New trends in the application of electron ionization to liquid chromatography—mass spectrometry interfacing

I. Introduction 88 II. Cap-EI Interface 90 A. Interface Performance 92 III. Direct-EI Interface 93 A. Interface Performance 97 IV. Conclusions 103 Acknowledgments 103 References 103 Two recent approaches for coupling capillary scale liquid chromatography and electron ionization mass spectrometry are reviewed and discussed. The first one, Cap-EI, is the latest evolution of the micro-scale particle beam interface, in which the nebulizer has been optimized to overcome the limitations of the former approach, in terms of sensitivity and linearity. It can be easily hosted in pre-existing instruments without major modifications and can use helium and the less-expensive nitrogen to generate library-matchable electron ionization spectra. The second one is a miniaturized interface for nano- and micro-HPLC, in which the interfacing process takes place into a suitably modified ion source. Because the eluate from the column is completely transferred into the ion source for ionization, superior sensitivity, linearity, and reproducibility are obtained. No signs of chemical ionization are observed at flow rates up to 1.5 μL/min. These two interfaces demonstrate that electron ionization can be successfully used for the analysis of small—medium molecules of various polarities, and also at the trace level. The possibility to record library-matchable electron ionization spectra offers the analyst a powerful tool that can be particularly useful in real-world applications.