RESUMEN
Mass spectrometry (MS) enables precise identification and quantification of molecules, particularly when combined with chromatography. The advent of atmospheric pressure ionization (API) techniques allowed the efficient coupling of liquid chromatography with MS (LC-MS), extending analyses to nonvolatile and thermolabile compounds. API techniques present limitations such as low informative capacity and reproducibility of mass spectra, increasing instrument complexity and costs. Other challenges include analyzing poorly polar molecules and matrix effects (ME), which negatively impact quantitative analyses, necessitating extensive sample purification or using expensive labeled standards. These limitations prompted the exploration of alternative solutions, leading to the development of the Liquid Electron Ionization (LEI) interface. The system has demonstrated excellent robustness and reproducibility. LEI has been employed to analyze various compounds, including pesticides, drugs of abuse, phenols, polycyclic aromatic hydrocarbons (PAHs), phthalates, and many others. Its versatility has been validated with single quadrupole, triple quadrupole, and QToF detectors, operating in electron ionization (EI) or chemical ionization (CI) modes and with both reverse phase liquid chromatography (RPLC) and normal phase liquid chromatography (NPLC). LEI has also been successfully integrated with the Microfluidic Open Interface (MOI), Membrane Introduction Mass Spectrometry (MIMS), and Microfluidic Water-Assisted Trap Focusing (M-WATF), broadening its application scope and consistently demonstrating promising results in terms of sensitivity and identification power. The most recent advancement is the development of Extractive-Liquid Sampling Electron Ionization-Mass Spectrometry (E-LEI-MS), a surface sampling and real-time analysis technique based on the LEI concept. This review article offers a comprehensive and up-to-date picture of the potential of LEI.
RESUMEN
Normal-phase liquid chromatography (NPLC) plays a pivotal role in the rapid separation of non-polar compounds, facilitating isomer separation and finding applications in various crucial areas where aprotic solvents are necessary. Similar to reversed-phase liquid chromatography (RPLC), NPLC requires a robust and sensitive detector to unequivocally identify the analytes, such as a mass spectrometer. However, coupling NPLC with mass spectrometry (MS) poses challenges due to the incompatibility between the non-polar solvents used as the mobile phase and the primary ionization techniques employed in MS. Several analytical methods have been developed to combine NPLC with electrospray ionization (ESI), but these methods are restricted to the analysis of polar compounds. In most cases, atmospheric pressure chemical ionization (APCI) becomes necessary to expand the range of analysis applications. To overcome these limitations and fully realize the potential of NPLC-MS coupling, a technique termed liquid electron ionization-mass spectrometry (LEI-MS) can be used. LEI-MS offers a straightforward solution by enabling the effective coupling of NPLC with both low and high-resolution MS. LEI allows for the comprehensive analysis of non-polar compounds and provides a powerful tool for isomer separation and precise identification of analytes. Optimal separations, mass spectral qualities, and matches with the NIST library were obtained in both configurations, demonstrating the potential of the proposed approach.