Duvivier Wilco F, van Beek Teris A, Pennings Ed J M, Nielen Michel W F
Laboratory of Organic Chemistry, Wageningen University, Dreijenplein 8, 6703 HB, Wageningen, The Netherlands.
Rapid Commun Mass Spectrom. 2014 Apr 15;28(7):682-90. doi: 10.1002/rcm.6831.
Forensic hair analysis methods are laborious, time-consuming and provide only a rough retrospective estimate of the time of drug intake. Recently, hair imaging methods using matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) were reported, but these methods require the application of MALDI matrix and are performed under vacuum. Direct analysis of entire locks of hair without any sample pretreatment and with improved spatial resolution would thus address a need.
Hair samples were attached to stainless steel mesh screens and scanned in the X-direction using direct analysis in real time (DART) ambient ionization orbitrap MS. The DART gas temperature and the accuracy of the probed hair zone were optimized using Δ-9-tetrahydrocannabinol (THC) as a model compound. Since external contamination is a major issue in forensic hair analysis, sub-samples were measured before and after dichloromethane decontamination.
The relative intensity of the THC signal in spiked blank hair versus that of quinine as the internal standard showed good reproducibility (26% RSD) and linearity of the method (R(2) = 0.991). With the DART hair scan THC could be detected in hair samples from different chronic cannabis users. The presence of THC was confirmed by quantitative liquid chromatography/tandem mass spectrometry. Zones with different THC content could be clearly distinguished, indicating that the method might be used for retrospective timeline assessments. Detection of THC in decontaminated drug user hair showed that the DART hair scan not only probes THC on the surface of hair, but penetrates deeply enough to measure incorporated THC.
A new approach in forensic hair analysis has been developed by probing complete locks of hair using DART-MS. Longitudinal scanning enables detection of incorporated compounds and can be used as pre-screening for THC without sample preparation. The method could also be adjusted for the analysis of other drugs of abuse.
法医毛发分析方法繁琐、耗时,且只能对药物摄入时间进行粗略的回顾性估计。最近,有报道称使用基质辅助激光解吸/电离质谱(MALDI-MS)的毛发成像方法,但这些方法需要应用MALDI基质且在真空条件下进行。因此,无需任何样品预处理且具有更高空间分辨率的直接分析整束毛发的方法将满足这一需求。
将毛发样品附着在不锈钢筛网上,并使用实时直接分析(DART)常压电离轨道阱质谱在X方向上进行扫描。以Δ-9-四氢大麻酚(THC)作为模型化合物,对DART气体温度和探测毛发区域的精度进行了优化。由于外部污染是法医毛发分析中的一个主要问题,因此在二氯甲烷去污前后对亚样品进行了测量。
加标空白毛发中THC信号与作为内标的奎宁信号的相对强度显示出良好的重现性(相对标准偏差为26%)和方法线性(R(2) = 0.991)。通过DART毛发扫描,可以在不同慢性大麻使用者的毛发样品中检测到THC。通过定量液相色谱/串联质谱法确认了THC的存在。可以清楚地区分具有不同THC含量的区域,这表明该方法可能用于回顾性时间线评估。对去污后的吸毒者毛发中THC的检测表明,DART毛发扫描不仅能探测毛发表面的THC,还能深入到足以测量掺入的THC。
通过使用DART-MS探测完整的毛发束,开发了一种法医毛发分析的新方法。纵向扫描能够检测掺入的化合物,并且可以在无需样品制备的情况下用作THC的预筛选。该方法也可调整用于分析其他滥用药物。