Electrospray ionization developed by Lidija Gall's group

Abstract

This historical review is dedicated to Prof. Lidija Gall. She was awarded the Thomson medal (2022) for her contribution to the development of electrospray ionization mass spectrometry in the early 1980s in Leningrad, Soviet Union. We describe the rationale and provide historical references that highlight her way to the discovery of a method of solvated ion extraction at atmospheric pressure (SIEAP), known by the Russian abbreviation ЭРИАД (ERIAD), which is the direct analogue of electrospray ionization developed in the West. Even at the early prototype stage, ERIAD was able to determine the intact masses of a broad scope of polar biomolecules including peptides, small proteins, nucleotides, carbohydrates, and prostanglandins. The ERIAD source was directly coupled to microbore liquid chromatography and was applied to analyze protein digests, to characterize the substrate specificity of proteolytic enzymes, to mapping of mutation sites in physiologically important proteins and also to increase the confidence in protein sequence determinations. In inorganic chemistry, ERIAD was successfully applied to analyze the solutions of rare-earth metals and metal complexes. Altogether, a set of experimental studies and a broad scope of applications contributed to better understanding of the ionization mechanism and the methods needed to acquire and interpret ERIAD spectra. The method was first implemented on a magnetic sector mass spectrometer and then was adopted to a variety of mass analyzers and mobility separators in collaboration with Russian mass spectrometry groups.