Abstract
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.

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Acknowledgments
This work was funded in part by the National Science Foundation through grant DBI-1062846. Partial salary support was provided by the US Department of Energy through grant DE-FG02-09ER14980. The authors would like to thank the Edward G. Blair Mechanical Instrument Services and the Electronic Instrument Services Facilities at Indiana University for their assistance with instrument construction. This work was performed in collaboration with Pacific Northwest National Laboratory, operated for the US Department of Energy by Battelle Memorial Institute under contract DE-AC06-76RLO-1830op.
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Published in the topical collection Emerging Concepts and Strategies in Analytical Glow Discharges with guest editors Rosario Pereiro and Steven Ray.
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Dennis, E.A., Gundlach-Graham, A.W., Ray, S.J. et al. Zoom-TOFMS: addition of a constant-momentum-acceleration “zoom” mode to time-of-flight mass spectrometry. Anal Bioanal Chem 406, 7419–7430 (2014). https://doi.org/10.1007/s00216-014-7875-8
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DOI: https://doi.org/10.1007/s00216-014-7875-8