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-对映体被兴奋剂滥用者服用。L-对映体很少被滥用，但在毒理学分析中有可能被检测到。左旋甲基苯丙胺和左旋苯丙胺也是治疗药物司来吉兰的主要代谢产物。滥用药物与治疗药物的鉴别是法医毒物分析中的重要环节。本文建立了两种苯丙胺类药物手性的气相色谱-质谱联用分析方法。这些试验方法制备成功，但色谱性能耗时。因此，我们尝试缩短这些方法的色谱周期。方法I：将样品溶液的pH值调节至12.6，然后上样至硅藻土柱并用三氟乙酰脯氨酰化进行萃取。采用DB-5窄孔柱在高压下通过GC/MS分析衍生的安非他明，进行首次色谱性能。方法二：将样品溶液置于含有氯化钠堆的顶空小瓶中，碱化（不强）并加入七氟丁酰氯。将小瓶置于用于固相微萃取（SPME）的自动进样器上，用于在手性柱Rt-betaDEXsm（0.25 mm i.d. x 30 m，膜厚0.25 μm）。在这种情况下，安非他明被检测为七氟丁酰衍生物。在方法I中，观察到具有非常短的周期的可区分的对映异构体峰。在方法II中，观察到的峰比常规条件更快。作为常规的手性分析，方法Ⅰ上级方法Ⅱ.同时，方法II可用于使用腐烂或分解的尸体材料进行法医毒理学分析。

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.