Application of solid-phase microextraction/high-performance liquid chromatography mass spectrometry to forensic toxicology

在法医毒理学中，如果受害人的死亡被认为是由于或与毒品和毒药中毒有关，那么提取、鉴定和定量某种化学品是必不可少的。对这些领域的主要兴趣集中在方法上，即如何迅速、准确和敏感地检测化学品。本研究建立了固相微萃取(SPME)-高效液相色谱(HPLC)/质谱（MS）联用技术测定人体样品中兴奋剂、阿片类药物、吩噻嗪类药物、丁苯类药物、苯二氮卓类药物、有机磷农药、氨基甲酸酯类农药和天然毒物的方法。用聚二甲基硅氧烷（PDMS）测定兴奋剂或有机磷农药，用碳蜡/二乙烯基苯（DVB）测定阿片类药物，用聚丙烯酸酯测定吩噻嗪类或丁苯类，用PDMS/DVB测定苯二氮卓类、氨基甲酸酯类农药或amanitins测定人全血、血清和尿液样本。除有机磷农药检测采用常压化学电离法外，所有药物和毒物检测均采用电喷雾电离（ESI）为界面、电离方式的高效液相色谱/质谱法。在吩噻嗪类、丁苯类和苯二氮卓类药物的分析中，HPLC/串联质谱法（MS/MS）的灵敏度明显高于HPLC/MS。除加标后的人体体液外，该方法还应用于一起医学法律案件中含有甲基苯丙胺和安非他明的尿液样本，以及男性志愿者口服吩噻嗪后的全血和尿液样本，这些药物可以通过SPME从人体样本中分离出来，并通过HPLC/MS或HPLC/MS/MS进行敏感定量。该方法可用于治疗监测、临床毒理学和法医毒理学。

In forensic toxicology, the extraction, identification and quantification of a chemical (s) are essential in the case of victims whose case of death is considered due to or related to intoxication by drugs and poisons. The main interest in these fields is focused on methodologies, with regard to how rapidly, accurately and sensitively chemicals can be detected. In the present study, we established a procedure for the determination of stimulants, opioids, phenothiazines, butyrophenones, benzodiazepines, organophosphate pesticides, carbamate pesticides and naturally occurring poisons in human samples by solid-phase microextraction (SPME)-high performance liquid chromatography (HPLC)/mass spectrometry (MS).SPME was achieved with polydimethylsiloxane (PDMS) for stimulants or organophosphate pesticides, carbowax/divinylbenzene (DVB) for opioids, polyacrylate for phenothiazines or butyrophenones and PDMS/DVB for benzodiazepines, carbamate pesticides or amanitins from human whole blood, serum and urine samples. HPLC/MS with electrospray ionization (ESI) as interface and ionization mode was used for detection of all drugs and poisons, except for atmospheric pressure chemical ionization for detection of organophosphate pesticides. In the analysis of phenothiazines, butyrophenones and benzodiazepines, HPLC/tandem MS (MS/MS) showed much higher sensitivity than HPLC/MS.In addition to the spiked human body fluids, the method was applied to urine samples containing methamphetamine and amphetamine in a medico-legal case, and to samples of whole blood and urine after oral administration of phenothiazines by a male volunteer, these drugs could be isolated from human samples by SPME and sensitively quantified by HPLC/MS or HPLC/MS/MS.The present SPME-HPLC/MS method can be recommended for use in therapeutic monitoring, clinical toxicology and forensic toxicology.