Polymers for Traveling Wave Ion Mobility Spectrometry Calibration

Duez, Quentin; Chirot, Fabien; Liénard, Romain; Josse, Thomas; Choi, Chang Min; Coulembier, Olivier; Dugourd, Philippe; Cornil, Jérôme; Gerbaux, Pascal; Winter, Julien De

doi:10.1007/s13361-017-1762-4

Cited by 42 publications

(55 citation statements)

References 33 publications

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“…Specifically, the 1+ charge state and the low-or high-DP complexes for multiply charged ions seem to present robust IM behaviors. This is of crucial interest for the robustness and reproducibility of IM calibration strategies based on synthetic homopolymers [38,49], especially if based solely on singly charged synthetic homopolymers [38]. Our data indeed suggest that the activation energy provided to the polymer ions by collisions with, e.g., the drying gas does not affect their resulting apparent CCS values.…”

Section: General Cid and Etd Reactivity Assessmentmentioning

confidence: 63%

“…Furthermore, the results demonstrated the robustness and reproducibility of the polymer ion drift times and CCS (or K 0 ) values. This makes them well suited as IM calibrating substances, especially the singly charged (PEO) polymer ions [38,49]. These ions could even be created in the gas phase as fragmentation product ions from higher DP and higher charge state precursor ions, thus also opening the way for accurate IM calibrations in CIU experiments.…”

Section: Discussionmentioning

confidence: 99%

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Gas-Phase Dynamics of Collision Induced Unfolding, Collision Induced Dissociation, and Electron Transfer Dissociation-Activated Polymer Ions

Haler

Massonnet

Far

et al. 2018

J. Am. Soc. Mass Spectrom.

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Polymer characterizations are often performed using mass spectrometry (MS). Aside from MS and different tandem MS (MS/MS) techniques, ion mobility-mass spectrometry (IM-MS) has been recently added to the inventory of characterization technique. However, only few studies have focused on the reproducibility and robustness of polymer IM-MS analyses. Here, we perform collisional and electron-mediated activation of polymer ions before measuring IM drift times, collision cross-sections (CCS), or reduced ion mobilities (K 0 ). The resulting IM behavior of different activated product ions is then compared to non-activated native intact polymer ions. First, we analyzed collision induced unfolding (CIU) of precursor ions to test the robustness of polymer ion shapes. Then, we focused on fragmentation product ions to test for shape retentions from the precursor ions: cation ejection species (CES) and product ions with m/z and charge state values identical to native intact polymer ions. The CES species are formed using both collision induced dissociation (CID) and electron transfer dissociation (ETD, formally ETnoD) experiments. Only small drift time, CCS, or K 0 deviations between the activated/formed ions are observed compared to the native intact polymer ions. The polymer ion shapes seem to depend solely on their mass and charge state. The experiments were performed on three synthetic homopolymers: poly(ethoxy phosphate) (PEtP), poly(2-n-propyl-2-oxazoline) (Pn-PrOx), and poly(ethylene oxide) (PEO). These results confirm the robustness of polymer ion CCSs for IM calibration, especially singly charged polymer ions. The results are also discussed in the context of polymer analyses, CCS predictions, and probing ion-drift gas interaction potentials.

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Section: General Cid and Etd Reactivity Assessmentmentioning

confidence: 63%

Section: Discussionmentioning

confidence: 99%

Gas-Phase Dynamics of Collision Induced Unfolding, Collision Induced Dissociation, and Electron Transfer Dissociation-Activated Polymer Ions

Haler

Massonnet

Far

et al. 2018

J. Am. Soc. Mass Spectrom.

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“…The hexakis‐fluoropropoxyphospahzines (Agilent Tunemix calibration standard (Stow et al, )) and polyalanine (Allen et al, ) satisfy the criteria and are compatible with ESI. Several other synthetic polymers (Duez et al, ; Haler et al, , ) or supramolecular assemblies (Hupin et al, ) have recently been proposed as alternative calibrants. Finding new reference materials is currently a very active area of research, and it is expected that a few more years of testing will be necessary to reach consensus on the species and their mobilities.…”

