
基于非目标筛查技术的甲基苯丙胺合成路线分析
郑晓雨, 赵彦彪, 闻武, 郑珲
基于非目标筛查技术的甲基苯丙胺合成路线分析
Non-Targeted Profiling of Methamphetamine in China
本文基于气相色谱-质谱联用和多变量分析,建立对样品中痕量杂质成分的非目标筛查技术,实现制毒合成工艺路线推断。优化甲基苯丙胺中杂质成分的气相色谱-质谱联用分析条件,通过主成分分析(PCA)、正交偏最小二乘法判别分析(OPLS-DA)和层次聚类法(HCA)等多变量分析方法对已知合成工艺路线的甲基苯丙胺进行分类处理,进而对未知缴获样品进行关联性分析及合成工艺路线推断。结果显示,本方法可在缺少杂质成分标准物质的情况下,实现对缴获甲基苯丙胺关联性分析和合成工艺路线推断。所建立的非目标筛查技术具有操作简单、可靠性高、无需杂质的标准物质等优势,可为打击涉甲基苯丙胺犯罪提供情报支撑。
Based on gas chromatography mass spectrometry and multivariate analysis, non-targeted profiling of methamphetamine in China was established to deduce the synthetic routes. After optimizing analysis condition with gas chromatography mass spectrometry, following appropriate examination of all the peaks, 32 impurities were selected as the specific components in seized methamphetamine samples. Unsupervised (principal component analysis, PCA; hierarchical cluster analysis, HCA) and supervised (orthogonal projections to latent structures-DA, OPLS-DA) techniques were employed for classifying the 190 MA seizures. The results of PCA, HCA and OPLS-DA were in good agreement and showed a good tool for analyzing seizures correlation and synthesis routes. The established non-targeted screening technology has the advantage of simple operation, high reliability, not needing standard materials of impurities and can provide informative support to crack down the methamphetamine-related crime.
毒品 / 气相色谱-质谱联用 / 非目标筛查 / 甲基苯丙胺 / 合成路线 {{custom_keyword}} /
illicit drug / gas chromatography mass spectrometry (GC-MS) / non-targeted screening / methamphetamine / synthesis routes {{custom_keyword}} /
表1 特征离子丰度比的最大允许相对偏差范围Table 1 Acceptable maximum RSD (relative standard deviation) of ratios of characteristic ions abundance |
特征离子 丰度比 | >50% | >20%~50% | >10%~20% | ≤10% |
---|---|---|---|---|
最大允差 | ±10% | ±15% | ±20% | ±50% |
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Impurity profiling and classification of seized methamphetamine may play an important role in the interpretation of analytical results, the determination of the synthetic method employed, and the criminal investigations of drug traffic routes. Our study is focused on classifying seized methamphetamine samples according to the groups sorted by the types and quantities of impurities present in illicit methamphetamine samples. The samples (100mg) were dissolved in 2 mL of potassium phosphate buffer (pH 7.0), extracted with 200 microL of ethyl acetate under basic condition, and then analyzed by gas chromatography-mass spectrometry (GC-MS) with a DB-1 capillary column (30 m x 0.25 mm i.d., 0.25 microm). Five impurities are used as criteria for the classification of seized methamphetamine samples by Emde and Nagai method. A total of fifty-two samples of seized methamphetamine were analyzed by GC-MS and classified by five organic impurities, and then sorted into four groups, which are Nagai type, Emde Type, Undetermined I type, and Undetermined II type.
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In this study, stable isotope ratio analysis was used to track the precursor information of methamphetamine. The δ C and δ N values of 30 nature ephedra plants, 12 synthetic ephedrine/pseudoephedrine (ephedrine), 14 natural ephedrine, and 987 seized methamphetamine samples were measured and compared. Due to different weather and earth conditions, the δ C and δ N values of ephedra plants grown in the east and the west of Inner Mongolia showed great difference. The δ N values of ephedra plants were consistent with related ephedrine extracted from them. Moreover, the criteria to infer the synthetic origin of ephedrine were set up after the analysis of natural and synthetic ephedrine samples. Finally, the precursor origins of 949 seized methamphetamine samples synthesized by Emde and Nagai method were tentatively inferred. Influenced by different preprecursors, the δ C values of seized methamphetamine samples that synthesized from P2P also showed great difference, and this result is consistent with the reported data.© 2017 American Academy of Forensic Sciences.
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Impurity profiling of seized methamphetamine can provide very useful information in criminal investigations and, specifically, on drug trafficking routes, sources of supply, and relationships between seizures. Particularly important is the identification of "route specific" impurities or those which indicate the synthetic method used for manufacture in illicit laboratories. Previous researchers have suggested impurities which are characteristic of the Leuckart and reductive amination (Al/Hg) methods of preparation. However, to date and importantly, these two synthetic methods have not been compared in a single study utilizing methamphetamine hydrochloride synthesized in-house and, therefore, of known synthetic origin. Using the same starting material, 1-phenyl-2-propanone (P2P), 40 batches of methamphetamine hydrochloride were synthesized by the Leuckart and reductive amination methods (20 batches per method). Both basic and acidic impurities were extracted separately and analyzed by GC/MS. From this controlled study, two route specific impurities for the Leuckart method and one route specific impurity for the reductive amination method are reported. The intra- and inter-batch variation of these route specific impurities was assessed. Also, the variation of the "target impurities" recently recommended for methamphetamine profiling is discussed in relation to their variation within and between production batches synthesized using the Leuckart and reductive amination routes.
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GRANATO, DANIELSANTOS,
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Methamphetamine hydrochloride is one of the most widely used illicit drugs in the Philippines. In this study, we describe the application of cluster analysis of trace impurities in the profiling of the seized methamphetamine drug samples. Thirty milligrams of a homogenized drug sample were dissolved in 1 mL of pH 10.5 buffer solution and extracted with ethyl acetate containing three internal standards. The trace impurities were identified using gas chromatography-mass spectrometry (GC-MS) and quantified by gas chromatography with a flame ionization detector (GC-FID). Following previously reported methodologies, 30 impurity peaks were selected from the GC-FID chromatograms. The peak areas and retention times were referenced to the internal standards. The peak areas of the selected peaks were then grouped for cluster analysis. In order to check for consistency of clustering, two further cluster analyses were performed using 40 and 50 impurity peaks. Changes in clustering were observed in going from 30 to 40 impurity peaks, while analyses using 40 and 50 impurity peaks gave similar results. Thus, for the seized drug samples used in this study, cluster analysis using at least 40 impurity peaks showed better consistency of clustering as compared to analysis using 30 peaks only. Ten of the impurity peaks were identified, of which four were identified for the first time in methamphetamine drug samples. These are p-bromotoluene, N-benzyl amphetamine, N-ethyl amphetamine, and N-ethyl methamphetamine. The presence of phenyl-2-propanone (P2P), N,N-dimethyl amphetamine, and N-formyl amphetamine is indicative that these casework samples were synthesized using the Leuckart method.
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