Endothermic ion molecule reactions

Ron Orlando, Catherine Fenselau, Robert J. Cotter

Research output: Contribution to journalArticlepeer-review


Endothermic ion-molecule reactions in a tandem mass spectrometer have been used for a number of years for determining thermodynamic quantities, such as heats of formation and proton affinities, for gaseous ions. Recently, the reactive, endothermic collision has been exploited as an analytical technique for the structural analysis of peptides and other biomolecules. The technique is based upon the endothermic transfer of protons associated with amide bonds to ammonia. This reaction proceeds via a long-lived collision complex. When additional beam energy is supplied, other dissociation channels are opened up, leading to the production of sequence ions for the mass-selected, protonated analyte that are normally observed in high energy collision-induced dissociation spectra. The advantage, however, is that such spectra can be produced at very low beam energies. In this article, the rationale for developing this scheme, and its roots in previous ion-molecule studies, are explored.

Original languageEnglish (US)
Pages (from-to)189-197
Number of pages9
JournalJournal of the American Society for Mass Spectrometry
Issue number3
StatePublished - May 1991

ASJC Scopus subject areas

  • Structural Biology
  • Spectroscopy


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