Gas Chromatographic-Ion Trap Mass Spectrometric Analysis of Volatile Organic Compounds by Ion–Molecule Reactions Using the Electron-Deficient Reagent Ion CCl₃⁺

Abstract

When using tetrachloromethane as the reagent gas in gas chromatography-ion trap mass spectrometry equipped with hybrid ionization source, the cation CCl(3)(+) was generated in high abundance and further gas-phase experiments showed that such an electron-deficient reagent ion CCl(3)(+) could undergo interesting ion-molecule reactions with various volatile organic compounds, which not only present some informative gas-phase reactions, but also facilitate qualitative analysis of diverse volatile compounds by providing unique mass spectral data that are characteristic of particular chemical structures. The ion-molecule reactions of the reagent ion CCl(3)(+) with different types of compounds were studied, and results showed that such reactions could give rise to structurally diagnostic ions, such as [M+CCl(3) - HCl](+) for aromatic hydrocarbons, [M - OH](+) for saturated cyclic ether, ketone, and alcoholic compounds, [M - H](+) ion for monoterpenes, M(·+) for sesquiterpenes, [M - CH(3)CO](+) for esters, as well as the further fragment ions. The mechanisms of ion-molecule reactions of aromatic hydrocarbons, aliphatic ketones and alcoholic compounds with the reagent ion CCl(3)(+) were investigated and proposed according to the information provided by MS/MS experiments and theoretical calculations. Then, this method was applied to study volatile organic compounds in Dendranthema indicum var. aromaticum and 20 compounds, including monoterpenes and their oxygen-containing derivatives, aromatic hydrocarbon and sesquiterpenes were identified using such ion-molecule reactions. This study offers a perspective and an alternative tool for the analysis and identification of various volatile compounds.

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

“…This work is consistent with the related (GC/MS) results obtained by Wang et al ., who used tetrachloromethane as a reagent gas to effect the CI of VOCs that were first separated by GC. To further verify the nature of the ion‐molecule chemistry that we observe, an isotopically labeled reagent ion (CDCl 2 + ) was used to confirm that the hydrogen is abstracted from the phenyl ring during the neutral HCl loss (Supplementary Fig.…”

Analysis of Trace‐Level Volatile Compounds in Fresh Turf Crop (Lolium perenne L.) by Gas Chromatography Quadrupole Time‐of‐Flight Mass Spectrometry

“…[ [29][30][31][32][33] Figure 1 Total ion current chromatogram of volatile compounds from fresh Lolium perenne L. by static headspace gas chromatography mass spectrometry.…”

Novel Linear Ion Trap Mass Analyzer Built with Triangular Electrodes

“…Mass spectrometry is a very important analysis technique in modern analytical science, being widely used in many areas on account of its high speed, high specificity, high sensitivity, and high resolving power. − Conventional mass spectrometers tend to be of relatively large size and weight, consume significant power, and in terms of manufacture and maintenance, are relatively complex. As a consequence, such features have limited the application of mass spectrometers in many key areas.…”