Applications and mechanisms of charge-remote fragmentation.

Studies on the applications, energetics, and mechanisms of charge-remote fragmentations are reviewed, with emphasis given to those articles published after 1992. Independent of the charge status, charge-remote fragmentations are analogous to gas-phase thermolysis. Under collisional activation and with a fixed charge, ions containing long-chain or poly-ring structures undergo charge-remote fragmentations, generating productions that are structurally informative. Interpretation of the production spectra enables one to elucidate molecular structures. Although charge-remote fragmentations have been successfully used in the structural determination of fatty acids, phospholipids, glycolipids, triacylglycerols, steroids, peptides, ceramides, and other systems, the energetics and mechanisms of these reactions are still debated because none of the existing mechanisms can explain all the experimental data.