Electrospray ionization–principles and practice

TLDR: Electrospray (E S ) ionization has recently shown itself capable of producing intact ions, with multiple charges, from remarkably large, complex, and fragile parent species as mentioned in this paper, which is the state-of-the-art in mass spectrometric analysis.

Abstract: Chemistry has its origins as a quantitative science in the careful weighing of products and reactants by Lavoisier and his followers beginning some 200 years ago. Ever since then, the constantly evolving gravimetric balance has been a faithful servant of the laboratory chemist and has played a major role in developing the analytical methods that are the foundation of contemporary chemical science. Perhaps the ultimate stage in the evolution of that balance is represented by the modern mass spectrometer. It is able to determine with high precision the masses of individual atoms and molecules by transforming them into ions and measuring the response of their trajectories in vacuo to various combinations of electric and magnetic fields. Clearly, the sine qua non of such mass determination is the transformation of analyte atoms and molecules from their initial state in a sample to ions in vacuo ready for ”weighing.” Over the years, ingenious investigators have produced a variety of methods for achieving this transformation. One of them, electrospray ( E S ) ionization, has recently shown itself capable of producing intact ions, with multiple charges, from remarkably large, complex, and fragile parent species. Our assignment here is to review what has thus far been learned about this still uncommon technique and what it seems able to offer practitioners of mass spectrometric analysis. Our approach will be to set forth the present state of the ES ionization art in terms of a sort of menu of its procedures, processes, performance, and promise. Until very recently we have been almost the only group that has worked with ES ionization since the pioneering efforts of Malcolm Dole (1) some 20 years ago. Consequently, this review is more tutorial than most. Moreover, it may seem like a cook book that is overly preoccupied with the authors’ own culinary adventures. The reasoil is that many of the dishes to be described were first tried out in our own kitchen. Therefore, we earnestly urge the reader to remember what every gourmet knows: the piquancy of any dish on a bill of fare is due much less to its ingredients than to the skill of the chef whc. prepares it.