Study for practical use of two chiral analyses of amphetamines by gas chromatography-mass spectrometry

安非他明分别具有对称异构体（对映体）。通常，d-对映体是兴奋剂滥用者服用的。l -对映体很少被滥用，但在毒理学分析中可以检测到这些化合物。l-甲基安非他明和l-安非他明，因为它们也是治疗药物selegiline的主要代谢物。在法医毒理学分析中，鉴别滥用药物与治疗药物具有重要意义。建立了两种苯丙胺类药物的气相色谱-质谱（GC/MS）手性分析方法。这些实验方法制备成功，但色谱性能较耗时。因此，我们试图缩短这些方法的色谱周期。方法一：将样品溶液ph调整为12.6，然后将样品溶液置于硅藻土柱上，用三氟乙酰化法提取。采用DB-5窄孔色谱柱，在高压条件下对衍生苯丙胺进行气相色谱/质谱分析。方法二：将样品溶液置于顶空小瓶中，其中含有一堆氯化钠，碱化（不强）并加入七氟丁酰氯。将样品置于自动进样器上进行固相微萃取（SPME），在Rt-betaDEXsm （0.25 mm id x 30 m，膜厚0.25 μm）手性柱上进行GC/MS分析。在这种情况下，安非他明被检测为七氟丁基衍生物。在方法1中，在很短的周期内观察到可区分的对映体峰。在方法二中，观察到的峰比常规条件下更快。作为常规手性分析，方法1优于方法2。同时，方法二对于使用腐烂或腐烂的尸体材料进行法医毒理学分析是有用的。

Amphetamines possess respectively symmetric isomers (enantiomers). Usually, d-enantiomers are taken by stimulant abusers. L-enantiomers are rarely abused, but the compounds are possible to be detected in toxicological analysis. L-methamphetamine and l-amphetamine, because, are also main metabolites of a therapeutic drug, selegiline. It is important to distinguish the abused drugs with the therapeutic drugs in forensic toxicological analysis. We have been developing two methods for chiral analysis of amphetamines by gas chromatography-mass spectrometry (GC/MS). Those trial methods were successfully prepared, but the chromatographic performances were time-consuming. Therefore, we attempted to shorten the chromatographic periods on those methods. Method I : A sample solution was pH-adjusted at 12.6 then applied to a diatomaceous earth column and extracted with trifluoroacetylprolylation. The derivatized amphetamines were analyzed by GC/MS with a DB-5 narrow-bore column at a high-pressure for first chromatographic performance. Method II : A sample solution was placed in a headspace vial containing a heap of sodium chloride, alkalized (not strong) and added heptaflurobutyryl chloride. The vial was set onto an auto-sampler for solid-phase microextraction (SPME) for GC/MS analyzing in a chiral column Rt-betaDEXsm (0.25 mm i.d. x 30 m, film thickness 0.25 μm). In this case, amphetamines were detected as heptafluorobutyryl derivatives. In method I, distinguishable enantiomer peaks with very short periods were observed. In method II, the observed peaks were faster than conventional conditions. As regular chiral analysis, method I is superior to method II. Meanwhile, method II is useful for forensic toxicological analysis using putrefied or decomposed body materials.