Details
Original language | English |
---|---|
Pages (from-to) | 535-547 |
Number of pages | 13 |
Journal | Journal of the American Society for Mass Spectrometry |
Volume | 33 |
Issue number | 3 |
Early online date | 31 Jan 2022 |
Publication status | E-pub ahead of print - 31 Jan 2022 |
Externally published | Yes |
Abstract
Differential mobility spectrometry is a separation technique that may be applied to a variety of analytes ranging from small molecule drugs to peptides and proteins. Although rudimentary theoretical models of differential mobility exist, these models are often only applied to small molecules and atomic ions without considering the effects of dynamic microsolvation. Here, we advance our theoretical description of differential ion mobility in pure N2 and microsolvating environments by incorporating higher order corrections to two-temperature theory (2TT) and a pseudoequilibrium approach to describe ion-neutral interactions. When comparing theoretical predictions to experimentally measured dispersion plots of over 300 different compounds, we find that higher order corrections to 2TT reduce errors by roughly a factor of 2 when compared to first order. Model predictions are accurate especially for pure N2 environments (mean absolute error of 4 V at SV = 4000 V). For strongly clustering environments, accurate thermochemical corrections for ion-solvent clustering are likely required to reliably predict differential ion mobility behavior. Within our model, general trends associated with clustering strength, solvent vapor concentration, and background gas temperature are well reproduced, and fine structure visible in some dispersion plots is captured. These results provide insight into the dynamic ion-solvent clustering process that underpins the phenomenon of differential ion mobility.
Keywords
- collision cross section, density functional theory, differential ion mobility, ion−solvent cluster, two-temperature theory
ASJC Scopus subject areas
- Biochemistry, Genetics and Molecular Biology(all)
- Structural Biology
- Chemistry(all)
- Spectroscopy
Cite this
- Standard
- Harvard
- Apa
- Vancouver
- BibTeX
- RIS
In: Journal of the American Society for Mass Spectrometry, Vol. 33, No. 3, 31.01.2022, p. 535-547.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Improved First-Principles Model of Differential Mobility Using Higher Order Two-Temperature Theory
AU - Haack, Alexander
AU - Bissonnette, Justine R.
AU - Ieritano, Christian
AU - Hopkins, W. Scott
N1 - Funding Information: We acknowledge the high-performance computing support from Compute Canada. W.S.H. acknowledges 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. A.H. gratefully acknowledges this work being funded by the Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) - 449651261. J.R.B. acknowledges financial support from the NSERC Undergraduate Student Research Award (USRA). C.I. acknowledges financial support from the Government of Canada through the Vanier Canada Graduate Scholarship.
PY - 2022/1/31
Y1 - 2022/1/31
N2 - Differential mobility spectrometry is a separation technique that may be applied to a variety of analytes ranging from small molecule drugs to peptides and proteins. Although rudimentary theoretical models of differential mobility exist, these models are often only applied to small molecules and atomic ions without considering the effects of dynamic microsolvation. Here, we advance our theoretical description of differential ion mobility in pure N2 and microsolvating environments by incorporating higher order corrections to two-temperature theory (2TT) and a pseudoequilibrium approach to describe ion-neutral interactions. When comparing theoretical predictions to experimentally measured dispersion plots of over 300 different compounds, we find that higher order corrections to 2TT reduce errors by roughly a factor of 2 when compared to first order. Model predictions are accurate especially for pure N2 environments (mean absolute error of 4 V at SV = 4000 V). For strongly clustering environments, accurate thermochemical corrections for ion-solvent clustering are likely required to reliably predict differential ion mobility behavior. Within our model, general trends associated with clustering strength, solvent vapor concentration, and background gas temperature are well reproduced, and fine structure visible in some dispersion plots is captured. These results provide insight into the dynamic ion-solvent clustering process that underpins the phenomenon of differential ion mobility.
AB - Differential mobility spectrometry is a separation technique that may be applied to a variety of analytes ranging from small molecule drugs to peptides and proteins. Although rudimentary theoretical models of differential mobility exist, these models are often only applied to small molecules and atomic ions without considering the effects of dynamic microsolvation. Here, we advance our theoretical description of differential ion mobility in pure N2 and microsolvating environments by incorporating higher order corrections to two-temperature theory (2TT) and a pseudoequilibrium approach to describe ion-neutral interactions. When comparing theoretical predictions to experimentally measured dispersion plots of over 300 different compounds, we find that higher order corrections to 2TT reduce errors by roughly a factor of 2 when compared to first order. Model predictions are accurate especially for pure N2 environments (mean absolute error of 4 V at SV = 4000 V). For strongly clustering environments, accurate thermochemical corrections for ion-solvent clustering are likely required to reliably predict differential ion mobility behavior. Within our model, general trends associated with clustering strength, solvent vapor concentration, and background gas temperature are well reproduced, and fine structure visible in some dispersion plots is captured. These results provide insight into the dynamic ion-solvent clustering process that underpins the phenomenon of differential ion mobility.
KW - collision cross section
KW - density functional theory
KW - differential ion mobility
KW - ion−solvent cluster
KW - two-temperature theory
UR - http://www.scopus.com/inward/record.url?scp=85124032087&partnerID=8YFLogxK
U2 - 10.1021/jasms.1c00354
DO - 10.1021/jasms.1c00354
M3 - Article
C2 - 35099948
AN - SCOPUS:85124032087
VL - 33
SP - 535
EP - 547
JO - Journal of the American Society for Mass Spectrometry
JF - Journal of the American Society for Mass Spectrometry
SN - 1044-0305
IS - 3
ER -