Gas Chromatography–Atmospheric Pressure Inlet–Mass Spectrometer Utilizing Plasma-Based Soft Ionization for the Analysis of Saturated, Aliphatic Hydrocarbons

Weber, Markus; Wolf, Jan-Christoph; Haisch, Christoph

doi:10.1021/jasms.0c00476

Cited by 16 publications

(24 citation statements)

References 38 publications

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“…By classification, API Group III base oils, such as that used in the present work, may contain less than or equal to 10% unsaturated hydrocarbon content, suggesting that the presence of some alkenes is likely 25 . Hydride abstraction has been posited as the initial step in the ionisation of alkanes using DBDI, where the formed ions undergo additional reactions in many cases 15 . To investigate the hypothesis of stabilised hydride abstraction in alkene ionisation, two linear alkenes, namely 1‐decene and 1‐dodecene, in addition to two linear alkanes, namely n ‐decane and n ‐dodecane, were analysed.…”

Section: Resultsmentioning

confidence: 99%

“…13,14 A range of alkanes, including those in a diesel sample, have been effectively quantified using GC coupled to this source design. 15 Herein the application of DBDI-MS in determining the chemical composition of an FFO is reported. A commercially available experimental set-up has been adapted to allow analysis of an FFO using active capillary DBDI in both positive and negative ion mode MS, directly from appropriately diluted liquid samples.…”

Section: •+mentioning

confidence: 99%

“…Discontinuous data at 25 carbons in both polarities arises from ionisation of residual phenolic antioxidant [Color figure can be viewed at wileyonlinelibrary.com] alkanes using DBDI, where the formed ions undergo additional reactions in many cases. 15 To investigate the hypothesis of stabilised hydride abstraction in alkene ionisation, two linear alkenes, namely 1-decene and 1-dodecene, in addition to two linear alkanes, namely ndecane and n-dodecane, were analysed. Visualisation of the ratios of ions generated allows the propensity of ion formation to be compared (Figure 6).…”

Section: Negative Ion Mode Dbdi-msmentioning

confidence: 99%

“…Not only does the development of a non‐ambient DBDI source allow coupling to more automated sampling methods, such as gas chromatography (GC) and solid‐phase microextraction (SPME), but also allows low limits of detection for particular analytes to be demonstrated 13,14 . A range of alkanes, including those in a diesel sample, have been effectively quantified using GC coupled to this source design 15 …”

Section: Introductionmentioning

confidence: 99%

“… 13 , 14 A range of alkanes, including those in a diesel sample, have been effectively quantified using GC coupled to this source design. 15 …”

Section: Introductionmentioning

confidence: 99%

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Detailed chemical analysis of a fully formulated oil using dielectric barrier discharge ionisation–mass spectrometry

Vincent

Hancock²,

Mckendrick

et al. 2022

Rapid Comm Mass Spectrometry

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Rationale Fully formulated oils (FFOs) are integral to automotive lubrication; however, detailed compositional analysis is challenging due to high levels of chemical complexity. In particular, existing mass spectrometric approaches often target particular FFO components, leading to poor analytical coverage of the overall formulation, with increased overheads and analytical timescales. Methods Herein we report the application of a commercially available SICRIT SC‐20 dielectric barrier discharge ionisation (DBDI) source and Thermo Fisher Scientific LTQ Orbitrap XL to the analysis of an FFO. Nitrogen was used as a discharge gas for the DBDI source, and was modified using a range of commonplace solvents to tailor the experimental conditions for the analysis of various components. Results The reported method allowed analysis of a range of FFO components of interest, encompassing a wide range of chemistries, in under 1 min. By modifying the discharge gas used for ionisation, experiments could be optimised for the analysis of particular FFO components across positive and negative ion modes. In particular, use of water vapour as a discharge gas modifier with positive ion mode mass spectrometry permitted concomitant analysis of antioxidants and base oil hydrocarbons. Furthermore, case studies of selected linear alkanes and alkenes profile the differences in the range of ions formed across these saturated and unsaturated aliphatic compounds, giving insight into the fate of base oil hydrocarbons in FFO analyses. Conclusions A rapid method for analysis of FFO compositions has been developed and provides coverage of a range of components of interest. The results indicate that the method presented may be of utility in analysis of other FFOs or similarly challenging complex mixtures.

