Loss of Internal Backbone Carbonyls: Additional Evidence for Sequence-Scrambling in Collision-Induced Dissociation of y-Type Ions
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  • 作者:Brett Harper ; Mahsan Miladi ; Touradj Solouki
  • 关键词:Collision ; induced dissociation (CID) ; Ion mobility spectrometry (IMS) ; Mass spectrometry (MS) ; Peptide fragmentation ; Sequence ; scrambling ; y Fragment
  • 刊名:Journal of The American Society for Mass Spectrometry
  • 出版年:2014
  • 出版时间:October 2014
  • 年:2014
  • 卷:25
  • 期:10
  • 页码:1716-1729
  • 全文大小:1,088 KB
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  • 作者单位:Brett Harper (1)
    Mahsan Miladi (2)
    Touradj Solouki (2)

    1. Institute of Biomedical Studies, Baylor University, Waco, TX, 76798, USA
    2. Department of Chemistry and Biochemistry, Baylor University, Waco, TX, 76798, USA
  • ISSN:1879-1123
文摘
It is shown that y-type ions, after losing C-terminal H2O or NH3, can lose an internal backbone carbonyl (CO) from different peptide positions and yield structurally different product fragment ions upon collision-induced dissociation (CID). Such CO losses from internal peptide backbones of y-fragment ions are not unique to a single peptide and were observed in four of five model peptides studied herein. Experimental details on examples of CO losses from y-type fragment ions for an isotopically labeled AAAAHAA-NH2 heptapeptide and des-acetylated-α-melanocyte-stimulating hormone (dα-MSH) (SYSMEHFRWGKPV-NH2) are reported. Results from isotope labeling, tandem mass spectrometry (MSn), and ion mobility-mass spectrometry (IM-MS) confirm that CO losses from different amino acids of m/z-isolated y-type ions yield structurally different ions. It is shown that losses of internal backbone carbonyls (as CID products of m/z-isolated y-type ions) are among intermediate steps towards formation of rearranged or permutated product fragment ions. Possible mechanisms for generation of the observed sequence-scrambled a-“like-ions, as intermediates in sequence-scrambling pathways of y-type ions, are proposed and discussed. ?span class="a-plus-plus figure category-standard float-no id-figa">

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