A membrane introduction mass spectrometer utilizing ion-molecule reactions for the on-line speciation and quantitation of volatile organic molecules

Davey, Nicholas G.; Bell, Ryan J.; Krogh, Erik; Gill, Chris G.

doi:10.1002/rcm.7380

Cited by 7 publications

(4 citation statements)

References 43 publications

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“…The main drawback of the use of EI sources is the complexity of the mixture spectra as EI fragments each molecular ion into a large number of daughter ions, most of them being not specific of the molecule. On the contrary, chemical ionization (CI) methods produce low fragmentation, and then an easy-to-read mass spectrum without further separation [7,8]. In instruments such as Selective Ion Flow Tube (SIFT) [9] or Fourier Transform Ion Cyclotron Resonance (FT-ICR) [10], controlled conditions in the ionization zone enable direct quantification of the gas introduced.…”

Section: Introductionmentioning

confidence: 99%

Evidence of Reactivity in the Membrane for the Unstable Monochloramine during MIMS Analysis

Louarn

Asri-Idlibi

Leprovost

et al. 2018

Sensors

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Membrane Inlet Mass Spectrometry (MIMS) was used to analyze monochloramine solutions (NH2Cl) and ammonia solutions in a compact FTICR. Chemical ionization enables identification and quantification of the products present in the permeate. The responses of protonated monochloramine and ammonium increase linearly with the solution concentration. The enrichments were respectively 1.2 and 5.5. Pervaporation is dependent on pH and only the basic form of ammonia NH3 pervaporates through the membrane. Unexpectedly, the small ammonia molecule permeated very slowly. It could be due to interactions with water molecules inside the membrane that create clusters. Moreover, NH2Cl solutions, in addition to the NH3Cl+ signal, presented a strong NH4+ signal at m/z 18.034. Ammonia presence in the low-pressure zone before ionization is probable as NH4+ was detected with all the precursors used, particularly CF3+ and trimethylbenzene that presents a proton affinity higher than monochloramine. Ammonia may be formed inside the membrane due to the fact that NH2Cl is unstable and may react with the water present in the membrane. Those results highlight the need for caution when dealing with chloramines in MIMS and more generally with unstable molecules.

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Section: Introductionmentioning

confidence: 99%

Evidence of Reactivity in the Membrane for the Unstable Monochloramine during MIMS Analysis

Louarn

Asri-Idlibi

Leprovost

et al. 2018

Sensors

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“…Analysis of the constructed VOC mixtures was used to systematically test our ability to discriminate and classify samples of known composition and concentration using PCA, cluster analysis, and kNN. The sample mixtures were constructed to include compounds with relatively unique mass spectra (e.g., biphenyl, naphthalene) as well as those where significant isobaric interferences are known to exist (e.g., the tropylium ion (C 7 H 7 + ), m/z 91, is a fragment ion of toluene, α‐pinene, and m ‐xylene) . MCR tested our ability to derive the pure component mass spectra and the contribution profiles of each component in the mixtures.…”

Section: Resultsmentioning

confidence: 99%

Discrimination of constructed air samples using multivariate analysis of full scan membrane introduction mass spectrometry (MIMS) data

Richards

Davey

Fyles

et al. 2018

Rapid Comm Mass Spectrometry

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“…Membrane‐based ionization reagent addition has been employed by our group for gas‐phase MIMS measurements utilizing chemical ionization. Davey et al utilized a MIMS system employing a second membrane system to introduce chemical ionization (CI) reagents to a flowing helium acceptor prior to analyte sampling 28 . This allowed the on‐line addition of gas‐phase CI reagent, and the flexible utilization of CI reagent ions in a quadrupole ion trap without significant hardware modifications.…”

Section: Introductionmentioning

confidence: 99%

“…Davey et al utilized a MIMS system employing a second membrane system to introduce chemical ionization (CI) reagents to a flowing helium acceptor prior to analyte sampling. 28 This allowed the on-line addition of gas-phase CI reagent, and the flexible utilization of CI reagent ions in a quadrupole ion trap without significant hardware modifications. This work, and the electrodialysis approaches used in ion chromatography, inspired us to develop the membrane-based liquid ionization reagent addition strategy for MS, with potential applications in LC/MS and other separation approaches.…”

mentioning

confidence: 99%

A passive membrane system for on‐line mass spectrometry reagent addition

Zarkovic

Borden

Krogh

et al. 2023

Rapid Comm Mass Spectrometry

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Rationale: Post-separation addition of chemical modifiers in liquid chromatographymass spectrometry is widely used for improving ionization sensitivity and selectivity. This is typically accomplished using a post-column T-junction, which can result in sample dilution and imperfect mixing. We present a passive semi-permeable hollow fiber membrane approach for the addition of chemical modifiers that avoids these issues.Methods: Model compounds were directly infused by flow injection to an electrospray ionization triple quadrupole mass spectrometer after passing through a polydimethylsiloxane hollow fiber membrane. Ionization enhancement reagents were introduced into the flowing stream by membrane permeation from aqueous solutions. Ionization enhancement from volatile acids and bases in positive and negative electrospray ionization was evaluated to assess the feasibility of this approach.Results: The membrane-based apparatus resulted in relative ionization enhancement factors of up to 14Â, depending upon the analyte, reagent, and ionization mode used. Ionization enhancement signal stability is reasonable (relative standard deviation of 5-7%) for extended periods from the same reagent solution, and minimal analyte dilution is observed. A proof-of-concept demonstration of the chromatographic "trifluoroacetic acid fix" strategy is presented.Conclusions: An on-line mass spectrometry ionization reagent addition method with potential post-chromatography reagent addition applications was developed using a hollow fiber polydimethylsiloxane membrane. This approach offers a promising alternative to traditional methods requiring additional hardware such as pumps and T-junctions that can result in sample dilution and imperfect reagent mixing. | INTRODUCTIONThe post-separation infusion of derivatizing reagents and chemical modifiers in liquid chromatography-mass spectrometry (LC/MS) workflows has been widely used to enhance ionization without altering chromatographic performance. This is done because optimal separation solvent systems can be quite different from those needed for efficient ionization. 1,2 Reagents are frequently introduced to the LC eluent via a T-junction, infusing reagent via a second pumping system. Other post-column addition techniques (still utilizing secondary liquid handling pumps) include the use of reaction coils 3 and triaxial electrospray probes. 4 Although analyte ionization is

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A membrane introduction mass spectrometer utilizing ion-molecule reactions for the on-line speciation and quantitation of volatile organic molecules

Cited by 7 publications

References 43 publications

Evidence of Reactivity in the Membrane for the Unstable Monochloramine during MIMS Analysis

Evidence of Reactivity in the Membrane for the Unstable Monochloramine during MIMS Analysis

Discrimination of constructed air samples using multivariate analysis of full scan membrane introduction mass spectrometry (MIMS) data

A passive membrane system for on‐line mass spectrometry reagent addition

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