Differentiation of ring-substituted bromoamphetamine analogs by gas chromatography-tandem mass spectrometry.
Differentiation of ring-substituted bromoamphetamine analogs by gas chromatography-tandem mass spectrometry.
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DOI：
10.1007/s11419-015-0296-3
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发表时间：
2016
影响因子：
2.2
通讯作者：
Kasuya F
中科院分区：
文献类型：
--
作者：
Inoue H;Negishi S;Nakazono Y;Iwata YT;Tsujikawa K;Ohtsuru O;Miyamoto K;Yamashita T;Kasuya F
在过去十年中，新的非管制精神活性物质的出现迅速增加。经常对这些化合物的化学结构进行微小的改变，例如延长烷基残基或替换单一取代基，以避免监管控制，从而导致许多新的潜在危险药物的生产。溴苯丙胺类似物(溴苯丙胺[BR-AP]和溴甲基苯丙胺(BR-MA))是环取代的苯丙胺，可起兴奋剂的作用，对单胺氧化酶表现出与苯丙胺相同的抑制活性。采用气相色谱-串联质谱法(GC-MS-MS)对环取代的溴苯丙胺类似物进行了鉴别。用DB-1MS和DB-5MS色谱柱成功地分离了6种分析物的游离碱、三氟乙酰基和三甲基硅基(TMS)衍生物。TMS衍生物的电子电离MS-MS分析允许区分三个区域异构体。2位异构体的TMS衍生物提供了重要的产物离子。3位和4位异构体的谱型不同。[M+H-Hbr]+离子在m/z 134和148的游离碱的化学电离MS-MS分析允许区分区域异构体。2BrAP和2BrMA的2位异构体光谱分别含有m/z 132和m/z 146的脱氢产物离子。三位异构体的光谱以α裂解的金属阳离子为基峰。四位异构体的光谱显示m/z为91的基峰为基峰。这些结果表明，GC-MS-MS可以用于法医实践中区域异构体BR-AP类似物的鉴别。
There has been a rapid increase over the last decade in the appearance of new non-controlled psychoactive substances. Minor changes in the chemical structures of these compounds, such as the extension of an alkyl residue or replacement of a single substituent, are regularly made to avoid regulatory control, leading to the manufacture of many new potentially dangerous drugs. Bromoamphetamine analogs (bromoamphetamine [Br-AP] and bromomethamphetamine (Br-MA]) are ring-substituted amphetamines that can behave as stimulants, as well as exhibiting inhibitory activity towards monoamine oxidases in the same way as amphetamines. Gas chromatography–tandem mass spectrometry (GC–MS–MS) was used in this study to differentiate ring-substituted bromoamphetamine analogs. Free bases, trifluoroacetyl derivatives, and trimethylsilyl (TMS) derivatives of six analytes were successfully separated using DB-1ms and DB-5ms columns. Electron ionization MS–MS analysis of the TMS derivatives allowed for the differentiation of three regioisomers. TMS derivatives of 2-positional isomers provided significant product ions. The spectral patterns of 3- and 4-positional isomers were different. Chemical ionization MS–MS analysis of free bases for [M+H–HBr]+ ions at m/z 134 and 148 allowed for differentiation of the regioisomers. The spectra of 2-positional isomers contained characteristic product ions formed by dehydrogenation at m/z 132 and m/z 146 for 2Br-AP and 2Br-MA, respectively. The spectra of 3-positional isomers contained α-cleaved iminium cations as the base peaks. The spectra of 4-positional isomers showed a tropylium cation at m/z 91 as the base peak. These results demonstrate that GC–MS–MS can be used for the differentiation of regioisomeric Br-AP analogs in forensic practice.