Humidity Effects on Fragmentation in Plasma-Based Ambient Ionization Sources

Newsome, G. Asher; Ackerman, Luke K.; Johnson, Kevin

doi:10.1007/s13361-015-1259-y

Cited by 33 publications

(31 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The hydronium cluster model can again not explain these findings, since no (or at most, a constant) in-source fragmentation would be expected for proton transfer alone. The increase in in-source fragmentation for decreasing relative humidity was also observed with the flowing atmosphericpressure afterglow (FAPA) and DART, but has so far not been explained mechanistically [25]. With increasing amount of protons available for abstraction (higher humidity), the formation of the protonated analyte is favored and therefore the in-source fragmentation is reduced.…”

Section: Resultsmentioning

confidence: 96%

A Radical-Mediated Pathway for the Formation of [M + H]⁺ in Dielectric Barrier Discharge Ionization

Wolf

Gyr

Mirabelli

et al. 2016

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

Abstract. Active capillary plasma ionization is a highly efficient ambient ionization method. Its general principle of ion formation is closely related to atmospheric pressure chemical ionization (APCI). The method is based on dielectric barrier discharge ionization (DBDI), and can be constructed in the form of a direct flowthrough interface to a mass spectrometer. Protonated species ([M + H] + ) are predominantly formed, although in some cases radical cations are also observed. We investigated the underlying ionization mechanisms and reaction pathways for the formation of protonated analyte ([M + H] + ). We found that ionization occurs in the presence and in the absence of water vapor. Therefore, the mechanism cannot exclusively rely on hydronium clusters, as generally accepted for APCI. Based on isotope labeling experiments, protons were shown to originate from various solvents (other than water) and, to a minor extent, from gaseous impurities and/or self-protonation. By using CO 2 instead of air or N 2 as plasma gas, additional species like [M + OH] + and [M − H] + were observed. These gas-phase reaction products of CO 2 with the analyte (tertiary amines) indicate the presence of a radical-mediated ionization pathway, which proceeds by direct reaction of the ionized plasma gas with the analyte. The proposed reaction pathway is supported with density functional theory (DFT) calculations. These findings add a new ionization pathway leading to the protonated species to those currently known for APCI.

show abstract

Section: Resultsmentioning

confidence: 96%

A Radical-Mediated Pathway for the Formation of [M + H]⁺ in Dielectric Barrier Discharge Ionization

Wolf

Gyr

Mirabelli

et al. 2016

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

show abstract

“…Previous studies demonstrate an effect of humidity on low temperature plasma ionization sources [57][58][59] . Overall, previous work shows that water concentration can change relative reagent ion abundances, analyte signal intensities and extent of fragmentation.…”

Section: Impact Of Humidity On Ionization Of Organic Acidsmentioning

confidence: 97%

Combining Mass Spectrometry of Picoliter Samples with a Multicompartment Electrodynamic Trap for Probing the Chemistry of Droplet Arrays

2020

View full text Add to dashboard Cite

Single droplet levitation provides contactless access to the microphysical and chemical properties of micron-sized samples. Most applications of droplet levitation to chemical and biological systems use non-destructive optical techniques to probe droplet properties. To provide improved chemical specificity, we couple a multi-compartment quadrupole electrodynamic trap (QET) to single droplet mass spectrometry. Our QET continuously traps a monodisperse droplet population (∼10's -100's of droplets), and allows for simultaneous sizing of a single droplet using its Mie scattering pattern. Single droplets are subsequently ejected to the ionization region of an ambient pressure inlet mass spectrometer. We optimize two complementary soft ionization techniques for picoliter aqueous droplets: paper spray (PS) ionization and thermal desorption glow discharge (TDGD) ionization. Both techniques detect oxygenated organic acids in single droplets with signal-to-noise ratios >100 and detection limits on the order of

show abstract

“…Also, analytical conditions may significantly affect this particular signal response, making it more susceptible to interference from unknown co-eluting ion suppressors or enhancers. Lastly, other factors may influence the formation of peroxide products [96].…”

Section: Detectionmentioning

confidence: 99%

“…Significant changes in molecular adduct ion signal abundance especially impair trace detection and quantitation or MS/MS ion statistics. One remedy is to indirectly control humidity by elevating discharge temperature so that humidity effects are diminished without also causing excessive fragmentation [96].…”

Section: Detectionmentioning

confidence: 99%

Peroxide Based Organic Explosives

Türker

2021

EJCS

View full text Add to dashboard Cite

In recent years progressively increasing terrorist activities, which use homemade explosives; such as acetone peroxide and other cyclic organic peroxides have led to worldwide awareness by security and defense agencies. Then the development of methodologies for the detection of cyclic organic peroxides have become an urgent need. Until quite recently, most of the current technology in use for trace detection of explosives had been unable to detect these energetic compounds. Differences in physical properties between cyclic organic peroxides is the main barrier for the development of a general method for analysis and detection of the peroxide explosives. In this short review, the most relevant contributions related to preparation, characterization and detection of the most important cyclic organic peroxides have been presented. It also includes few recent investigations about the toxicity and metabolism of some peroxide explosives.

show abstract

Humidity Effects on Fragmentation in Plasma-Based Ambient Ionization Sources

Cited by 33 publications

References 30 publications

A Radical-Mediated Pathway for the Formation of [M + H]⁺ in Dielectric Barrier Discharge Ionization

A Radical-Mediated Pathway for the Formation of [M + H]⁺ in Dielectric Barrier Discharge Ionization

Combining Mass Spectrometry of Picoliter Samples with a Multicompartment Electrodynamic Trap for Probing the Chemistry of Droplet Arrays

Peroxide Based Organic Explosives

Contact Info

Product

Resources

About

Humidity Effects on Fragmentation in Plasma-Based Ambient Ionization Sources

Cited by 33 publications

References 30 publications

A Radical-Mediated Pathway for the Formation of [M + H]+ in Dielectric Barrier Discharge Ionization

A Radical-Mediated Pathway for the Formation of [M + H]+ in Dielectric Barrier Discharge Ionization

Combining Mass Spectrometry of Picoliter Samples with a Multicompartment Electrodynamic Trap for Probing the Chemistry of Droplet Arrays

Peroxide Based Organic Explosives

Contact Info

Product

Resources

About

A Radical-Mediated Pathway for the Formation of [M + H]⁺ in Dielectric Barrier Discharge Ionization

A Radical-Mediated Pathway for the Formation of [M + H]⁺ in Dielectric Barrier Discharge Ionization