Campbell J Larry, Kafle Amol, Bowman Zack, Blanc J C Yves Le, Liu Chang, Hopkins W Scott
SCIEX Concord Ontario Canada.
Department of Chemistry University of Waterloo 200 University Avenue West Waterloo Ontario Canada.
Anal Sci Adv. 2020 Sep 12;1(4):233-244. doi: 10.1002/ansa.202000066. eCollection 2020 Dec.
The separation and analysis of chiral compounds, especially enantiomers, presents a great challenge to modern analytical chemistry, particularly to mass spectrometry (MS). As a result, integrated orthogonal separations, such as chiral liquid chromatography (chiral LC), gas chromatography (GC), or capillary electrophoresis (CE), are often employed to separate enantiomers prior to MS analysis. Here, we combine chemical derivatization with differential mobility spectrometry (DMS) and MS to separate and quantitate the transformed enantiomeric pairs R- and S-amphetamine, as well as R- and S-methamphetamine. We also demonstrate separation of these drugs by using reverse-phase LC. However, while the LC method requires ∼5 min to provide separation, we have developed a flow-injection analysis (FIA) method using DMS as the exclusive mode of separation (FIA-DMS), requiring only ∼1.5 min with equivalent quantitative metrics (1-1000 ng/mL range) to the LC method. The DMS-based separation of each diastereomeric pair is driven by differences in binding energies between the analyte ions and the chemical modifier molecules (acetonitrile) added to the DMS environment.
手性化合物，尤其是对映体的分离和分析，对现代分析化学，特别是对质谱分析（MS）提出了巨大挑战。因此，在进行质谱分析之前，常常采用手性液相色谱（chiral LC）、气相色谱（GC）或毛细管电泳（CE）等集成正交分离方法来分离对映体。在此，我们将化学衍生化与差分离子迁移谱（DMS）及质谱相结合，以分离和定量转化后的对映体对R-和S-苯丙胺以及R-和S-甲基苯丙胺。我们还展示了使用反相液相色谱法对这些药物的分离。然而，液相色谱法需要约5分钟才能实现分离，而我们开发了一种以DMS作为唯一分离模式的流动注射分析（FIA）方法（FIA-DMS），在等效定量指标（1 - 1000 ng/mL范围）下，仅需约1.5分钟，与液相色谱法相当。基于DMS的每个非对映体对的分离是由分析物离子与添加到DMS环境中的化学改性剂分子（乙腈）之间结合能的差异驱动的。
