Influence of Reduced Field Strength on Product Ion Formation in High Kinetic Energy Ion Mobility Spectrometry (HiKE-IMS)

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Original languageEnglish
Pages (from-to)1810-1820
Number of pages11
JournalJournal of the American Society for Mass Spectrometry
Volume32
Issue number7
Early online date25 Jun 2021
Publication statusPublished - 7 Jul 2021

Abstract

Classical ion mobility spectrometers (IMS) operated at ambient pressure, often use atmospheric pressure chemical ionization (APCI) sources to ionize organic compounds. In APCI, reactant ions ionize neutral analyte molecules via gas-phase ion-molecule reactions. The positively charged reactant ions in purified, dry air are H3O+, NO+, and O2+•. However, the hydration of reactant ions in classical IMS operated at ambient pressure renders ionization of certain analytes difficult. In contrast to classical IMS operated at ambient pressure, High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) are operated at a decreased pressure of 10-40 mbar, allowing operation at high reduced electric field strengths of up to 120 Td. At such high reduced field strengths, ions reach high effective temperatures causing collision-induced cluster dissociation of the hydrated gas-phase ions, allowing ionization of nonpolar and low proton affinity analytes. The reactant ion population, consisting of H3O+(H2O)n, NO+(H2O)m, and O2+•(H2O)p with an individual abundance that strongly depends on the reduced field strength, differs from the reactant ion population in IMS operated at ambient pressure, which affects the ionization of analyte molecules. In this work, we investigate the influence of reduced field strength on the product ion formation of aromatic hydrocarbons used as model substances. A HiKE-IMS-MS coupling was used to identify the detected ion species. The results show that the analytes form parent cations via charge transfer with NO+(H2O)m and O2+•(H2O)p depending on ionization energy and protonated parent molecules via proton transfer and ligand switching with H3O+(H2O)n mainly depending on proton affinity.

Keywords

    APCI, corona discharge ionization, high kinetic energy ion mobility spectrometry, HiKE-IMS, IMS, ion mobility spectrometry, ionization

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Influence of Reduced Field Strength on Product Ion Formation in High Kinetic Energy Ion Mobility Spectrometry (HiKE-IMS). / Schaefer, Christoph; Allers, Maria; Kirk, Ansgar T. et al.
In: Journal of the American Society for Mass Spectrometry, Vol. 32, No. 7, 07.07.2021, p. 1810-1820.

Research output: Contribution to journalArticleResearchpeer review

Schaefer C, Allers M, Kirk AT, Schlottmann F, Zimmermann S. Influence of Reduced Field Strength on Product Ion Formation in High Kinetic Energy Ion Mobility Spectrometry (HiKE-IMS). Journal of the American Society for Mass Spectrometry. 2021 Jul 7;32(7):1810-1820. Epub 2021 Jun 25. doi: 10.15488/14299, 10.1021/jasms.1c00156
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title = "Influence of Reduced Field Strength on Product Ion Formation in High Kinetic Energy Ion Mobility Spectrometry (HiKE-IMS)",
abstract = "Classical ion mobility spectrometers (IMS) operated at ambient pressure, often use atmospheric pressure chemical ionization (APCI) sources to ionize organic compounds. In APCI, reactant ions ionize neutral analyte molecules via gas-phase ion-molecule reactions. The positively charged reactant ions in purified, dry air are H3O+, NO+, and O2+•. However, the hydration of reactant ions in classical IMS operated at ambient pressure renders ionization of certain analytes difficult. In contrast to classical IMS operated at ambient pressure, High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) are operated at a decreased pressure of 10-40 mbar, allowing operation at high reduced electric field strengths of up to 120 Td. At such high reduced field strengths, ions reach high effective temperatures causing collision-induced cluster dissociation of the hydrated gas-phase ions, allowing ionization of nonpolar and low proton affinity analytes. The reactant ion population, consisting of H3O+(H2O)n, NO+(H2O)m, and O2+•(H2O)p with an individual abundance that strongly depends on the reduced field strength, differs from the reactant ion population in IMS operated at ambient pressure, which affects the ionization of analyte molecules. In this work, we investigate the influence of reduced field strength on the product ion formation of aromatic hydrocarbons used as model substances. A HiKE-IMS-MS coupling was used to identify the detected ion species. The results show that the analytes form parent cations via charge transfer with NO+(H2O)m and O2+•(H2O)p depending on ionization energy and protonated parent molecules via proton transfer and ligand switching with H3O+(H2O)n mainly depending on proton affinity.",
keywords = "APCI, corona discharge ionization, high kinetic energy ion mobility spectrometry, HiKE-IMS, IMS, ion mobility spectrometry, ionization",
author = "Christoph Schaefer and Maria Allers and Kirk, {Ansgar T.} and Florian Schlottmann and Stefan Zimmermann",
note = "Funding Information: Funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) - 318063177. ",
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T1 - Influence of Reduced Field Strength on Product Ion Formation in High Kinetic Energy Ion Mobility Spectrometry (HiKE-IMS)

