Analysis of Compounds Dissolved in Nonpolar Solvents by Electrospray Ionization on Conductive Nanomaterials.

Electrospray ionization mass spectrometry (ESI-MS) technique has limitations in analysis of compounds that are dissolved in nonpolar solvents. In this study, ambient ionization of compounds in solvents that are not "friendly" to electrospray ionization, such as n-hexane, is achieved by conductive nanomaterials spray ionization (CNMSI) on nanomaterial emitters, including carbon nanotubes paper and mesodendritic silver covered metal, which applies high voltages to emitters made of these materials without the assistance of polar solvents. Although the time intensity curves (TIC) commonly vary from 4.5% to 23.7% over analyses, protonated molecular ions were found to be the most abundant species, demonstrating good reproducibility of the technique in terms of ionized species. Higher mass spectrometric responses are observed in analyzing nonpolar systems than polar systems. 2-Methoxyacetophenone, 4-methylacetophenone, benzothiazole, quinolone, and cycloheptanone as low as 2 pg in n-hexane can be directly detected using the developed method. The developed technique expands the analysis capability of ESI-MS for direct, online analysis of nonpolar systems, such as low polarity extracts, normal phase liquid chromatography eluates, and synthetic mixtures. Graphical Abstract.