Dennis Elise A, Gundlach-Graham Alexander W, Ray Steven J, Enke Christie G, Barinaga Charles J, Koppenaal David W, Hieftje Gary M
Department of Chemistry, Indiana University, Bloomington, IN, 47405, USA.
Anal Bioanal Chem. 2014 Nov;406(29):7419-30. doi: 10.1007/s00216-014-7875-8. Epub 2014 May 28.
In this study, we demonstrate the performance of a new mass spectrometry concept called zoom time-of-flight mass spectrometry (zoom-TOFMS). In our zoom-TOFMS instrument, we combine two complementary types of TOFMS: conventional, constant-energy acceleration (CEA) TOFMS and constant-momentum acceleration (CMA) TOFMS to provide complete mass-spectral coverage as well as enhanced resolution and duty factor for a narrow, targeted mass region, respectively. Alternation between CEA- and CMA-TOFMS requires only that electrostatic instrument settings (i.e., reflectron and ion optics) and ion acceleration conditions be changed. The prototype zoom-TOFMS instrument has orthogonal-acceleration geometry, a total field-free distance of 43 cm, and a direct-current glow-discharge ionization source. Experimental results demonstrate that the CMA-TOFMS "zoom" mode offers resolution enhancement of 1.6 times over single-stage acceleration CEA-TOFMS. For the atomic mass range studied here, the maximum resolving power at full-width half-maximum observed for CEA-TOFMS was 1,610 and for CMA-TOFMS the maximum was 2,550. No difference in signal-to-noise (S/N) ratio was observed between the operating modes of zoom-TOFMS when both were operated at equivalent repetition rates. For a 10-kHz repetition rate, S/N values for CEA-TOFMS varied from 45 to 990 and from 67 to 10,000 for CMA-TOFMS. This resolution improvement is the result of a linear TOF-to-mass scale and the energy-focusing capability of CMA-TOFMS. Use of CMA also allows ions outside a given m/z range to be rejected by simple ion-energy barriers to provide a substantial improvement in duty factor.
在本研究中,我们展示了一种名为变焦飞行时间质谱(zoom-TOFMS)的新质谱概念的性能。在我们的变焦飞行时间质谱仪中,我们将两种互补类型的飞行时间质谱相结合:传统的恒能加速(CEA)飞行时间质谱和恒动量加速(CMA)飞行时间质谱,分别为窄的目标质量区域提供完整的质谱覆盖以及更高的分辨率和占空比。CEA-TOFMS和CMA-TOFMS之间的切换仅需改变静电仪器设置(即反射器和离子光学)以及离子加速条件。原型变焦飞行时间质谱仪具有正交加速几何结构、43厘米的总无场距离以及直流辉光放电电离源。实验结果表明,CMA-TOFMS的“变焦”模式比单级加速CEA-TOFMS的分辨率提高了1.6倍。对于此处研究的原子质量范围,CEA-TOFMS在半高宽处观察到的最大分辨能力为1610,而CMA-TOFMS的最大值为2550。当变焦飞行时间质谱的两种操作模式以等效重复率运行时,未观察到信噪比(S/N)的差异。对于10 kHz的重复率,CEA-TOFMS的S/N值在45至990之间变化,而CMA-TOFMS的S/N值在67至10000之间变化。这种分辨率的提高是线性飞行时间与质量比例以及CMA-TOFMS的能量聚焦能力的结果。使用CMA还允许通过简单的离子能量屏障排除给定m/z范围之外的离子,从而显著提高占空比。