AU - Schaefer, Christoph

AU - Allers, Maria

AU - Kirk, Ansgar T.

AU - Schlottmann, Florian

AU - Zimmermann, Stefan

N1 - Funding Information: Funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) - 318063177.

PY - 2021/7/7

Y1 - 2021/7/7

N2 - Classical ion mobility spectrometers (IMS) operated at ambient pressure, often use atmospheric pressure chemical ionization (APCI) sources to ionize organic compounds. In APCI, reactant ions ionize neutral analyte molecules via gas-phase ion-molecule reactions. The positively charged reactant ions in purified, dry air are H3O+, NO+, and O2+•. However, the hydration of reactant ions in classical IMS operated at ambient pressure renders ionization of certain analytes difficult. In contrast to classical IMS operated at ambient pressure, High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) are operated at a decreased pressure of 10-40 mbar, allowing operation at high reduced electric field strengths of up to 120 Td. At such high reduced field strengths, ions reach high effective temperatures causing collision-induced cluster dissociation of the hydrated gas-phase ions, allowing ionization of nonpolar and low proton affinity analytes. The reactant ion population, consisting of H3O+(H2O)n, NO+(H2O)m, and O2+•(H2O)p with an individual abundance that strongly depends on the reduced field strength, differs from the reactant ion population in IMS operated at ambient pressure, which affects the ionization of analyte molecules. In this work, we investigate the influence of reduced field strength on the product ion formation of aromatic hydrocarbons used as model substances. A HiKE-IMS-MS coupling was used to identify the detected ion species. The results show that the analytes form parent cations via charge transfer with NO+(H2O)m and O2+•(H2O)p depending on ionization energy and protonated parent molecules via proton transfer and ligand switching with H3O+(H2O)n mainly depending on proton affinity.

AB - Classical ion mobility spectrometers (IMS) operated at ambient pressure, often use atmospheric pressure chemical ionization (APCI) sources to ionize organic compounds. In APCI, reactant ions ionize neutral analyte molecules via gas-phase ion-molecule reactions. The positively charged reactant ions in purified, dry air are H3O+, NO+, and O2+•. However, the hydration of reactant ions in classical IMS operated at ambient pressure renders ionization of certain analytes difficult. In contrast to classical IMS operated at ambient pressure, High Kinetic Energy Ion Mobility Spectrometers (HiKE-IMS) are operated at a decreased pressure of 10-40 mbar, allowing operation at high reduced electric field strengths of up to 120 Td. At such high reduced field strengths, ions reach high effective temperatures causing collision-induced cluster dissociation of the hydrated gas-phase ions, allowing ionization of nonpolar and low proton affinity analytes. The reactant ion population, consisting of H3O+(H2O)n, NO+(H2O)m, and O2+•(H2O)p with an individual abundance that strongly depends on the reduced field strength, differs from the reactant ion population in IMS operated at ambient pressure, which affects the ionization of analyte molecules. In this work, we investigate the influence of reduced field strength on the product ion formation of aromatic hydrocarbons used as model substances. A HiKE-IMS-MS coupling was used to identify the detected ion species. The results show that the analytes form parent cations via charge transfer with NO+(H2O)m and O2+•(H2O)p depending on ionization energy and protonated parent molecules via proton transfer and ligand switching with H3O+(H2O)n mainly depending on proton affinity.

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KW - corona discharge ionization

KW - high kinetic energy ion mobility spectrometry

KW - HiKE-IMS

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KW - ion mobility spectrometry

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DO - 10.15488/14299

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C2 - 34170133

AN - SCOPUS:85110276958

VL - 32

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JO - Journal of the American Society for Mass Spectrometry

JF - Journal of the American Society for Mass Spectrometry

SN - 1044-0305

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