Ojanperä Ilkka, Mesihää Samuel, Rasanen Ilpo, Pelander Anna, Ketola Raimo A
Department of Forensic Medicine, University of Helsinki, PO Box 40, 00014, Helsinki, Finland.
Forensic Toxicology Unit, National Institute for Health and Welfare, PO Box 30, 00271, Helsinki, Finland.
Anal Bioanal Chem. 2016 May;408(13):3395-400. doi: 10.1007/s00216-016-9461-8. Epub 2016 Mar 11.
A novel platform is introduced for simultaneous identification and quantification of new psychoactive substances (NPS) in blood matrix, without the necessity of using authentic reference standards. The instrumentation consisted of gas chromatography (GC) coupled to nitrogen chemiluminescence detection (NCD) and atmospheric pressure chemical ionization quadrupole time-of-flight mass spectrometry (APCI-QTOFMS). In this concept, the GC flow is divided in appropriate proportions between NCD for single-calibrant quantification, utilizing the detector's equimolar response to nitrogen, and QTOFMS for accurate mass-based identification. The principle was proven by analyzing five NPS, bupropion, desoxypipradrol (2-DPMP), mephedrone, methylone, and naphyrone, in sheep blood. The samples were spiked with the analytes post-extraction to avoid recovery considerations at this point. All the NPS studies produced a protonated molecule in APCI resulting in predictable fragmentation with high mass accuracy. The N-equimolarity of quantification by NCD was investigated by using external calibration with the secondary standard caffeine at five concentration levels between 0.17 and 1.7 mg/L in blood matrix as five replicates. The equimolarity was on average 98.7%, and the range of individual equimolarity determinations was 76.7-130.1%. The current analysis platform affords a promising approach to instant simultaneous qualitative and quantitative analysis of drugs in the absence of authentic reference standards, not only in forensic and clinical toxicology but also in other bioanalytical applications.
介绍了一种新型平台，用于同时鉴定和定量血液基质中的新型精神活性物质（NPS），无需使用真实的参考标准品。该仪器由气相色谱（GC）与氮化学发光检测（NCD）以及大气压化学电离四极杆飞行时间质谱（APCI-QTOFMS）联用组成。在此概念中，GC流在用于单校准物定量的NCD（利用检测器对氮的等摩尔响应）和用于基于精确质量的鉴定的QTOFMS之间按适当比例分配。通过分析绵羊血液中的五种NPS（安非他酮、去氧哌醋甲酯（2-DPMP）、甲麻黄碱、亚甲基二氧吡咯戊酮和萘黄酮）证明了该原理。在提取后将分析物添加到样品中，以避免此时的回收率问题。所有NPS研究在APCI中均产生了质子化分子，从而产生了具有高质量准确度的可预测碎片。通过在血液基质中使用二级标准咖啡因在0.17至1.7 mg/L的五个浓度水平进行外部校准，以五次重复的方式研究了NCD定量的N等摩尔性。等摩尔性平均为98.7%，个体等摩尔性测定范围为76.7-130.1%。当前的分析平台为在没有真实参考标准品的情况下即时同时进行药物的定性和定量分析提供了一种有前景的方法，不仅适用于法医和临床毒理学，也适用于其他生物分析应用。
