Evidence for Sequence Scrambling in Collision-Induced Dissociation of y-Type Fragment Ions

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• 作者：Mahsan Miladi (1)
  Brett Harper (2)
  Touradj Solouki (1)
  
• 关键词：Collision ; induced dissociation (CID) ; Mass spectrometry (MS) ; Peptide fragmentation ; Sequence scrambling ; y Fragment
• 刊名：Journal of The American Society for Mass Spectrometry
• 出版年：2013
• 出版时间：November 2013
• 年：2013
• 卷：24
• 期：11
• 页码：1755-1766
• 全文大小：
• 作者单位：Mahsan Miladi (1)
  Brett Harper (2)
  Touradj Solouki (1)
  
  1. Department of Chemistry and Biochemistry, Baylor University, Waco, TX, 76798, USA
  2. Institute of Biomedical Studies, Baylor University, Waco, TX, 76798, USA
  
• ISSN：1879-1123

文摘

Sequence scrambling from y-type fragment ions has not been previously reported. In a study designed to probe structural variations among b-type fragment ions, it was noted that y fragment ions might also yield sequence-scrambled ions. In this study, we examined the possibility and extent of sequence-scrambled fragment ion generation from collision-induced dissociation (CID) of y-type ions from four peptides (all containing basic residues near the C-terminus) including: AAAAHAA-NH2 (where span class="a-plus-plus emphasis type-underline">Adenotes carbon thirteen (13C1) isotope on the alanine carbonyl group), des-acetylated-melanocyte (SYSMEHFRWGKPV-NH2), angiotensin II antipeptide (EGVYVHPV), and glu-fibrinopeptide b (EGVNDNEEGFFSAR). We investigated fragmentation patterns of 32 y-type fragment ions, including y fragment ions with different charge states (+1 to +3) and sizes (3 to 12 amino acids). Sequence-scrambled fragment ions were observed from ~50% (16 out of 32) of the studied y-type ions. However, observed sequence-scrambled ions had low relative intensities from ~0.1% to a maximum of ~12%. We present and discuss potential mechanisms for generation of sequence-scrambled fragment ions. To the best of our knowledge, results on y fragment dissociation presented here provide the first experimental evidence for generation of sequence-scrambled fragments from CID of y ions through intermediate cyclic -typeions. Figure