Details
| Original language | English |
|---|---|
| Pages (from-to) | 1035–1046 |
| Number of pages | 12 |
| Journal | Journal of the American Society for Mass Spectrometry |
| Volume | 34 |
| Issue number | 6 |
| Early online date | 28 Apr 2023 |
| Publication status | Published - 7 Jun 2023 |
Abstract
Ion mobility spectrometry is widely used in analytical chemistry, either as a stand-alone technique or coupled to mass spectrometry. Ions in the gas phase tend to form loosely bound clusters with surrounding solvent vapors, artificially increasing the collisional cross section and the mass of the ion. This, in turn, affects ion mobility and influences separation. Further, ion-solvent clusters play an important role in most ionization mechanisms occurring in the gas phase. Consequently, a deeper understanding of ion-solvent cluster association and dissociation processes is desirable to guide experimental design and interpretation. A few computational models exist, which aim to describe the amount of clustering as a function of the reduced electric field strength, bath gas pressure and temperature, and the chemical species probed. It is especially challenging to model ion mobility under high reduced electrical field strengths due to the nonthermal conditions created by the field. In this work, we aim to validate a recently proposed first-principles model by comparing its predictions with direct measurements of cluster size distributions over a range of 20-120 Td as observed using a High Kinetic Energy Ion Mobility Spectrometer coupled to a mass spectrometer (HiKE-IMS-MS). By studying H+(H2O)n, [MeOH + H + n(H2O)]+, [ACE + H + n(H2O)]+, and [PhNH2 + H + n(H2O)]+ as test systems, we find very good agreement between model and experiment, supporting the validity of the computational workflow. Further, the detailed information gained from the modeling yields important insights into the cluster dynamics within the HiKE-IMS, allowing for better interpretation of the measured ion mobility spectra.
Keywords
- collision cross section, high kinetic energy ion mobility spectrometry, HiKE-IMS, ion mobility, ion−solvent clusters, kinetics
ASJC Scopus subject areas
- Biochemistry, Genetics and Molecular Biology(all)
- Structural Biology
- Chemistry(all)
- Spectroscopy
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In: Journal of the American Society for Mass Spectrometry, Vol. 34, No. 6, 07.06.2023, p. 1035–1046.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Validation of Field-Dependent Ion-Solvent Cluster Modeling via Direct Measurement of Cluster Size Distributions
AU - Haack, Alexander
AU - Schaefer, Christoph
AU - Zimmermann, Stefan
AU - Hopkins, W. Scott
N1 - Funding Information: The authors would like to acknowledge the high-performance computing support from the Digital Research Alliance of Canada. W.S.H. would like to acknowledge the financial support provided by the Natural Sciences and Engineering Research Council (NSERC) of Canada in the form of Discovery and Alliance grants, as well as the government of Ontario for an Ontario Early Researcher Award. Further, W.S.H. acknowledges the support from the InnoHK Initiative and the Hong Kong Special Administrative Region Government. A.H. gratefully acknowledges this work being funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) – 449651261. C.S. and S.Z. gratefully acknowledge this work being funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) – 390583968.
PY - 2023/6/7
Y1 - 2023/6/7
N2 - Ion mobility spectrometry is widely used in analytical chemistry, either as a stand-alone technique or coupled to mass spectrometry. Ions in the gas phase tend to form loosely bound clusters with surrounding solvent vapors, artificially increasing the collisional cross section and the mass of the ion. This, in turn, affects ion mobility and influences separation. Further, ion-solvent clusters play an important role in most ionization mechanisms occurring in the gas phase. Consequently, a deeper understanding of ion-solvent cluster association and dissociation processes is desirable to guide experimental design and interpretation. A few computational models exist, which aim to describe the amount of clustering as a function of the reduced electric field strength, bath gas pressure and temperature, and the chemical species probed. It is especially challenging to model ion mobility under high reduced electrical field strengths due to the nonthermal conditions created by the field. In this work, we aim to validate a recently proposed first-principles model by comparing its predictions with direct measurements of cluster size distributions over a range of 20-120 Td as observed using a High Kinetic Energy Ion Mobility Spectrometer coupled to a mass spectrometer (HiKE-IMS-MS). By studying H+(H2O)n, [MeOH + H + n(H2O)]+, [ACE + H + n(H2O)]+, and [PhNH2 + H + n(H2O)]+ as test systems, we find very good agreement between model and experiment, supporting the validity of the computational workflow. Further, the detailed information gained from the modeling yields important insights into the cluster dynamics within the HiKE-IMS, allowing for better interpretation of the measured ion mobility spectra.
AB - Ion mobility spectrometry is widely used in analytical chemistry, either as a stand-alone technique or coupled to mass spectrometry. Ions in the gas phase tend to form loosely bound clusters with surrounding solvent vapors, artificially increasing the collisional cross section and the mass of the ion. This, in turn, affects ion mobility and influences separation. Further, ion-solvent clusters play an important role in most ionization mechanisms occurring in the gas phase. Consequently, a deeper understanding of ion-solvent cluster association and dissociation processes is desirable to guide experimental design and interpretation. A few computational models exist, which aim to describe the amount of clustering as a function of the reduced electric field strength, bath gas pressure and temperature, and the chemical species probed. It is especially challenging to model ion mobility under high reduced electrical field strengths due to the nonthermal conditions created by the field. In this work, we aim to validate a recently proposed first-principles model by comparing its predictions with direct measurements of cluster size distributions over a range of 20-120 Td as observed using a High Kinetic Energy Ion Mobility Spectrometer coupled to a mass spectrometer (HiKE-IMS-MS). By studying H+(H2O)n, [MeOH + H + n(H2O)]+, [ACE + H + n(H2O)]+, and [PhNH2 + H + n(H2O)]+ as test systems, we find very good agreement between model and experiment, supporting the validity of the computational workflow. Further, the detailed information gained from the modeling yields important insights into the cluster dynamics within the HiKE-IMS, allowing for better interpretation of the measured ion mobility spectra.
KW - collision cross section
KW - high kinetic energy ion mobility spectrometry
KW - HiKE-IMS
KW - ion mobility
KW - ion−solvent clusters
KW - kinetics
UR - http://www.scopus.com/inward/record.url?scp=85156235861&partnerID=8YFLogxK
U2 - 10.1021/jasms.3c00012
DO - 10.1021/jasms.3c00012
M3 - Article
C2 - 37116175
AN - SCOPUS:85156235861
VL - 34
SP - 1035
EP - 1046
JO - Journal of the American Society for Mass Spectrometry
JF - Journal of the American Society for Mass Spectrometry
SN - 1044-0305
IS - 6
ER -