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Using Metal Complex Ion-Molecule Reactions in a Miniature Rectilinear Ion Trap Mass Spectrometer to Detect Chemical Warfare Agents

  • Research Article
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Journal of The American Society for Mass Spectrometry

Abstract

The gas-phase reactions of a series of coordinatively unsaturated [Ni(L)n]y+ complexes, where L is a nitrogen-containing ligand, with chemical warfare agent (CWA) simulants in a miniature rectilinear ion trap mass spectrometer were investigated as part of a new approach to detect CWAs. Results show that upon entering the vacuum system via a poly(dimethylsiloxane) (PDMS) membrane introduction, low concentrations of several CWA simulants, including dipropyl sulfide (simulant for mustard gas), acetonitrile (simulant for the nerve agent tabun), and diethyl phosphite (simulant for nerve agents sarin, soman, tabun, and VX), can react with metal complex ions generated by electrospray ionization (ESI), thereby providing a sensitive means of detecting these compounds. The [Ni(L)n]2+ complexes are found to be particularly reactive with the simulants of mustard gas and tabun, allowing their detection at low parts-per-billion (ppb) levels. These detection limits are well below reported exposure limits for these CWAs, which indicates the applicability of this new approach, and are about two orders of magnitude lower than electron ionization detection limits on the same mass spectrometer. The use of coordinatively unsaturated metal complexes as reagent ions offers the possibility of further tuning the ion-molecule chemistry so that desired compounds can be detected selectively or at even lower concentrations.

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Acknowledgments

The authors thank the Office of Naval Research through the DURIP program (grant N000-14-07-1-0980) for support of this work. They also thank Professor Graham Cooks, Dr. Robert Noll, Dr. Ewa Sokol, Dr. Nathan Sanders, and Dr. Guangming Huang from Purdue University for technical assistance with the Mini 10.

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  1. Department of Chemistry, University of Massachusetts, Amherst, MA, USA

    Adam M. Graichen & Richard W. Vachet

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  1. Adam M. Graichen
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Correspondence to Richard W. Vachet.

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Graichen, A.M., Vachet, R.W. Using Metal Complex Ion-Molecule Reactions in a Miniature Rectilinear Ion Trap Mass Spectrometer to Detect Chemical Warfare Agents. J. Am. Soc. Mass Spectrom. 24, 917–925 (2013). https://doi.org/10.1007/s13361-013-0592-2

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