Combining linear retention index and electron ionization mass spectrometry for a reliable identification in nano liquid chromatography

The present research is focused on the object to improve identification capability in liquid chromatography (LC), by creating a system as similar as possible to gas chromatography (GC), where the combination/complementarity of Linear Retention Index (LRI) and Electron Ionization Mass Spectrometry (EI-MS) data makes the identification process easy, automatic and reliable. Conversely, in LC the untargeted characterization of real-world samples is still a challenge, due to the not repeatable and poorly informative nature of typical atmospheric pressure ionization mass spectrometry, normally hyphenated to LC. In the last decades the miniaturization of LC instrumentation together with the considerable progresses in MS vacuum pump capability has made the LC-EI-MS hyphenation more feasible. In the present work, a prototypal nanoLC-EI-MS system was used for the determination of typically LC-amenable compunds, such as coumarins, furocoumarins and polymethoxyflavones in citrus essential oils. All the compounds provided high quality EI-MS spectra, evaluated by the comparison with thousands of spectra present in commercial EI-MS libraries. Spectral similarities major than 80% were achieved. Furthermore, an LRI system, based on the use of an alkyl aryl ketone homologue reference series, was proposed as additional filter to achieve a univocal identification. Then, a novel dual-filter LRI/EI-MS library was built and resulted very helpful in the case of isomeric compounds characterized by identical EI-MS spectrum, but different retention behaviour. The very low inter-day variability attained for each LRI value, together with the satisfactory chromatographic resolution of the developed method, led to a 100% reliability of the identification process based on LRI.