MODERN PLASMA-BASED DESORPTION/IONIZATION: FROM ATOMS AND MOLECULES TO CHEMICAL SYNTHESIS.

Since the first mass spectrometry (MS) experiments were conducted by Thomson and Aston, plasmas have been used as ionization sources. Historically, plasma ion sources were used for these experiments because they were one of the few known sources of gas-phase ions at the time and they were relatively simple to setup and operate. Since then, developments in plasma ionization have continued to inform and motivate advances in other areas of MS. For example, plasma-desorption MS demonstrated ionization of large peptides and polymers more than 10 years before the first descriptions of electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). As a result, significant effort was placed on development of ionization approaches, mass analysis, and detection approaches for very large molecules: even before the advent of ESI and MALDI. Since then, new analytical challenges and opportunities in plasma ionization have arisen. In this review, the emerging trends in plasma-based ionization for several areas of MS will be discussed, including molecular ionization, elemental ionization, hybrid elemental and molecular ion sources, and unique chemical transformations. © 2020 John Wiley & Sons Ltd. Mass Spec Rev.