Details
| Original language | English |
|---|---|
| Pages (from-to) | 12433-12443 |
| Journal | Analytical chemistry |
| Volume | 96 |
| Issue number | 30 |
| Early online date | 15 Jul 2024 |
| Publication status | Published - 30 Jul 2024 |
Abstract
ASJC Scopus subject areas
- Chemistry(all)
- Analytical Chemistry
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In: Analytical chemistry, Vol. 96, No. 30, 30.07.2024, p. 12433-12443.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - On the Arrival Time Distribution of Reacting Systems in Ion Mobility Spectrometry
AU - Haack, A.
AU - Schaefer, C.
AU - Zimmermann, S.
N1 - Publisher Copyright: © 2024 The Authors. Published by American Chemical Society.
PY - 2024/7/30
Y1 - 2024/7/30
N2 - Ion mobility spectrometry (IMS) is a widely used gas-phase separation technique, particularly when coupled with mass spectrometry (MS). Modern IMS instruments often apply elevated reduced field strengths for improved ion separation and ion focusing. These alter the collision dynamics and further drive ion reaction processes that can change the analyte’s structure. As a result, the measured arrival time distribution (ATD) can change with the applied reduced field strengths. In this work, we systematically study how the ion collision dynamics and the ion reaction dynamics, as a function of the reduced field strength, can alter the ATD. To this end, we investigate 2,6-di-tert-butylpyridine, methanol, and ethyl acetate using a home-built drift tube IMS coupled to a home-built MS and extensive first-principles Monte Carlo modeling. We show how elevated reduced field strengths can actually lower resolving power through increased ion diffusion and how the field dependency of the ion mobility can introduce uncertainties to collision cross sections (CCS) calculated from the measured mobilities. On top of the collision dynamics, we show how chemical transformation processes that alter the analyte’s CCS, e.g., dynamic clustering or fragmentation, can lead to broadened, shifted, or non-Gaussian ATDs and how sensitive these processes are to the applied field strengths. We highlight how first-principles ion dynamics simulations can help to understand and even harness the mentioned effects.
AB - Ion mobility spectrometry (IMS) is a widely used gas-phase separation technique, particularly when coupled with mass spectrometry (MS). Modern IMS instruments often apply elevated reduced field strengths for improved ion separation and ion focusing. These alter the collision dynamics and further drive ion reaction processes that can change the analyte’s structure. As a result, the measured arrival time distribution (ATD) can change with the applied reduced field strengths. In this work, we systematically study how the ion collision dynamics and the ion reaction dynamics, as a function of the reduced field strength, can alter the ATD. To this end, we investigate 2,6-di-tert-butylpyridine, methanol, and ethyl acetate using a home-built drift tube IMS coupled to a home-built MS and extensive first-principles Monte Carlo modeling. We show how elevated reduced field strengths can actually lower resolving power through increased ion diffusion and how the field dependency of the ion mobility can introduce uncertainties to collision cross sections (CCS) calculated from the measured mobilities. On top of the collision dynamics, we show how chemical transformation processes that alter the analyte’s CCS, e.g., dynamic clustering or fragmentation, can lead to broadened, shifted, or non-Gaussian ATDs and how sensitive these processes are to the applied field strengths. We highlight how first-principles ion dynamics simulations can help to understand and even harness the mentioned effects.
UR - http://www.scopus.com/inward/record.url?scp=85199017469&partnerID=8YFLogxK
U2 - 10.1021/acs.analchem.4c02010
DO - 10.1021/acs.analchem.4c02010
M3 - Article
VL - 96
SP - 12433
EP - 12443
JO - Analytical chemistry
JF - Analytical chemistry
SN - 0003-2700
IS - 30
ER -