Dielectric barrier discharge ionization (DBDI) is a versatile tool for small-molecule mass spectrometry applications, helping cover from polar to low polar molecules. However, the plasma gas-phase interactions are highly complex and have been scarcely investigated. The ionization mechanisms of plasmas have long been assumed to be somewhat similar to atmospheric pressure chemical ionization (APCI). Here, we evaluated the ionization mechanisms of a two-ring DBDI ion source, using different discharge gases to analyze vaporized liquid samples. Polycyclic aromatic hydrocarbons (PAHs) were used as model analytes to assess the mechanisms' dominance: protonation, [M + H] + , or radical ion species formation, [M] •+ . In the present work, two different ionization trends were observed for APCI and DBDI during the PAH analysis; the compounds with proton affinities (PA) over 856 kJ/mol were detected as [M + H] + when APCI was used as ionization source. Meanwhile, independently of the PA, DBDI showed the prevalence of charge exchange reactions. The addition of dopants in the gas-phase region shifted the ionization mechanisms toward charge exchange reactions, facilitating the formation of [M] •+ ion species, showing anisole a significant boost of the PAH radical ion species signals, over nine times for Ar-Prop-DBDI analysis. The presence of high-energy metastable atoms (e.g., He M ) with high ionization potentials (IE = 19.80 eV) did not show boosted PAH abundances or extensive molecule fragmentation. Moreover, other species in the plasma jet region with closer and more appropriate IE, such as N 2 B 3 Π g excited molecules, are likely responsible for PAH Penning ionization.
Dielectric barrier discharge ionization has gained attention in the last few years due to its versatility and the vast array of molecules that can be ionized. In this study, we report on the assessment of liquid chromatography coupled to dielectric barrier discharge ionization with mass spectrometry for neutral lipid analysis. A set of different neutral lipid subclasses (triacylglycerides, diacylglycerides, and sterols) were selected for the study. The main species detected from our ionization source were [M‐H2O+H]+, [M+H]+ or [M‐R‐H2O+H]+, attributed to sterol dehydration, protonation or the fragmentation of an acyl chain accompanied by a water loss of the glycerolipids, respectively. In terms of sensitivity, the dielectric barrier discharge displayed overall improved abundances and comparable or better limits of quantitation than atmospheric pressure chemical ionization for both acylglycerols and sterols. As a case study, different archaeological samples with variable content in neutral lipids, particularly triacylglycerides, were studied. The identification was carried out by combining accurate mass and the tentative formula associated with the exact mass, retention time matching with standards, and additional structural information from in‐source fragmentation. The high degree of unsaturation and the presence of sterols revealed the potential vegetal origin of the material stored in the analyzed samples.
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