Institute of Legal Medicine, University Hospital Schleswig-Holstein, Campus Kiel, Arnold-Heller-Str. 12, 24105 Kiel, Germany.
Forensic Sci Int. 2012 Feb 10;215(1-3):171-4. doi: 10.1016/j.forsciint.2011.03.001. Epub 2011 Mar 31.
The aim of the present investigations was to find markers for differentiating between the consumption of illegal cannabis products and legal medication containing fully synthetic Δ9-tetrahydrocannabinol (Δ9-THC), e.g., Marinol capsules. Δ9-Tetrahydrocannabinolic acid A (Δ9-THCA-A) and Δ9-tetrahydrocannabivarinic acid A (Δ9-THCVA-A) were taken into consideration for analysis, because these substances are the precursors of Δ9-THC and Δ9-tetrahydrocannabivarin (Δ9-THCV) in plant material of Cannabis sativa and are not contained in medical THC formulations. Whereas Δ9-THCA-A is an already well investigated substance, there is little analytical data on Δ9-THCVA-A. The reason for the presented investigations was a case in which a man was tested positive for Δ9-THC during a routine traffic control claiming that the positive serum sample resulted from the intake of a THC medication (Marinol) and not from consuming illegal cannabis products. Sample preparation consisted of a protein precipitation with acetonitrile. Analysis was carried out on a Thermo Fisher LCQ Deca ion trap LC-MS-MS-system using electron spray ionization (ESI) in negative mode. MS(2)- and MS(3)-full scan spectra were recorded for Δ9-THCA-A and Δ9-THCVA-A starting from M-H. Reference spectra were obtained by measuring a Δ9-THCA-A reference solution and an ethanolic cannabis extract for Δ9-THCVA-A as there is no reference material for this cannabinoid available on the market yet. Main transitions for Δ9-THCA-A were m/z 357→313 and 339 in the MS(2)-spectrum and m/z 313→245 and 191 in the MS(3)-spectrum. Fragmentation pattern of Δ9-THCVA-A was identical with a difference of 28 amu less for the precursor ion as well as the fragments due to a shorter alkyl side chain in the molecule (MS(2): m/z 329→285 and 311; MS(3): m/z 285→217 and 163). The two plant cannabinoids Δ9-THCA-A and Δ9-THCVA-A could be detected in the serum sample by LC-MS-MS which proved the intake of illegal cannabis products derived from plant material of C. sativa in the described case.
本研究的目的是寻找区分吸食非法大麻制品和含有全合成 Δ9-四氢大麻酚（Δ9-THC）的合法药物（如 Marinol 胶囊）的标志物。Δ9-四氢大麻酸 A（Δ9-THCA-A）和 Δ9-四氢大麻素酸 A（Δ9-THCVA-A）被考虑用于分析，因为这些物质是大麻植物材料中 Δ9-THC 和 Δ9-四氢大麻素（Δ9-THCV）的前体，而不包含在医用 THC 制剂中。虽然 Δ9-THCA-A 是一种已经得到充分研究的物质，但关于 Δ9-THCVA-A 的分析数据很少。进行本次研究的原因是，一名男子在例行交通管制中被检测出 Δ9-THC 呈阳性，他声称阳性血清样本是由于摄入了 THC 药物（Marinol）而不是吸食非法大麻制品所致。样品制备包括用乙腈进行蛋白质沉淀。分析在 Thermo Fisher LCQ Deca 离子阱 LC-MS-MS 系统上进行，采用电喷雾电离（ESI）在负离子模式下进行。对 Δ9-THCA-A 和 Δ9-THCVA-A 进行了 MS(2)-和 MS(3)-全扫描谱图记录，从 M-H开始。由于市场上尚未有这种大麻素的参考物质，因此通过测量 Δ9-THCA-A 参考溶液和乙醇大麻提取物获得了 Δ9-THCVA-A 的参考谱图。Δ9-THCA-A 的主要跃迁为 MS(2)-谱图中的 m/z 357→313 和 339，以及 MS(3)-谱图中的 m/z 313→245 和 191。Δ9-THCVA-A 的碎片模式与前体离子以及由于分子中较短的烷基侧链而减少 28 amu 的碎片相同（MS(2): m/z 329→285 和 311；MS(3): m/z 285→217 和 163）。通过 LC-MS-MS 在血清样本中检测到两种植物大麻素 Δ9-THCA-A 和 Δ9-THCVA-A，证明在描述的情况下摄入了源自 C. sativa 植物材料的非法大麻制品。
