Chemical analysis of electronic cigarette liquids (e-liquids) and direct nicotine quantitation using surface-assisted flowing atmospheric-pressure afterglow desorption/ionization mass spectrometry (SA-FAPA-MS).

Abstract

Ambient desorption/ionization mass spectrometry (ADI-MS) has been widely used for direct analysis of real samples without sample preparation or separation. Studies on the quantification of low molecular weight compounds in complex matrices with ADI-MS remain scarce. In this paper, we report the application of surface-assisted flowing atmospheric-pressure afterglow mass spectrometry (SA-FAPA-MS) for fast qualitative screening of electronic cigarette liquid (e-liquids) ingredients and direct quantification of nicotine. The quantification approach is rapid, uses a deuterated D4-nicotine standard spike, and does not require a preceding chromatography step or other methods to remove the complex sample matrix. Selected e-liquids were directly applied on thin-layer chromatography (TLC) plate surfaces (normal phase (NP) silica, reversed phase (RP) modified silica, cyano (CN) modified silica, and dimethyl (RP2) modified silica) after dilution and internal standard spiking. The plates served purely as sample carriers and no analyte separation was performed. Promising qualitative results were obtained, demonstrating the ability to detect nicotine alkaloids using this approach and the ability to differentiate e-liquids based on their flavor variations. In addition, dimethyl- (RP2-) and cyano-modified (CN-) silica surfaces were selected for quantification based on performance results of previous studies. It was shown that results were in high accordance with high-performance liquid chromatography (HPLC) experiments with lowest deviations <3% on dimethyl surfaces. Additional quantitative experiments including a certified reference material achieved equally satisfying results with lowest deviations of -1.1% from the certified nicotine content. For nicotine, detection limits down to the fmol range (96 fmol on CN and 20 fmol on RP2) were obtained. A detailed comparison of glass surfaces with functionalized surfaces showed that the functionalized surfaces were superior in terms of sample application reproducibility, mass spectra quality, sensitivity, and information density. Thus, functionalized thin-layer surfaces are considered promising tools for both qualitative and quantitative ADI-MS analysis of complex samples.