Kawamura Maiko, Kikura-Hanajiri Ruri, Goda Yukihiro
National Institute of Health Sciences, Tokyo, Japan.
Yakugaku Zasshi. 2011;131(5):827-33. doi: 10.1248/yakushi.131.827.
An ionization technique, direct analysis in real time (DART) has recently been developed for the ambient ionization of a variety samples. The DART coupled with time-of-flight mass spectrometry (TOFMS) would be useful as a simple and rapid screening for the targeted compounds in various samples, because it provides the molecular information of these compounds without time-consuming extraction. In this study, we investigated rapid screening methods of illicit drugs and their metabolites, such as methamphetamine (MA), 3,4-methylenedioxymethamphetamine (MDMA), amphetamine (AP) and 3,4-methylenedioxyamphetamine (MDA) in human urine using DART-TOFMS. As serious matrix effects caused by urea in urine samples and ionizations of the targeted compounds were greatly suppressed in the DART-TOFMS analyses, simple pretreatment methods to remove the urea from the samples were investigated. When a pipette tip-type solid-phase extraction with a dichloromethane and isopropanol mixed solution as an eluent was used for the pretreatment, the limits of detection (LODs) of 4 compounds added to control urine samples were 0.25 µg/ml. On the other hand, the LODs of these compounds were 0.5 µg/ml by a liquid-liquid extraction using a dichloromethane and hexane mixed solution. In both extractions, the recoveries of 4 compounds from urine samples were over 70% and these extraction methods showed good linearity in the range of 0.5-5 µg/ml by GC-MS analyses. In conclusion, our proposed method using DART-TOFMS could simultaneously detect MA, MDMA and their metabolites in urine at 0.5 µg/ml without time-consuming pretreatment steps. Therefore it would be useful for screening drugs in urine with the molecular information.
一种电离技术——实时直接分析(DART)最近已被开发用于多种样品的常压电离。DART与飞行时间质谱(TOFMS)联用,可作为一种简单快速的方法,用于筛查各种样品中的目标化合物,因为它无需耗时的提取过程就能提供这些化合物的分子信息。在本研究中,我们使用DART-TOFMS研究了人体尿液中非法药物及其代谢物,如甲基苯丙胺(MA)、3,4-亚甲基二氧基甲基苯丙胺(MDMA)、苯丙胺(AP)和3,4-亚甲基二氧基苯丙胺(MDA)的快速筛查方法。由于尿液样品中的尿素会引起严重的基质效应,且在DART-TOFMS分析中目标化合物的电离受到极大抑制,因此我们研究了从样品中去除尿素的简单预处理方法。当使用二氯甲烷和异丙醇混合溶液作为洗脱剂的移液器吸头型固相萃取进行预处理时,添加到对照尿液样品中的4种化合物的检测限(LOD)为0.25μg/ml。另一方面,通过使用二氯甲烷和己烷混合溶液的液液萃取,这些化合物的LOD为0.5μg/ml。在两种萃取方法中,尿液样品中4种化合物的回收率均超过70%,并且通过气相色谱-质谱(GC-MS)分析,这些萃取方法在0.5-5μg/ml范围内显示出良好的线性。总之,我们提出的使用DART-TOFMS的方法可以在无需耗时预处理步骤的情况下,同时检测尿液中浓度为0.5μg/ml的MA、MDMA及其代谢物。因此,它将有助于利用分子信息对尿液中的药物进行筛查。