Journal
EUROPEAN PHYSICAL JOURNAL D
Volume 76, Issue 10, Pages -Publisher
SPRINGER
DOI: 10.1140/epjd/s10053-022-00501-8
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- University of Innsbruck
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This study reports the first High Kinetic Energy-Ion Mobility Spectrometry-Mass Spectrometry (HiKE-IMS-MS) studies involving six volatiles and their fully deuterated analogues. The goal is to understand the ion-molecule chemistry occurring in the HiKE-IMS. The reactions of different reagent ions with the volatiles and the influence of sample air humidity and reduced electric field on the reactions are discussed.
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 O-2(+center dot). 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, O-2(+center dot) 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-d(6) and acetonitrile-d(3), 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.
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