• Login
    View Item 
    •   Shocker Open Access Repository Home
    • Fairmount College of Liberal Arts and Sciences
    • Chemistry and Biochemistry
    • CHEM Faculty Scholarship
    • CHEM Faculty Publications
    • View Item
    •   Shocker Open Access Repository Home
    • Fairmount College of Liberal Arts and Sciences
    • Chemistry and Biochemistry
    • CHEM Faculty Scholarship
    • CHEM Faculty Publications
    • View Item
    JavaScript is disabled for your browser. Some features of this site may not work without it.

    McLafferty-type rearrangement in the collision-induced dissociation of Li+, Na+ and Ag+ cationized esters of N-acetylated peptides

    Date
    2003-01-01
    Author
    Anbalagan, Victor
    Patel, J. N.
    Niyakorn, G.
    Van Stipdonk, Michael J.
    Metadata
    Show full item record
    Citation
    Rapid communications in mass spectrometry : RCM. 2003; 17(4): 291-300.
    Abstract
    In this study we investigated the multi-stage collision-induced dissociation (CID) of N-terminally acetylated di-, tri- and tetrapeptides in the form of C-terminal ethyl, n-propyl, isopropyl, n-butyl and tert-butyl esters and cationized by the attachment of Li(+), Na(+) and Ag(+). While methyl ester versions of the metal cationized peptides primarily eliminate H(2)O following collisional activation and dissociation, the ethyl, propyl and butyl ester versions of the peptides exhibit a dissociation pathway consistent with gamma-hydrogen transfer to the C-terminal carbonyl group, with associated elimination of an alkene, in a McLafferty-type rearrangement. The rearrangement leaves a metal cationized, free-acid form of the peptide, as confirmed by comparing the multi-stage CID of rearrangement products generated from peptide esters with the CID of corresponding metal cationized free-acid peptides. The transfer of a gamma-hydrogen in the rearrangement reaction was confirmed by investigating the CID of ethyl esters for which the terminal methyl group was labeled with deuterium. We found that the rearrangement product was significantly more abundant, relative to other product ions, when derived from isopropyl and tert-butyl esters than from ethyl, n-propyl or n-butyl ester analogues.
    Description
    Click on the DOI link below to access the article (may not be free).
    URI
    http://dx.doi.org/10.1002/rcm.912
    http://hdl.handle.net/10057/4322
    Collections
    • CHEM Faculty Publications

    Browse

    All of Shocker Open Access RepositoryCommunities & CollectionsBy Issue DateAuthorsTitlesSubjectsBy TypeThis CollectionBy Issue DateAuthorsTitlesSubjectsBy Type

    My Account

    LoginRegister

    Statistics

    Most Popular ItemsStatistics by CountryMost Popular Authors

    DSpace software copyright © 2002-2023  DuraSpace
    DSpace Express is a service operated by 
    Atmire NV