Section: Reference Materials For Ion Mobilitymentioning

confidence: 99%

Recommendations for reporting ion mobility Mass Spectrometry measurements

Gabelica

Shvartsburg

Afonso

et al. 2019

Mass Spectrometry Reviews

337

464

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Here we present a guide to ion mobility mass spectrometry experiments, which covers both linear and nonlinear methods: what is measured, how the measurements are done, and how to report the results, including the uncertainties of mobility and collision cross section values. The guide aims to clarify some possibly confusing concepts, and the reporting recommendations should help researchers, authors and reviewers to contribute comprehensive reports, so that the ion mobility data can be reused more confidently. Starting from the concept of the definition of the measurand, we emphasize that (i) mobility values ( K 0 ) depend intrinsically on ion structure, the nature of the bath gas, temperature, and E / N ; (ii) ion mobility does not measure molecular surfaces directly, but collision cross section (CCS) values are derived from mobility values using a physical model; (iii) methods relying on calibration are empirical (and thus may provide method‐dependent results) only if the gas nature, temperature or E / N cannot match those of the primary method. Our analysis highlights the urgency of a community effort toward establishing primary standards and reference materials for ion mobility, and provides recommendations to do so. © 2019 The Authors. Mass Spectrometry Reviews Published by Wiley Periodicals, Inc.

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“…Arrival time distributions (ATDs) are recorded by selecting the most abundant isotope for each ion composition to avoid unspecific selection. ATDs are converted into collisional cross‐section (CCS) distributions in helium by means of a polymer calibration following a procedure detailed in the literature using commercial PEG samples with average molecular weights of 600 and 1000 g.mol −1 . The CCSs in Table were determined at the APEX of the CCS distributions.…”

Section: Methodsmentioning

confidence: 99%

Ion mobility mass spectrometry of saponin ions

Decroo

Colson

Lemaur

et al. 2018

Rapid Comm Mass Spectrometry

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Rationale Saponins are natural compounds presenting a high structural diversity whose structural characterization remains extremely challenging. Ideally, saponin structures are best established using nuclear magnetic resonance experiments conducted on isolated molecules. However, saponins are also increasingly characterized using tandem mass spectrometry (MS/MS) coupled with liquid chromatography, even if collision‐induced dissociation (CID) experiments are often quite limited in accurately determining the saponin structure. Methods We consider here ion mobility mass spectrometry (IMMS) as an orthogonal tool for the structural characterization of saponin isomers by comparing the experimental collisional cross sections (CCSs) of saponin ions with theoretical CCSs for candidate ion structures. Indeed, state‐of‐the‐art theoretical calculations perfectly complement the experimental results, allowing the ion structures to be deciphered at the molecular level. Results We demonstrate that ion mobility can contribute to the structural characterization of saponins because different saponin ions present significantly distinct CCSs. Depending on the nature of the cation (in the positive ion mode), the differences in CCSs can also be exacerbated, optimizing the gas‐phase separation. When associated with molecular dynamics simulations, the CCS data can be used to describe the interactions between the cations, i.e. H+, Na+ and K+, and the saponin molecules at a molecular level. Conclusions Our work contributes to resolve the relationship between the primary and secondary structures of saponin ions. However, it is obvious that the structural diversity and complexity of the saponins cannot be definitively unraveled by measuring a single numerical value, here the CCS. Consequently, the structural characterization of unknown saponins will be difficult to achieve based on IMMS alone. Nevertheless, we demonstrated that monodesmosidic and bidesmosidic saponins can be distinguished via IMMS.

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Polymers for Traveling Wave Ion Mobility Spectrometry Calibration

Cited by 42 publications

References 33 publications

Gas-Phase Dynamics of Collision Induced Unfolding, Collision Induced Dissociation, and Electron Transfer Dissociation-Activated Polymer Ions

Gas-Phase Dynamics of Collision Induced Unfolding, Collision Induced Dissociation, and Electron Transfer Dissociation-Activated Polymer Ions

Recommendations for reporting ion mobility Mass Spectrometry measurements

Ion mobility mass spectrometry of saponin ions

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