Life Sciences Mass Spectrometry, Department of Inorganic and Analytical Chemistry, University of Geneva, 24 Quai Ernest Ansermet, CH-1211 Geneva 4, Switzerland.
Shimadzu Research Laboratory, Wharfside, Trafford Wharf Road, Manchester M17 1GP, UK.
J Chromatogr A. 2023 Aug 30;1705:464174. doi: 10.1016/j.chroma.2023.464174. Epub 2023 Jun 19.
The benefit of combining liquid chromatography (LC), supercritical fluid chromatography (SFC) and vacuum Differential Mobility Spectrometry - Mass Spectrometry (vDMS-MS) was investigated for the analysis of fourteen diastereomeric pyrrolizidine alkaloids (PA); intermedine, echinatine, lycopsamine, indicine, intermedine-N-oxide, echinatine-N-oxide, indicine-N-oxide, lycopsamine-N-oxide, senecivernine, senecionine, jacobine, senecivernine-N-oxide, senecionine-N-oxide, retrorsine. The mobile phase composition (15-100% MeOH and ACN), flow rate (8-100 µL/min), vDMS cell pressure, and F value showed an effect on the mobility behavior of the analytes. At 15% MeOH with a flow rate of 100 µL/min and 33 mbar vDMS pressure, 8 out 14 PA could be partially or totally separated by vDMS-MS. As well as providing an additional separation dimension vDMS improved the selectivity and a 5-minute assay method was developed for the quantification of 10 out of 14 single diastereomeric PA in tea samples, using a short LC column-switching and hyphenated to vDMS-MS in the selected ion monitoring mode. The performance of the method was found to be comparable with a 12-minute standard LC-MS/MS method using detection in the selected reaction monitoring mode. Additionally, the combination of vDMS and SFC-MS was investigated and suggests that the mixture of CO/MeOH influences the CV shifting of the PA to more negative compensation voltage, and the signal-to-noise ratio is improved by a factor of three compared to SFC-MS without vDMS.
研究了将液相色谱 (LC)、超临界流体色谱 (SFC) 和真空差分迁移率光谱法-质谱法 (vDMS-MS) 相结合用于分析 14 种差向立体吡咯里西啶生物碱 (PA) 的优势；intermedine、echinatine、lycopsamine、indicine、intermedine-N-oxide、echinatine-N-oxide、indicine-N-oxide、lycopsamine-N-oxide、senecivernine、senecionine、jacobine、senecivernine-N-oxide、senecionine-N-oxide、retrorsine。流动相组成（15-100%甲醇和乙腈）、流速（8-100µL/min）、vDMS 池压力和 F 值对分析物的迁移行为有影响。在 15%甲醇、流速为 100µL/min 和 33 mbar vDMS 压力下，8 种 14 种 PA 中的 4 种可以部分或完全通过 vDMS-MS 分离。vDMS 不仅提供了额外的分离维度，还提高了选择性，开发了一种 5 分钟的测定方法，用于定量测定茶样中 14 种单差向立体 PA 中的 10 种，使用短 LC 柱切换并与 vDMS-MS 在选择离子监测模式下连接。该方法的性能与使用选择反应监测模式检测的 12 分钟标准 LC-MS/MS 方法相当。此外，还研究了 vDMS 和 SFC-MS 的组合，并表明 CO/MeOH 的混合物会影响 PA 的 CV 向更负的补偿电压漂移，并且与没有 vDMS 的 SFC-MS 相比，信噪比提高了三倍。