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Section: Resultsmentioning

confidence: 99%

Section: •+mentioning

confidence: 99%

Section: Negative Ion Mode Dbdi-msmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

“… 13 , 14 A range of alkanes, including those in a diesel sample, have been effectively quantified using GC coupled to this source design. 15 …”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Detailed chemical analysis of a fully formulated oil using dielectric barrier discharge ionisation–mass spectrometry

Vincent

Hancock²,

Mckendrick

et al. 2022

Rapid Comm Mass Spectrometry

View full text Add to dashboard Cite

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Rapid Untargeted Puff‐by‐Puff Analysis of (Electronic) Cigarette Emissions by Concentric Dielectric Barrier Discharge Ionisation Mass Spectrometry

Gao,

Gasilova,

Wolf

et al. 2024

Analysis & Sensing

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Despite the soaring popularity of e‐cigarettes among teenagers and young adults, our understanding of the full extent of their health hazards have remained limited. This is due to the vast complexities of e‐cigarette aerosols and the difficulty in their full characterisation. Conventional mass spectrometry methods of e‐cigarette analysis, though pioneering in driving political and medical discourse, have been limited in their capabilities to uncover all compounds in its emissions due to prominent limitations in experimental setup. To overcome this major hurdle, we have developed a setup for puff‐by‐puff analysis of electronic and conventional cigarette emissions by concentric dielectric barrier discharge ionisation mass spectrometry. In this pilot study, the simple setup of in‐line dilution and high‐resolution mass spectrometry analysis allowed us to directly uncover 225 compounds in e‐cigarette puffs across a wide spectrum of chemical characteristics in two sequential 5‐minute runs. These include acids, carbonyls, aromatic cyclics, heterocyclics, unsaturated and saturated hydrocarbons, alcohols, esters, alkaloids, sulfur‐containing compounds, oxides, and nitriles. As a result, our setup provided a significant improvement in rapid compound identification, and demonstrated a much broader chemical landscape in e‐cigarette emissions than previously reported.

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Discovery of Combustion‐Like in‐Source Oxidation of Linear Saturated Hydrocarbons Using GC‐APCI‐HRMS

Brown,

Seaton,

Powers

et al. 2024

J Mass Spectrom

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Atmospheric pressure chemical ionization (APCI) is often used in the analysis of linear saturated hydrocarbons (LSHs) as this ionization technique commonly produces [M − H]+ ions in high abundance. However, APCI (along with other atmospheric pressure sources) is often impacted by in‐source oxidation, leading to a variety of ionic products. Identifying these products and understanding their mechanisms of formation is crucial for characterizing complex mixtures with substantial hydrocarbon content, such as those found in the petrochemical industry. In this study, in‐source oxidation of LSHs was observed in gas chromatography (GC) coupled to high‐resolution mass spectrometry (HRMS) via a custom‐built APCI interface. Studies showed that the abundance of these oxidized ions correlated positively with atmospheric water, yet occurred without the inclusion of water‐based oxygen as judged by experiments with stable isotope‐labeled water. The oxidation of LSHs was further influenced by the reactive species in the ionization atmosphere. Fragmentation data using stable isotope‐labeled LSH standards unveiled multiple structurally unique ions with one or more oxidation sites on both primary and secondary carbons. These ionic products bear resemblance to combustion byproducts, suggesting the instrumental configuration fosters plasma‐assisted combustion‐like processes that encourage the radical‐mediated oxidation of LSHs rather than generate [M − H]+. Through these investigative efforts, a mechanism analogous to combustion was proposed for the formation of LSH oxidation products in GC‐APCI‐HRMS. Data demonstrate that these ions are robustly generated in petrochemical products, allowing for proper characterization of these complex mixtures.

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Gas Chromatography–Atmospheric Pressure Inlet–Mass Spectrometer Utilizing Plasma-Based Soft Ionization for the Analysis of Saturated, Aliphatic Hydrocarbons

Cited by 16 publications

References 38 publications

Detailed chemical analysis of a fully formulated oil using dielectric barrier discharge ionisation–mass spectrometry

Detailed chemical analysis of a fully formulated oil using dielectric barrier discharge ionisation–mass spectrometry

Rapid Untargeted Puff‐by‐Puff Analysis of (Electronic) Cigarette Emissions by Concentric Dielectric Barrier Discharge Ionisation Mass Spectrometry

Discovery of Combustion‐Like in‐Source Oxidation of Linear Saturated Hydrocarbons Using GC‐APCI‐HRMS

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