High-energy collision-induced dissociation by MALDI TOF/TOF causes charge-remote fragmentation of steroid sulfates

Yuetian Yan, Masaaki Ubukata, Robert B. Cody, Timothy E. Holy, Michael L. Gross

Research output: Contribution to journalArticlepeer-review

11 Scopus citations


A method for structural elucidation of biomolecules dating to the 1980s utilized high-energy collisions (∼10 keV, laboratory frame) that induced charge-remote fragmentations (CRF), a class of fragmentations particularly informative for lipids, steroids, surfactants, and peptides. Unfortunately, the capability for high-energy activation has largely disappeared with the demise of magnetic sector instruments. With the latest designs of tandem time-of-flight mass spectrometers (TOF/TOF), however, this capability is now being restored to coincide with the renewed interest in metabolites and lipids, including steroid-sulfates and other steroid metabolites. For these metabolites, structure determinations are required at concentration levels below that appropriate for NMR. To meet this need, we explored CRF with TOF/TOF mass spectrometry for two groups of steroid sulfates, 3-sulfates and 21-sulfates. We demonstrated that the current generation of MALDI TOF/TOF instruments can generate charge-remote fragmentations for these materials. The resulting collision-induced dissociation (CID) spectra are useful for positional isomer differentiation and very often allow the complete structure determination of the steroid. We also propose a new nomenclature that directly indicates the cleavage sites on the steroid ring with carbon numbers.

Original languageEnglish
Pages (from-to)1404-1411
Number of pages8
JournalJournal of the American Society for Mass Spectrometry
Issue number8
StatePublished - Aug 2014


  • Charge-remote fragmentation
  • High-energy activation
  • Steroid sulfates
  • Structure determination


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