How Hot Are Your Ions in Differential Mobility Spectrometry?

Research output: Contribution to journal › Article › Research › peer review

Authors

  • Christian Ieritano
  • Joshua Featherstone
  • Alexander Haack
  • Mircea Guna
  • J. Larry Campbell
  • W. Scott Hopkins

External Research Organisations

  • University of Waterloo
  • The University of Wuppertal
  • SCIEX
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Details

Original languageEnglish
Pages (from-to)582-593
Number of pages12
JournalJournal of the American Society for Mass Spectrometry
Volume31
Issue number3
Publication statusPublished - 4 Mar 2020
Externally publishedYes

Abstract

Ions can experience significant field-induced heating in a differential mobility cell. To investigate this phenomenon, the fragmentation of several para-substituted benzylpyridinium "thermometer" ions (R = OMe, Me, F, Cl, H, CN) was monitored in a commercial differential mobility spectrometer (DMS). The internal energy of each benzylpyridinium derivative was characterized by monitoring the degree of fragmentation to obtain an effective temperature, Teff, which corresponds to a temperature consistent with treating the observed fragmentation ratio using a unimolecular dissociation rate weighted by a Boltzmann distribution at a temperature T. It was found that ions are sufficiently thermalized after initial activation from the ESI process to the temperature of the bath gas, Tbath. Once a critical field strength was surpassed, significant fragmentation of the benzylpyridinium ions was detected. At the maximum bath gas temperature (450 K) and separation voltage (SV; 4400 V) for our instrument, Tefffor the benzylpyridinium derivatives ranged from 664 ± 9 K (p-OMe) to 759 ± 17 K (p-H). The extent of activation at a given SV depends on the ion's mass, degrees of freedom, (NDoF), and collision frequency as represented by the ion's collision cross section. Plots of Teffvs the product of ion mass and NDoFand the inverse of collision cross section produce strong linear relationships. This provides an attractive avenue to estimate ion temperatures at a given SV using only intrinsic properties. Moreover, experimentally determined Teffcorrelate with theoretically predicted Teffusing with a self-consistent method based on two-temperature theory. The various instrumental and external parameters that influence Teffare additionally discussed.

Keywords

    benzylpyridinium, differential mobility spectrometry, effective temperature, thermometer ion

ASJC Scopus subject areas

Cite this

How Hot Are Your Ions in Differential Mobility Spectrometry? / Ieritano, Christian; Featherstone, Joshua; Haack, Alexander et al.
In: Journal of the American Society for Mass Spectrometry, Vol. 31, No. 3, 04.03.2020, p. 582-593.

