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Mass Spectrom."],"published-print":{"date-parts":[[2015,11]]},"abstract":"<jats:p>A new type of electron ionization LC\u2010MS with supersonic molecular beams (EI\u2010LC\u2010MS with SMB) is described. This system and its operational methods are based on pneumatic spray formation of the LC liquid flow in a heated spray vaporization chamber, full sample thermal vaporization and subsequent electron ionization of vibrationally cold molecules in supersonic molecular beams. The vaporized sample compounds are transferred into a supersonic nozzle via a flow restrictor capillary. Consequently, while the pneumatic spray is formed and vaporized at above atmospheric pressure the supersonic nozzle backing pressure is about 0.15\u2009Bar for the formation of supersonic molecular beams with vibrationally cold sample molecules without cluster formation with the solvent vapor. The sample compounds are ionized in a fly\u2010though EI ion source as vibrationally cold molecules in the SMB, resulting in \u2018Cold EI\u2019 (EI of vibrationally cold molecules) mass spectra that exhibit the standard EI fragments combined with enhanced molecular ions. We evaluated the EI\u2010LC\u2010MS with SMB system and demonstrated its effectiveness in NIST library sample identification which is complemented with the availability of enhanced molecular ions. The EI\u2010LC\u2010MS with SMB system is characterized by linear response of five orders of magnitude and uniform compound independent response including for non\u2010polar compounds. This feature improves sample quantitation that can be approximated without compound specific calibration. Cold EI, like EI, is free from ion suppression and\/or enhancement effects (that plague ESI and\/or APCI) which facilitate faster LC separation because full separation is not essential. The absence of ion suppression effects enables the exploration of fast flow injection MS\u2010MS as an alternative to lengthy LC\u2010MS analysis. These features are demonstrated in a few examples, and the analysis of the main ingredients of Cannabis on a few Cannabis flower extracts is demonstrated. Finally, the advantages of EI\u2010LC\u2010MS with SMB are listed and discussed. 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