高效液相色谱–串联质谱法(HPLC-MS/MS)检测人体指甲中甲基苯丙胺含量

Determination of Methamphetamine in Nail by High Performance Liquid Chromatography-tandem Mass Spectrometry

滥用毒品已成为世界性的严重社会问题。安非他明类兴奋剂甲基苯丙胺直接作用于人体中枢神经系统,具有高度成瘾性。这类药物可在毛发和指甲样本中残留数月,能够用于准确判断嫌疑人员的吸毒史。本文旨在建立人体指甲中甲基苯丙胺的液相色谱–串联质谱检测方法。将指甲样品经水、甲醇依次清洗后,用1 mol/L NaOH溶液碱水解、乙酸乙酯萃取后,取有机层溶剂经氮气吹干,待测物用甲醇水溶液复溶,应用HSS T3色谱柱分离,采用电喷雾离子源(ESI)、正离子模式扫描,多反应监测模式(MRM)检测,空白基质配制标准曲线,以内标法定量。结果显示,甲基苯丙胺在0.1~5 ng/mg范围内线性关系良好,相关系数为0.9901,定量限为0.1 ng/mg;0.1、0.5、2.0 ng/mg三个水平添加下,提取回收率为98.5%~102.2%,精密度为4.35%~6.85%。运用该方法在两位吸毒嫌疑人员的指甲样品中成功检测出了甲基苯丙胺。该方法检测灵敏、结果准确,可用于司法鉴定中指甲样品中甲基苯丙胺的分析检验。

The abuse of drugs has become a serious social problem worldwide.Amphetamine-type stimulants such as methamphetamine are powerful,highly addictive stimulant that affects the central nervous system.Hair and nail samples often can be used to accurately judge the history of drug abuse because ingested drugs can stably remain in these specimens over several months.To demonstrate that nails may well represent an appropriate non-conventional biological matrix to provide additional information in forensic toxicology,we developed a method for determining methamphetamine in the nail by high performance liquid chromatography mass spectrometry(HPLC-MS/MS).The sampling nails were washed with water and methanol twice,hydrolyzed with 1 mol/L sodium hydroxide solution,extracted with ethyl acetate,and then dried with nitrogen.The analytes were dissolved in methanol and separated on a HSS T3 column by Thermo Fisher TSQ tandem mass spectrometry(MS/MS).Electrospray ionization(ESI+)and multiple reaction monitoring(MRM)modes were used for the detection.In the mobile phase system of 0.1%formic acid aqueous solution and methanol containing 20 mmol/L ammonium acetate,methamphetamine peak shape was poor and bifurcated.Linear gradient elution with methanol and 0.1%formic acid water was chosen,resulting in a complete separation of methamphetamine and co-extract interfering substances within 5 min.Methamphetamine was qualitatively analyzed with their respective retention time and two characteristic ion pairs(m/z 150.1/90.1 and m/z 150.1/119.1),with the internal standard curve constructed with the blank matrix.The calibration curves were linear within the range of 0.1–5.0 ng/mg for methamphetamine,with a correlation coeffi cient of 0.9901 and a detection limit of 0.1 ng/mg.Spiked at 0.1,0.5,and 2.0 ng/mg levels,recoveries ranging from 98.5%to 102.2%were obtained,with the intra-day RSD of 4.35%–6.85%.The established method was successfully used to analyze the nail samples of 4 local suspected drug users,in which methamphetamine was detected in 2 cases ranging from 1.25 ng/mg to 5.56 ng/mg.The results were consistent with the data on methamphetamine in the suspect hair samples.The method is sensitive and accurate and fully meets the requirement of judicial identification for analyzing methamphetamine in nail samples.The detection of methamphetamine in nails provides alternative information to that in the hair on their past abuse.This study has further confi rmed that fi ngernails can be used for detecting methamphetamine exposure.