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High-Energy Collision-Induced Dissociation by MALDI TOF/TOF Causes Charge-Remote Fragmentation of Steroid Sulfates

  • Research Article
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Journal of The American Society for Mass Spectrometry

Abstract

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.

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Acknowledgments

The authors acknowledge support for this research by the National Institute of General Medical Sciences (8 P41 GM103422-35 to M.L.G.) and the National Institute on Deafness and Other Communication Disorders (R01 DC005964 to T.E.H.), both of the National Institutes of Health.

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Authors and Affiliations

  1. Department of Chemistry, Washington University in St. Louis, St. Louis, MO, 63130, USA

    Yuetian Yan & Michael L. Gross

  2. Jeol USA, 11 Dearborn Road, Peabody, MA, 01960, USA

    Masaaki Ubukata & Robert B. Cody

  3. Department of Anatomy and Neurobiology, Washington University in St. Louis, St. Louis, MO, 63130, USA

    Timothy E. Holy

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  1. Yuetian Yan
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  2. Masaaki Ubukata
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Correspondence to Michael L. Gross.

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Yan, Y., Ubukata, M., Cody, R.B. et al. High-Energy Collision-Induced Dissociation by MALDI TOF/TOF Causes Charge-Remote Fragmentation of Steroid Sulfates. J. Am. Soc. Mass Spectrom. 25, 1404–1411 (2014). https://doi.org/10.1007/s13361-014-0901-4

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  • DOI: https://doi.org/10.1007/s13361-014-0901-4

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