https://doi.org/10.1140/epjd/s10053-022-00501-8
Regular Article - Atomic and Molecular Collisions
High kinetic energy-ion mobility spectrometry-mass spectrometry investigations of several volatiles and their fully deuterated analogues
1
Institute for Breath Research, University of Innsbruck, Innrain 66, 6020, Innsbruck, Austria
2
Department of Chemistry and Biochemistry, New Mexico State University, 88003, Las Cruces, NM, USA
3
Department of Chemistry, VERIFIN, Finnish Institute for the Verification of the Chemical Weapons Convention, University of Helsinki, 00014, Helsinki, Finland
4
Institute for Ion Physics and Applied Physics, University of Innsbruck, 6020, Innsbruck, Austria
5
Tyrolean Cancer Research Institute, Innrain 66, 6020, Innsbruck, Austria
6
Institute of Electrical Engineering and Measurement Technology, Leibniz University Hannover, 30167, Hannover, Germany
Received:
17
June
2022
Accepted:
10
September
2022
Published online:
7
October
2022
The first High Kinetic Energy-Ion Mobility Spectrometry-Mass Spectrometry (HiKE-IMS-MS) studies involving six volatiles (acetone, acetonitrile, methanol, ethanol, 2-propanol, and 1-butanol) and their fully deuterated analogues are reported. The goal is to further our understanding of the ion–molecule chemistry occurring in the HiKE-IMS. This is needed for its full analytical potential to be reached. Product ions are identified as a function of the reduced electric field (30–115 Td) and the influence of sample air humidity in the reaction region on deuterium/hydrogen (D/H) exchange reactions is discussed. Reagent ions include H3O+(H2O)m (n = 0, 1, 2 or 3), NO+(H2O)n (m = 0 or 1) and O2+·. Reactions with H3O+(H2O)m lead to protonated monomers (through either proton transfer or ligand switching). Reactions with NO+ involve association with acetone and acetonitrile, hydride anion abstraction from ethanol, 2-propanol, and 1-butanol, and hydroxide abstraction from 2-propanol and 1-butanol. With the exception of acetonitrile, O2+· predominantly reacts with the volatiles via dissociative charge transfer. A number of sequential secondary ion-volatile processes occur leading to the formation of dimer and trimer-containing ion species, whose intensities depend on a volatile’s concentration and the reduced electric field in the reaction region. Deuterium/hydrogen (D/H) exchange does not occur for product ions from acetone-d6 and acetonitrile-d3, owing to their inert methyl functional groups. For the deuterated alcohols, rapid D/H-exchange reaction at the hydroxy group is observed, the amount of which increased with the increasing humidity of the sample air and/or lowering of the reduced electric field.
© The Author(s) 2022. corrected publication 2023
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