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Ion-Molecule Clustering in Differential Mobility Spectrometry: Lessons Learned from Tetraalkylammonium Cations and their Isomers

  • Research Article
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Journal of The American Society for Mass Spectrometry

Abstract

Differential mobility spectrometry (DMS) can distinguish ions based upon the differences in their high- and low-field ion mobilities as they experience the asymmetric waveform applied to the DMS cell. These mobilities are known to be influenced by the ions’ structure, m/z, and charge distribution (i.e., resonance structures) within the ions themselves, as well as by the gas-phase environment of the DMS cell. While these associations have been developed over time through empirical observations, the exact role of ion structures or their interactions with clustering molecules remains generally unknown. In this study, that relationship is explored by observing the DMS behaviors of a series of tetraalkylammonium ions as a function of their structures and the gas-phase environment of the DMS cell. To support the DMS experiments, the basin-hopping search strategy was employed to identify candidate cluster structures for density functional theory treatment. More than a million cluster structures distributed across 72 different ion-molecule cluster systems were sampled to determine global minimum structures and cluster binding energies. This joint computational and experimental approach suggests that cluster geometry, in particular ion-molecule intermolecular separation, plays a critical role in DMS.

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Acknowledgments

The authors gratefully acknowledge high performance computing support from the SHARCNET consortium of Compute Canada. The authors acknowledge financial support from the Natural Sciences and Engineering Research Council (NSERC) of Canada for financial support in the form of a Discovery grant and an ENGAGE grant (EGP #449354-13). The authors thank Mr. John Lape for help with computational aspects of this study. They also thank Professor Scott McLuckey (Purdue University) and Professor Terry McMahon (University of Waterloo), as well as Dr. Bradley Schneider and Dr. Yves Le Blanc (AB SCIEX) for helpful conversations and critical review of this manuscript.

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Authors and Affiliations

  1. AB SCIEX, Concord, ON, L4K 4V8, Canada

    J. Larry Campbell

  2. Department of Chemistry, University of Waterloo, Waterloo, ON, N2L 3G1, Canada

    Mabel Zhu & W. Scott Hopkins

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  1. J. Larry Campbell
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  2. Mabel Zhu
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Correspondence to J. Larry Campbell or W. Scott Hopkins.

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Campbell, J.L., Zhu, M. & Hopkins, W.S. Ion-Molecule Clustering in Differential Mobility Spectrometry: Lessons Learned from Tetraalkylammonium Cations and their Isomers. J. Am. Soc. Mass Spectrom. 25, 1583–1591 (2014). https://doi.org/10.1007/s13361-014-0939-3

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  • DOI: https://doi.org/10.1007/s13361-014-0939-3

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