Gas phase fragmentation of protonated esters in air at ambient pressure through ion heating by electric field in differential mobility spectrometry

An, Xinxia; Eiceman, Gary A.; Rodriguez, Jaime E.; Stone, John A.

doi:10.1016/j.ijms.2011.01.031

Cited by 26 publications

(44 citation statements)

References 26 publications

(35 reference statements)

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“…This has been observed with butyl acetates in a conventional IMS drift tube [36], and with esters in other DMS studies [32]. This behaviour has been attributed to the energy partition and the heat capacity of the larger proton bound dimer compared to the protonated monomer.…”

Section: Concentration Dependence Of Differential Mobility Spectra Ofsupporting

confidence: 57%

Fragmentation, auto-modification and post ionisation proton bound dimer ion formation: the differential mobility spectrometry of low molecular weight alcohols

Ruszkiewicz

Thomas

Eiceman

2016

Analyst

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Section: Concentration Dependence Of Differential Mobility Spectra Ofsupporting

confidence: 57%

Fragmentation, auto-modification and post ionisation proton bound dimer ion formation: the differential mobility spectrometry of low molecular weight alcohols

Ruszkiewicz

Thomas

Eiceman

2016

Analyst

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“…For labile 11-α GTX and CTX epimers, relative intensity increases rapidly with % modifier up to about 0.8%. This can be attributed to the protective effect of the clustered modifier to field-induced fragmentation in the DMS [28][29][30][31], similar to that reported previously for the use of CO 2 as a gas additive in FAIMS [32,33]. For more stable 11-β epimers (Figure 2d), a decrease in relative intensity with increasing modifier content was observed.…”

Section: Dms Optimizationsupporting

confidence: 87%

“…Finally, fragmentation of GTX2 can also be induced during the DMS separation by increasing the temperature in the analyzer (T DMS ), as shown in Figure 6c. It has previously been shown that T DMS and field strength have an additive effect in inducing dissociation in DMS [28,31]. Unlike altering ESI or MS inlet conditions, increasing T DMS leads to a change in the dynamics of the DMS separation and thus in CV of transmission.…”

Section: Fragmentation Of Labile Psts Before During and After Dmsmentioning

confidence: 99%

Differential Mobility Spectrometry for Improved Selectivity in Hydrophilic Interaction Liquid Chromatography-Tandem Mass Spectrometry Analysis of Paralytic Shellfish Toxins

Beach

2017

J. Am. Soc. Mass Spectrom.

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Paralytic shellfish toxins (PSTs) are neurotoxins produced by dinoflagellates and cyanobacteria that cause paralytic shellfish poisoning in humans. PST quantitation by LC-MS is challenging because of their high polarity, lability as gas-phase ions, and large number of potentially interfering analogues. Differential mobility spectrometry (DMS) has the potential to improve the performance of LC-MS methods for PSTs in terms of selectivity and limits of detection. This work describes a comprehensive investigation of the separation of 16 regulated PSTs by DMS and the development of highly selective LC-DMS-MS methods for PST quantitation. The effects of all DMS parameters on the separation of PSTs from one another were first investigated in detail. The labile nature of 11α-gonyautoxin epimers gave unique insight into fragmentation of labile analytes before, during, and after the DMS analyzer. Two sets of DMS parameters were identified that either optimized the resolution of PSTs from one another or transmitted them at a limited number of compensation voltage (CV) values corresponding to structural subclasses. These were used to develop multidimensional LC-DMS-MS/MS methods using existing HILIC-MS/MS parameters. In both cases, improved selectivity was observed when using DMS, and the quantitative capabilities of a rapid UPLC-DMS-MS/MS method were evaluated. Limits of detection of the developed method were similar to those without DMS, and differences were highly analyte-dependant. Analysis of shellfish matrix reference materials showed good agreement with established methods. The developed methods will be useful in cases where specific matrix interferences are encountered in the LC-MS/MS analysis of PSTs in complex biological samples. Graphical Abstract ᅟ.

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“…As temperature increases, the gas number density decreases and the applied field strength increases. Further, as has been previously shown [31], the dissociation of dimer ions (analogous to the clustered ions stud- (normal operating temperature) to ∼85 Td at the highest achievable temperature. Fig.…”

Section: Temperature Effectssupporting

confidence: 59%

Solvent vapor effects in planar high-field asymmetric waveform ion mobility spectrometry: Solvent trends and temperature effects

Rorrer

Yost

2015

International Journal of Mass Spectrometry

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Gas phase fragmentation of protonated esters in air at ambient pressure through ion heating by electric field in differential mobility spectrometry

Cited by 26 publications

References 26 publications

Fragmentation, auto-modification and post ionisation proton bound dimer ion formation: the differential mobility spectrometry of low molecular weight alcohols

Fragmentation, auto-modification and post ionisation proton bound dimer ion formation: the differential mobility spectrometry of low molecular weight alcohols

Differential Mobility Spectrometry for Improved Selectivity in Hydrophilic Interaction Liquid Chromatography-Tandem Mass Spectrometry Analysis of Paralytic Shellfish Toxins

Solvent vapor effects in planar high-field asymmetric waveform ion mobility spectrometry: Solvent trends and temperature effects

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