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Ion-molecule adduct formation in tandem mass spectrometry

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Abstract

Nowadays most LC-MS methods rely on tandem mass spectrometry not only for quantitation and confirmation of compounds by multiple reaction monitoring (MRM), but also for the identification of unknowns from their product ion spectra. However, gas-phase reactions between charged and neutral species inside the mass analyzer can occur, yielding product ions at m/z values higher than that of the precursor ion, or at m/z values difficult to explain by logical losses, which complicate mass spectral interpretation. In this work, the formation of adduct ions in the mass analyzer was studied using several mass spectrometers with different mass analyzers (ion trap, triple quadrupole, and quadrupole-Orbitrap). Heterocyclic amines (AαC, MeAαC, Trp-P-1, and Trp-P-2), photo-initiators (BP and THBP), and pharmaceuticals (phenacetin and levamisole) were selected as model compounds and infused in LCQ Classic, TSQ Quantum Ultra AM, and Q-Exactive Orbitrap (ThermoFisher Scientific) mass spectrometers using electrospray as ionization method. The generation of ion-molecule adducts depended on the compound and also on the instrument employed. Adducts with neutral organic solvents (methanol and acetonitrile) were only observed in the ion trap instrument (LCQ Classic), because of the ionization source on-axis configuration and the lack of gas-phase barriers, which allowed inertial entrance of the neutrals into the analyzer. Adduct formation (only with water) in the triple quadrupole instruments was less abundant than in the ion trap and quadrupole-Orbitrap mass spectrometers, because of the lower residence time of the reactive product ions in the mass analyzer. The moisture level of the CID and/or damper gas had a great effect in beam-like mass analyzers such as triple quadrupole, but not in trap-like mass analyzers, probably because of the long residence time that allowed adduct formation even with very low concentrations of water inside the mass spectrometer.

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Acknowledgments

The authors acknowledge financial support received from the Spanish Ministry of Economy and Competitiveness under the project CTQ2012-30836, and from the Agency for Administration of University and Research Grants (Generalitat de Catalunya, Spain) under the project 2014 SGR-539. The authors also acknowledge Dr. Josep Caixach’s assistance with the Exactive mass spectrometer.

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Authors and Affiliations

  1. Department of Analytical Chemistry, University of Barcelona, Diagonal 645, 08028, Barcelona, Spain

    Élida Alechaga, Encarnación Moyano & Maria Teresa Galceran

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  1. Élida Alechaga
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  2. Encarnación Moyano
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  3. Maria Teresa Galceran
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Correspondence to Encarnación Moyano.

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Alechaga, É., Moyano, E. & Galceran, M.T. Ion-molecule adduct formation in tandem mass spectrometry. Anal Bioanal Chem 408, 1269–1277 (2016). https://doi.org/10.1007/s00216-015-9237-6

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  • DOI: https://doi.org/10.1007/s00216-015-9237-6

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