Charge-remote fragmentation: An account of research on mechanisms and applications

Charge-remote fragmentation is one class of decomposition reactions of gas-phase ions. Their discovery and applications had to await the development of soft ionization, particularly fast atom bombardment, and tandem mass spectrometry. The decompositions are particularly informative and allow functional groups to be identified and located in fatty acids, surfactants, steroids, complex lipids, and related materials. These are difficult structure assignments to make by other mass-spectrometry methods or by nuclear magnetic resonance and other spectroscopic techniques. Thus, charge-remote fragmentation fills an important need in structural chemistry. The mechanisms of charge-remote fragmentation underpin their structural utility, and they are still a matter of some debate. In this account, we discuss the discovery of charge-remote fragmentation in our laboratory. Further, we describe our efforts to understand their mechanism and to exploit their high information content in structure determinations of fatty acid and related materials.