Miniaturized flexible micro-tube plasma ionization source for the effective ionization of non-easily ionizable pesticides in food with liquid chromatography/mass spectrometry.

In this article, we have studied the potential of flexible microtube plasma (FµTP) as ionization source for the liquid chromatography high-resolution mass spectrometry detection of non-easily ionizable pesticides (viz. nonpolar and non-ionizable by acid/basic moieties). Phthalimide-related compounds such as dicofol, dinocap, o-phenylphenol, captan, captafol, folpet and their metabolites were studied. Dielectric barrier discharge ionization (DBDI) was examined using two electrode configurations, including the miniaturized one based on a single high-voltage (HV) electrode and a virtual ground electrode configuration (FµTP), and also the two-ring electrode DBDI configuration. Different ionization pathways were observed to ionize these challenging, non-easily ionizable nonpolar compounds, involving nucleophilic substitutions and proton abstraction, with subtle differences in the spectra obtained compared with APCI. An average sensitivity increase of 5-fold was attained compared with the standard APCI source. In addition, more tolerance with matrix effects was observed in both DBDI sources. The importance of the data reported is not just limited to the sensitivity enhancement compared to APCI, but, more notably, to the ability to effectively ionize nonpolar, late-eluting (in reverse-phase chromatography) non-ionizable compounds. Besides o-phenylphenol ([M - H]-), all the parent species were efficiently ionized through different mechanisms involving bond cleavages through the effect of plasma reagent species or its combination with thermal degradation and subsequent ionization. This tool can be used to figure out overlooked nonpolar compounds in different environmental samples of societal interest through non-target screening (NTS) strategies.

Dielectric Barrier Discharge Ionization Mechanisms: Polycyclic Aromatic Hydrocarbons as a Case of Study.

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., HeM) 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 N2 B3Πg excited molecules, are likely responsible for PAH Penning ionization.

Liquid chromatography-dielectric barrier discharge ionization mass spectrometry for the analysis of neutral lipids of archaeological interest.

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-H2 O+H]+ , [M+H]+ or [M-R-H2 O+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.