Direct Infusion Resonance-Enhanced Multiphoton Ionization Mass Spectrometry of Liquid Samples under Vacuum Conditions.

Direct infusion resonance-enhanced multiphoton ionization (DI-REMPI) was performed on liquid samples, which were introduced to the ion source via a direct liquid interface, to enable the investigation of dissolved aromatic compounds. Desolvation and nebulization of the samples were supported by a heated repeller using flow rates in the upper nL min-1 range. The obtained mass spectra of five pure polycyclic aromatic hydrocarbons as well as complex petroleum samples revealed predominantly molecular ions without evidence of solvent or dopant effects as observed in atmospheric pressure photoionization (APPI) and laser ionization (APLI) with limits of detection in the lower pmol range. Furthermore, it is demonstrated by the analysis of different complex oil samples that DI-REMPI covers a larger m/z range than external volatilization of the sample prior to introduction to the ion source by using thermogravimetry (TG) hyphenated to REMPI time-of-flight mass spectrometry (TOFMS). Analogous to reported setups with direct liquid interface and electron ionization, direct-REMPI may be an option for soft ionization in liquid chromatography.