Department of Analytical Chemistry, Nutrition and Bromatology, Faculty of Chemistry, University of Santiago de Compostela, Santiago de Compostela, Spain.
Anal Chim Acta. 2011 Oct 17;704(1-2):123-32. doi: 10.1016/j.aca.2011.08.013. Epub 2011 Aug 11.
A fast and highly sensitive electrospray ionization tandem mass spectrometry (ESI-MS/MS) method has been developed for the simultaneous determination of morphine, 6-methylacetylmorphine (6-MAM), codeine, cocaine and benzoylecgonine (BZE) in hair from drug abusers. Pulverized hair samples were subjected to an optimized matrix solid phase dispersion (MSPD) procedure with alumina, followed by diluted hydrochloric acid elution on column solid-phase extraction (SPE) clean-up/pre-concentration. Alternatively, samples were also subjected to an optimized ultrasound assisted enzymatic hydrolysis (USEH) with Pronase E, followed by an off-line SPE clean up/pre-concentration procedure. Positive electrospray ionization and multiple reaction monitoring (MRM) with one precursor ion/product ion transition were used for the identification and quantification (deuterated analogues of each target as internal standards) of each analyte. The chromatographic pump and the autosampler were used for injecting the standards and the hair extracts (20 μL) as a flow injection analysis mode. The highest sensitivity was achieved when delivering the targets with an acetonitrile/water/formic acid (80/19.875/0.125) mixture. The limits of detection of the method were 39.2, 4.4, 6.8, 7.0 and 7.4 ng g(-1) for morphine, 6-MAM, codeine, cocaine and BZE, respectively. Relative standard deviations of intra- and inter-day precision were lower than 9 and 12%, respectively; whereas, analytical recoveries ranged from 96±5 to 106±4%. The developed method (MSPD-ESI-MS/MS) was applied to different hair samples from polydrug abusers, and results were statistically compared to those obtained after a conventional gas chromatography-mass spectrometry (GC-MS) analysis and also after USEH and ESI-MS/MS or GC-MS determinations.
一种快速灵敏的电喷雾串联质谱（ESI-MS/MS）法已被开发用于同时测定吸毒者头发中的吗啡、6-单乙酰吗啡（6-MAM）、可待因、可卡因和苯甲酰爱康宁（BZE）。将研磨后的头发样品用氧化铝进行优化的基质固相分散（MSPD）处理，然后用盐酸稀释洗脱，再通过柱固相萃取（SPE）进行净化/预浓缩。或者，也可以用蛋白酶 E 进行优化的超声辅助酶解（USEH），然后进行离线 SPE 净化/预浓缩处理。采用正电喷雾和多重反应监测（MRM），每个分析物使用一个前体离子/产物离子转换，进行鉴定和定量（每个目标物的氘代类似物作为内标）。用色谱泵和自动进样器以等度洗脱模式进样标准品和头发提取物（20 μL）。当用乙腈/水/甲酸（80/19.875/0.125）混合物输送目标物时，灵敏度最高。该方法的检出限（LOD）分别为吗啡、6-MAM、可待因、可卡因和 BZE 的 39.2、4.4、6.8、7.0 和 7.4 ng g(-1)。日内和日间精密度的相对标准偏差（RSD）分别低于 9%和 12%；而分析回收率范围为 96±5%至 106±4%。所开发的方法（MSPD-ESI-MS/MS）已应用于多种多药滥用者的头发样本，其结果与常规气相色谱-质谱（GC-MS）分析以及 USEH 和 ESI-MS/MS 或 GC-MS 测定的结果进行了统计学比较。
