Journal
JOURNAL OF THE AMERICAN SOCIETY FOR MASS SPECTROMETRY
Volume 25, Issue 8, Pages 1404-1411Publisher
SPRINGER
DOI: 10.1007/s13361-014-0901-4
Keywords
Charge-remote fragmentation; MALDI TOF-TOF; Steroid sulfates; Structure determination; High-energy activation
Funding
- National Institute of General Medical Sciences of the National Institutes of Health [8 P41 GM103422-35]
- National Institute on Deafness and Other Communication Disorders of the National Institutes of Health [R01 DC005964]
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A method for structural elucidation of biomolecules dating to the 1980s utilized high-energy collisions (similar to 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.
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