Quantitative Measurements of Small Molecule Mixtures Using Laser Electrospray Mass Spectrometry
Quantitative Measurements of Small Molecule Mixtures Using Laser Electrospray Mass Spectrometry
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DOI：
10.1021/ac303443q
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发表时间：
2013-04-02
影响因子：
7.4
通讯作者：
Levis, Robert J.
中科院分区：
文献类型：
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作者：
Flanigan, Paul M.;Perez, Johnny J.;Levis, Robert J.
使用激光电喷雾质谱 (LEMS) 对阿替洛尔、噻康唑、四乙基溴化铵和四丁基碘化铵进行定量测量，揭示了单一分析物、二组分和四组分等摩尔混合物以及二组分可变摩尔浓度混合物的单调信号响应作为浓度的函数。单一分析物的 LEMS 分析作为浓度的函数，所有四种分析物的线性关系均超过 2.5 个数量级，并且没有显示饱和的迹象。相应的电喷雾电离 (ESI) 测量结果显示，随着饱和度在较高浓度下发生，会出现非单调增加。与 LEMS 实验相反，由于表面活性较低的分析物的离子抑制，使用传统 ESI-MS 的对照实验的强度比偏离等摩尔混合物测量的预期值，特别是在四组分混合物的分析中。在双组分非等摩尔混合物的分析中，两种技术都能够在用响应因子调整后确定浓度比，尽管传统 ESI-MS 在较高分析物浓度下会受到更大程度的饱和和离子抑制。
Quantitative measurements of atenolol, tioconazole, tetraethylammonium bromide, and tetrabutylammonium iodide using laser electrospray mass spectrometry (LEMS) reveal monotonic signal response as a function of concentration for single analytes, two- and four-component equimolar mixtures, and two-component variable molarity mixtures. LEMS analyses of single analytes as a function of concentration were linear over similar to 2.5 orders of magnitude for all four analytes and displayed no sign of saturation. Corresponding electrospray ionization (ESI) measurements displayed a nonmonotonic increase as saturation occurred at higher concentrations. In contrast to the LEMS experiments, the intensity ratios from control experiments using conventional ESI-MS deviated from expected values for the equimolar mixture measurements due to ion suppression of less surface active analytes, particularly in the analysis of the four-component mixture. In the analyses of two-component nonequimolar mixtures, both techniques were able to determine the concentration ratios after adjustment with response factors although conventional ESI-MS was subject to a greater degree of saturation and ion suppression at higher analyte concentrations.