Tsai J L, Wu W S, Lee H H
Graduate Institute of Occupational Safety and Health, Kaohsiung Medical University, Taiwan.
Electrophoresis. 2000 May;21(8):1580-6. doi: 10.1002/(SICI)1522-2683(20000501)21:8<1580::AID-ELPS1580>3.0.CO;2-S.
A rapid, sensitive method for the determination of morphine and amphetamine was developed using capillary zone electrophoresis coupled with electrospray interface (ESI), ion-trap tandem mass spectrometry (CE-ESI-MS2). Morphine and amphetamine were separated in 20 mM ammonium acetate buffer (pH 6.6) and detected by ion-trap mass detector in different analytical time segments (0-6.25 min for amphetamine and 6.25-12.0 min for morphine) in which the tune file for each compound was used separately. Molecular ions of morphine (m/z 286) and amphetamine (m/z 136) were detected at 5.77 and 6.83 min, respectively, while product ions of MS2 for each compound (m/z 229, 201 for morphine and m/z 119 for amphetamine) were detected almost exactly at the same time with their parent compounds. The limits of detection (LOD) for MS2 determination were 30 and 50 ng/mL for amphetamine and morphine, respectively, with an S/N ratio of 3. For more sensitive detection of morphine, the sample was injected for a longer time (i.e., 80 s) and hydrodynamically transported into a CE capillary for MS detection. Morphine and its product ion appear at 0.36 and 0.39 min on the ion chromatogram, respectively, with a five-fold increase of detection sensitivity (LOD, 10 ng/mL). The CE-MS system thus established was further applied for forensic urine samples screened as morphine-positive by fluorescence polarization immunoassay (FPIA). These results indicated the feasibility of CE-ESI-MS2 for confirmative testing of morphine in urine sample.
开发了一种快速、灵敏的吗啡和苯丙胺测定方法，该方法采用毛细管区带电泳与电喷雾接口（ESI）、离子阱串联质谱联用（CE-ESI-MS2）。吗啡和苯丙胺在20 mM醋酸铵缓冲液（pH 6.6）中分离，并通过离子阱质量检测器在不同的分析时间段（苯丙胺为0 - 6.25分钟，吗啡为6.25 - 12.0分钟）进行检测，其中每种化合物的调谐文件单独使用。吗啡（m/z 286）和苯丙胺（m/z 136）的分子离子分别在5.77和6.83分钟检测到，而每种化合物的MS2产物离子（吗啡的m/z 229、201和苯丙胺的m/z 119）与其母体化合物几乎在同一时间检测到。MS2测定的检测限（LOD）分别为苯丙胺30 ng/mL和吗啡50 ng/mL，信噪比为3。为了更灵敏地检测吗啡，将样品进样更长时间（即80秒），并通过流体动力学方式输送到CE毛细管中进行MS检测。吗啡及其产物离子在离子色谱图上分别出现在0.36和0.39分钟，检测灵敏度提高了五倍（LOD，10 ng/mL）。由此建立的CE-MS系统进一步应用于通过荧光偏振免疫分析（FPIA）筛选为吗啡阳性的法医尿液样本。这些结果表明CE-ESI-MS2用于尿液样本中吗啡确证检测的可行性。
