Dipartimento Farmaco-chimico, Facoltà di Farmacia, Università degli Studi di Messina, viale Annunziata, 98168 Messina, Italy.
J Chromatogr A. 2013 Feb 22;1278:153-9. doi: 10.1016/j.chroma.2012.12.066. Epub 2013 Jan 8.
The present manuscript is focused on the evaluation of a novel high-speed triple quadrupole mass spectrometer (QqQ MS), carried out under extreme GC conditions, namely those generated by a flow-modulated (FM) comprehensive two-dimensional GC (GC×GC) system. The novel QqQ MS system is capable of operation under high speed conditions, in both full-scan (maximum scan speed: 20,000 amu/s) and multiple reaction monitoring (MRM) modes. Moreover, the QqQ MS instrument can generate simultaneous full scan/MRM data, also in a very rapid manner. An FM GC × GC-MSMS method was developed for the simultaneous full-scan qualitative analysis of untargeted essential oil compounds, and MRM quali/quantitative analysis of targeted ones, namely three preservatives [o-phenylphenol (OPP), butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA)]. The QqQMS system generated a sufficient number of data points per peak, for both qualitative and quantitative purposes. The degree of sensitivity, reached through the MRM analysis, widely exceeded current-day regulations. Method validation, related to the MRM analysis, was performed considering retention time, peak area and ion ratio repeatability, limits of detection and quantification, and accuracy. Additionally, a spearmint essential oil was spiked with 5 phytosanitary compounds at the 1 ppb level, and analysed through an MRM-only GC × GC-MSMS application. Emphasis was devoted not only on sensitivity (satisfactory for all the contaminants), but also on the importance of precursor ion selection, and of the GC × GC separation process. Finally, sensitivity was compared between the MRM and SIM modes, in scan/MRM, MRM, scan/SIM and SIM analyses, performed on a mixture of 22 phytosanitary products, at a concentration level in the 50-150 ppb range.
本手稿专注于评估一种新型高速三重四极杆质谱仪（QqQ MS），该质谱仪在极端 GC 条件下进行，即由流动调制（FM）全二维 GC（GC×GC）系统产生的条件。新型 QqQ MS 系统能够在高速条件下运行，无论是全扫描（最大扫描速度：20,000 amu/s）还是多重反应监测（MRM）模式。此外，QqQ MS 仪器还可以以非常快的速度同时生成全扫描/MRM 数据。开发了一种 FM GC×GC-MSMS 方法，用于同时对非靶向性精油化合物进行全扫描定性分析，以及对靶向性化合物进行 MRM 定性/定量分析，即三种防腐剂[邻苯二酚（OPP）、丁基羟基甲苯（BHT）、丁基羟基茴香醚（BHA）]。QqQMS 系统为定性和定量目的生成了足够数量的每个峰的数据点。通过 MRM 分析达到的灵敏度程度远远超过了当前的法规要求。与 MRM 分析相关的方法验证考虑了保留时间、峰面积和离子比重复性、检测限和定量限以及准确性。此外，还使用一种薄荷油对 5 种植物保护剂进行了加标，并用仅 MRM 的 GC×GC-MSMS 应用程序进行了分析。不仅强调了灵敏度（对所有污染物均令人满意），还强调了前体离子选择以及 GC×GC 分离过程的重要性。最后，在浓度范围为 50-150 ppb 的 22 种植物保护产品混合物上，在扫描/MRM、MRM、扫描/SIM 和 SIM 分析中，比较了 MRM 和 SIM 模式之间的灵敏度。
