Chèze Marjorie, Deveaux Marc, Martin Claire, Lhermitte Michel, Pépin Gilbert
Laboratoire TOXLAB, Paris, France.
Forensic Sci Int. 2007 Aug 6;170(2-3):100-4. doi: 10.1016/j.forsciint.2007.02.033. Epub 2007 Jul 16.
A rapid and sensitive method using LC-MS/MS triple stage quadrupole for the determination of traces of amphetamine (AP), methamphetamine (MA), 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxymethamphetamine (MDMA, "ecstasy"), 3,4-methylenedioxyethamphetamine (MDEA), and N-methyl-1-(3,4-methylenedioxyphenyl)-2-butanamine (MBDB) in hair, blood and urine has been developed and validated. Chromatography was carried out on an Uptisphere ODB C(18) 5 microm, 2.1 mm x 150 mm column (Interchim, France) with a gradient of acetonitrile and formate 2 mM pH 3.0 buffer. Urine and blood were extracted with Toxitube A (Varian, France). Segmented scalp hair was treated by incubation 15 min at 80 degrees C in NaOH 1M before liquid-liquid extraction with hexane/ethyl acetate (2/1, v/v). The limits of quantification (LOQ) in blood and urine were at 0.1 ng/mL for all analytes. In hair, LOQ was <5 pg/mg for MA, MDMA, MDEA and MBDB, at 14.7 pg/mg for AP and 15.7 pg/mg for MDA. Calibration curves were linear in the range 0.1-50 ng/mL in blood and urine; in the range 5-500 pg/mg for MA, MDMA, MDEA and MBDB, and 20-500 pg/mg for AP and MDA. Inter-day precisions were <13% for all analytes in all matrices. Accuracy was <20% in blood and urine at 1 and 50 ng/mL and <10% in hair at 20 and 250 pg/mg. This method was applied to the determination of MDMA in a forensic case of single administration of ecstasy to a 16-year-old female without her knowledge during a party. She suffered from hyperactivity, sweating and agitation. A first sample of urine was collected a few hours after (T+12h) and tested positive to amphetamines by immunoassay by a clinical laboratory. Blood and urine were sampled for forensic purposes at day 8 (D+8) and scalp hair at day 60 (D+60). No MDMA was detected in blood, but urine and hair were tested positive, respectively at 0.42 ng/mL and at 22 pg/mg in hair only in the segment corresponding to the period of the offence, while no MDA was detectable. This method allows the detection of MDMA up to 8 days in urine after single intake.
已开发并验证了一种使用液相色谱 - 串联质谱三重四极杆技术快速灵敏地测定毛发、血液和尿液中痕量苯丙胺（AP）、甲基苯丙胺（MA）、3,4 - 亚甲基二氧基苯丙胺（MDA）、3,4 - 亚甲基二氧基甲基苯丙胺（MDMA，“摇头丸”）、3,4 - 亚甲基二氧基乙胺（MDEA）和N - 甲基 - 1 -（3,4 - 亚甲基二氧基苯基）- 2 - 丁胺（MBDB）的方法。色谱分析在一根Uptisphere ODB C(18) 5微米、2.1毫米×150毫米的色谱柱（法国Interchim公司）上进行，流动相为乙腈和2 mM pH 3.0的甲酸缓冲液，采用梯度洗脱。尿液和血液用Toxitube A（法国瓦里安公司）进行萃取。分段头皮毛发在1M氢氧化钠溶液中于80℃孵育15分钟后，用正己烷/乙酸乙酯（2/1，v/v）进行液 - 液萃取。血液和尿液中所有分析物的定量限（LOQ）均为0.1 ng/mL。在毛发中，MA、MDMA、MDEA和MBDB的LOQ <5 pg/mg，AP的LOQ为14.7 pg/mg，MDA的LOQ为15.7 pg/mg。血液和尿液中的校准曲线在0.1 - 50 ng/mL范围内呈线性；MA、MDMA、MDEA和MBDB在5 - 500 pg/mg范围内，AP和MDA在2０ - 500 pg/mg范围内呈线性。所有基质中所有分析物的日间精密度均<13%。血液和尿液中在1和50 ng/mL时的准确度<20%，毛发中在20和250 pg/mg时的准确度<10%。该方法应用于一起法医案件的检测，一名16岁女性在派对上不知情的情况下单次服用摇头丸。她出现多动、出汗和烦躁症状。在服药后几小时（T + 12小时）采集了第一份尿液样本，临床实验室通过免疫测定法检测该样本对苯丙胺呈阳性。为法医目的，在第8天（D + 8）采集血液和尿液样本，在第60天（D + 60）采集头皮毛发样本。血液中未检测到MDMA，但尿液和毛发检测呈阳性，尿液中MDMA含量为0.42 ng/mL，毛发中仅在对应犯罪期间的片段中检测到MDMA，含量为22 pg/mg，而未检测到MDA。该方法可检测单次摄入后长达8天尿液中的MDMA。
