Two-dimensional MS/MS scans on a linear ion trap mass analyzer: Identification of V-series chemical warfare agents

Snyder, Dalton T.; Demond, Paul S.; Szalwinski, Lucas J.; Dhummakupt, Elizabeth S.; McBride, Ethan M.; Cooks, R. Graham; Glaros, Trevor; Mach, Phillip M.

doi:10.1016/j.ijms.2019.06.007

Cited by 18 publications

(15 citation statements)

References 32 publications

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“…Automated peak-assignment algorithms are being developed for routine analysis [26]. A pulse sequence for 2D MS in a linear ion trap has been proposed, which expands the potential of 2D MS to mass analyzers beyond FT-ICR MS [27][28][29]. Nevertheless, the question of how to improve the signal-to-noise ratio and the resolving power of 2D mass spectra remains.…”

Section: Introductionmentioning

confidence: 99%

Phase relationships in two-dimensional mass spectrometry

Agthoven

Kilgour

Lynch

et al. 2019

J. Am. Soc. Mass Spectrom.

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Two-dimensional mass spectrometry (2D MS) is a data-independent tandem mass spectrometry technique in which precursor and fragment ion species can be correlated without the need for prior ion isolation. The behavior of phase in 2D Fourier transform mass spectrometry is investigated with respect to the calculation of phase-corrected absorption-mode 2D mass spectra. 2D MS datasets have a phase that is defined differently in each dimension. In both dimensions, the phase behavior of precursor and fragment ions is found to be different. The dependence of the phase for both precursor and fragment ion signals on various parameters (e.g., modulation frequency, shape of the fragmentation zone) is discussed. Experimental data confirms the theoretical calculations of the phase in each dimension. Understanding the phase relationships in a 2D mass spectrum is beneficial to the development of possible algorithms for phase correction, which may improve both the signal-to-noise ratio and the resolving power of peaks in 2D mass spectra.

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Section: Introductionmentioning

confidence: 99%

Phase relationships in two-dimensional mass spectrometry

Agthoven

Kilgour

Lynch

et al. 2019

J. Am. Soc. Mass Spectrom.

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“…Weissberg et al 7 and Housman et al 8 demonstrated the use of ESI‐MS 3 to reveal their structures. Snyder et al 9 utilized two‐dimensional MS/MS scans on a linear ion trap mass analyzer for their identification. Saeidian et al 10 explored the low‐abundance characteristic ions using GC/EI‐MS analysis to differentiate between isomers of V‐type nerve agents.…”

Section: Introductionmentioning

confidence: 99%

Oxidative derivatization of V‐type nerve agents as a tool for their structural elucidation by liquid chromatography/tandem mass spectrometry

Yamin

Madmon

Prihed

et al. 2021

Rapid Comm Mass Spectrometry

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Rationale The identification of V‐type nerve agents poses an analytical challenge. Their spectra obtained by electron ionization mass spectrometry (EI‐MS) and electrospray ionization tandem mass spectrometry (ESI‐MS/MS) are dominated by ions originating from the N,N‐dialkylaminoethyl moiety, while ions representative of the alkyl phosphonothiolate part are absent from the spectra or present at negligible abundance. Hence, analogs or isomers with the same amine residue exhibit similar mass spectral patterns, leading to unavoidable ambiguity in their identification. Methods Chemical derivatization was utilized for the structural elucidation of a series of five V‐type nerve agents, including O‐ethyl S‐(2‐diisopropylamino)ethyl methylalkyl phosphonothiolate (VX), O‐isobutyl S‐(2‐diethylamino)ethyl methylalkyl phosphonothiolate (RVX) and O‐ethyl S‐(2‐diethylamino)ethyl methylalkyl phosphonothiolate (VM). The procedure consisted of “in‐vial” oxidation of the tertiary amine group with 3‐chloroperbenzoic acid (m‐CPBA) at ambient temperature followed by liquid chromatography (LC)/Orbitrap‐ESI‐MS/MS analysis with no other sample preparation. Results The generated N‐oxide of the V‐type nerve agents altered the charge distribution occurring during fragmentation and produced informative ESI‐MS/MS spectra characteristic of the alkyl phosphonothiolate structure, enabling a higher degree of certainty in their identification. Moreover, two VX isomers possessing an identical tertiary amine moiety that coeluted at practically the same retention time and displayed high mass spectral similarity were easily differentiated, and their structures elucidated once derivatized. Conclusions In contrast to the ESI‐MS/MS spectra of the V‐type nerve agents, which exhibited mostly/only information on the amine‐containing residue, the ESI‐MS/MS spectra of the V‐type nerve agent N‐oxides revealed ions indicative of both the alkyl phosphonothiolate and the amine parts, enabling their reliable structural elucidation.

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“…1 Although the use of G-nerve agents is much more frequent than the use of closely related V-nerve agents, there have been several instances of V-type nerve agents being used or produced in the last two decades. 2 The same terrorist group that perpetrated the Tokyo subway attacks also developed and produced VX for terrorist purposes. 3,4 In February 2017, a binary form of VX was used to assassinate the uncle of the North Korean head of state, Kim Jong-un.…”

Section: Introductionmentioning

confidence: 99%

“…Their production, stockpiling, and use are prohibited under the Chemical Weapons Convention 1 . Although the use of G‐nerve agents is much more frequent than the use of closely related V‐nerve agents, there have been several instances of V‐type nerve agents being used or produced in the last two decades 2 . The same terrorist group that perpetrated the Tokyo subway attacks also developed and produced VX for terrorist purposes 3,4 .…”

Section: Introductionmentioning

confidence: 99%

“…Weissberg et al 8 and Housman et al 9 demonstrated the use of ESI‐MS 2 and ESI‐MS 3 experiments in cases where the information derived from routine ESI‐MS 2 experiments was insufficient for structural elucidation. More recently, Snyder et al 2 demonstrated the applicability of a single‐linear quadrupole ion trap to acquire two‐dimensional mass spectrometry data (2D MS/MS) for the identification of V‐nerve agents. Saeidian et al 10 reported the differentiation between VX isomers based on some low abundance characteristic ions using GC‐EI‐MS analysis.…”

Section: Introductionmentioning

confidence: 99%

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Structural elucidation of V‐type nerve agents by liquid chromatography/electrospray ionization mass spectrometry

et al. 2020

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V-nerve agents present information-poor spectra, both in GC-EI-MS and LC-ESI-MS/MS, with dominant fragments/product ions corresponding to the amine-containing residue. Hence, derivatives/isomers with the same amine residue exhibit similar mass spectral patterns, leading to ambiguity in the phosphonate structure. We present a simple approach for their structural elucidation based on two complementary experiments: ESI-MS/MS of the original compound, which provides information about the amine moiety, and ESI-MS/MS of the phosphonic acid hydrolysis products generated by N-iodosuccinimide, which provides ions' characteristic of the phosphonate structure. This approach enables the structural elucidation of the original V-agents with a higher degree of certainty.

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Two-dimensional MS/MS scans on a linear ion trap mass analyzer: Identification of V-series chemical warfare agents

Cited by 18 publications

References 32 publications

Phase relationships in two-dimensional mass spectrometry

Phase relationships in two-dimensional mass spectrometry

Oxidative derivatization of V‐type nerve agents as a tool for their structural elucidation by liquid chromatography/tandem mass spectrometry

Structural elucidation of V‐type nerve agents by liquid chromatography/electrospray ionization mass spectrometry

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