哌酮)的对映体,另一种用于测定人尿液中9-羟基利培酮的对映体。血浆方法基于在混合模式吸附剂上对200微升样品进行固相萃取,然后在基于纤维素的液相色谱柱上进行分离,流动相为己烷、异丙醇和乙醇,梯度洗脱时间为13.5分钟。柱后加入乙醇/水中的10 mM醋酸铵后,采用离子喷雾串联质谱在正离子模式下进行检测。方法验证结果表明,该方法对7-羟基利培酮对映体具有足够的选择性,能够在0.2-100 ng/ml的浓度范围内以良好的精密度和准确度定量分析物。通过将流动相流速从1.0提高到2.0 ml/min并略微调整梯度条件,可获得一种加速(运行时间为4.3分钟)且同样有效的仅用于血浆中9-羟基利培酮对映体的方法。尿液方法基于与加速血浆方法相同的固相萃取和色谱方法。使用100微升样品,(+)-和(-)-9-羟基利培酮可在1-2000 ng/ml的浓度范围内进行定量。血浆加速方法和尿液方法仅在使用帕利哌酮而非利培酮给药时适用,因为9-羟基对映体与7-羟基对映体的分离不足,后者仅在利培酮给药后才会出现。