Research output: Contribution to journal › Article › Research › peer review

Ieritano, C, Featherstone, J, Haack, A, Guna, M, Campbell, JL & Hopkins, WS 2020, 'How Hot Are Your Ions in Differential Mobility Spectrometry?', Journal of the American Society for Mass Spectrometry, vol. 31, no. 3, pp. 582-593. https://doi.org/10.1021/jasms.9b00043
Ieritano, C., Featherstone, J., Haack, A., Guna, M., Campbell, J. L., & Hopkins, W. S. (2020). How Hot Are Your Ions in Differential Mobility Spectrometry? Journal of the American Society for Mass Spectrometry, 31(3), 582-593. https://doi.org/10.1021/jasms.9b00043
Ieritano C, Featherstone J, Haack A, Guna M, Campbell JL, Hopkins WS. How Hot Are Your Ions in Differential Mobility Spectrometry? Journal of the American Society for Mass Spectrometry. 2020 Mar 4;31(3):582-593. doi: 10.1021/jasms.9b00043
Ieritano, Christian ; Featherstone, Joshua ; Haack, Alexander et al. / How Hot Are Your Ions in Differential Mobility Spectrometry?. In: Journal of the American Society for Mass Spectrometry. 2020 ; Vol. 31, No. 3. pp. 582-593.
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title = "How Hot Are Your Ions in Differential Mobility Spectrometry?",
abstract = "Ions can experience significant field-induced heating in a differential mobility cell. To investigate this phenomenon, the fragmentation of several para-substituted benzylpyridinium {"}thermometer{"} ions (R = OMe, Me, F, Cl, H, CN) was monitored in a commercial differential mobility spectrometer (DMS). The internal energy of each benzylpyridinium derivative was characterized by monitoring the degree of fragmentation to obtain an effective temperature, Teff, which corresponds to a temperature consistent with treating the observed fragmentation ratio using a unimolecular dissociation rate weighted by a Boltzmann distribution at a temperature T. It was found that ions are sufficiently thermalized after initial activation from the ESI process to the temperature of the bath gas, Tbath. Once a critical field strength was surpassed, significant fragmentation of the benzylpyridinium ions was detected. At the maximum bath gas temperature (450 K) and separation voltage (SV; 4400 V) for our instrument, Tefffor the benzylpyridinium derivatives ranged from 664 ± 9 K (p-OMe) to 759 ± 17 K (p-H). The extent of activation at a given SV depends on the ion's mass, degrees of freedom, (NDoF), and collision frequency as represented by the ion's collision cross section. Plots of Teffvs the product of ion mass and NDoFand the inverse of collision cross section produce strong linear relationships. This provides an attractive avenue to estimate ion temperatures at a given SV using only intrinsic properties. Moreover, experimentally determined Teffcorrelate with theoretically predicted Teffusing with a self-consistent method based on two-temperature theory. The various instrumental and external parameters that influence Teffare additionally discussed.",
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note = "Funding Information: We acknowledge Bruce Collings (SCIEX), who contributed SIMION simulations, Prof. Terry McMahon (University of Waterloo) for helpful discussions, and the high-performance computing support from Compute Canada. We additionally thank the reviewers of this manuscript for their collective insights. W.S.H. acknowledges the financial support provided by the Natural Sciences and Engineering Research Council (NSERC) of Canada, the Ontario Centres of Excellence in the form of a VIP-II grant, as well as the government of Ontario for an Ontario Early Researcher Award. CI acknowledges financial support from the government of Ontario for an Ontario Graduate Scholarship. ",
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Download

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T1 - How Hot Are Your Ions in Differential Mobility Spectrometry?

AU - Ieritano, Christian

AU - Featherstone, Joshua

AU - Haack, Alexander

AU - Guna, Mircea

AU - Campbell, J. Larry

AU - Hopkins, W. Scott

N1 - Funding Information: We acknowledge Bruce Collings (SCIEX), who contributed SIMION simulations, Prof. Terry McMahon (University of Waterloo) for helpful discussions, and the high-performance computing support from Compute Canada. We additionally thank the reviewers of this manuscript for their collective insights. W.S.H. acknowledges the financial support provided by the Natural Sciences and Engineering Research Council (NSERC) of Canada, the Ontario Centres of Excellence in the form of a VIP-II grant, as well as the government of Ontario for an Ontario Early Researcher Award. CI acknowledges financial support from the government of Ontario for an Ontario Graduate Scholarship.

PY - 2020/3/4

Y1 - 2020/3/4

N2 - Ions can experience significant field-induced heating in a differential mobility cell. To investigate this phenomenon, the fragmentation of several para-substituted benzylpyridinium "thermometer" ions (R = OMe, Me, F, Cl, H, CN) was monitored in a commercial differential mobility spectrometer (DMS). The internal energy of each benzylpyridinium derivative was characterized by monitoring the degree of fragmentation to obtain an effective temperature, Teff, which corresponds to a temperature consistent with treating the observed fragmentation ratio using a unimolecular dissociation rate weighted by a Boltzmann distribution at a temperature T. It was found that ions are sufficiently thermalized after initial activation from the ESI process to the temperature of the bath gas, Tbath. Once a critical field strength was surpassed, significant fragmentation of the benzylpyridinium ions was detected. At the maximum bath gas temperature (450 K) and separation voltage (SV; 4400 V) for our instrument, Tefffor the benzylpyridinium derivatives ranged from 664 ± 9 K (p-OMe) to 759 ± 17 K (p-H). The extent of activation at a given SV depends on the ion's mass, degrees of freedom, (NDoF), and collision frequency as represented by the ion's collision cross section. Plots of Teffvs the product of ion mass and NDoFand the inverse of collision cross section produce strong linear relationships. This provides an attractive avenue to estimate ion temperatures at a given SV using only intrinsic properties. Moreover, experimentally determined Teffcorrelate with theoretically predicted Teffusing with a self-consistent method based on two-temperature theory. The various instrumental and external parameters that influence Teffare additionally discussed.

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