Thermo Fisher Scientific, San Jose, California 95134, United States.
Anal Chem. 2015 Aug 18;87(16):8234-41. doi: 10.1021/acs.analchem.5b01140. Epub 2015 Aug 5.
Ion sampling from an electrospray ionization (ESI) source was improved by increasing gas conductance of the MS inlet by 4.3-fold. Converting the gas throughput (Q) into sensitivity improvement was dependent on ion desolvation and handling of the gas load. Desolvation was addressed by using a novel slot shaped inlet that exhibited desolvation properties identical to the 0.58 mm i.d capillary. An assay tailored for "small molecules" at high chromatographic flow rate (500 μL/min) yielded a compound dependent 6.5 to 14-fold signal gain while analysis at nano chromatographic flow rate (300 nL/min) showed 2 to 3.5-fold improvement for doubly charged peptides. Improvement exceeding the Q (4.3-fold) at high chromatographic flow rate was explained by superior sampling of the spatially dispersed ion spray when using the slot shaped capillary. Sensitivity improvement across a wide range of chromatographic flow rate confirmed no compromise in ion desolvation with the increase in Q. Another improvement included less overflow of gas into the mass analyzer from the foreline region owing to the slot shape of the capillary. By doubling the roughing pump capacity and operating the electrodynamic ion funnel (EDIF) at ∼4 Torr, a single pumping stage was sufficient to handle the gas load. The transport of solvent clusters from the LC effluent into the mass analyzer was prevented by a "wavy shaped" transfer quadrupole and was compared with a benchmark approach that delivered ions orthogonally into a differentially pumped dual EDIF at comparable gas Q.
通过将 MS 入口的气体传导率提高 4.3 倍,改善了电喷雾电离 (ESI) 源的离子采样。将气体流量 (Q) 转换为灵敏度提高取决于离子去溶剂化和气体负载的处理。通过使用新型狭缝形入口解决了去溶剂化问题,该入口表现出与 0.58mm ID 毛细管相同的去溶剂化特性。针对高色谱流速(500μL/min)的“小分子”量身定制的分析方法,在化合物依赖性方面产生了 6.5 至 14 倍的信号增益,而在纳色谱流速(300nL/min)下分析时,双电荷肽的信号增益提高了 2 至 3.5 倍。在高色谱流速下,改善程度超过 Q(4.3 倍),这是由于使用狭缝形毛细管时,空间分散的离子喷雾的采样效果更好。在较宽的色谱流速范围内的灵敏度提高证实了在 Q 增加的情况下,离子去溶剂化没有妥协。另一个改进包括由于毛细管的狭缝形状,从前级区域进入质量分析器的气体溢出减少。通过将粗抽泵的容量增加一倍,并将电动离子阱 (EDIF) 操作在约 4 Torr,单个泵送阶段就足以处理气体负载。通过“波浪形”传输四极杆防止溶剂团从 LC 流出物进入质量分析器,将其与基准方法进行了比较,该基准方法以可比的气体 Q 将离子正交地输送到差分泵送的双 EDIF 中。