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Gas-phase fragmentation reactions of a(7) ions containing a glutamine residue

Atik, Ahmet; Arslanoglu, Alper; Yalcin, Talat


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{
  "DOI": "10.1002/jms.4776", 
  "abstract": "The gas-phase fragmentation reactions of the a(7) ions derived from glutamine (Q) containing model heptapeptides have been studied in detail with low-energy collision-induced dissociation (CID) tandem mass spectrometry (MS/MS). Specifically, the positional effect of the Q residue has been investigated on the fragmentation reactions of a(7) ions. The study involves two sets of permuted isomers of the Q containing model heptapeptides. The first set contains the QAAAAAA sequence, and the second set involves of QYAGFLV sequence, where the position of the Q residue is changed from N- to C-terminal gradually for both peptide series. An intense loss of ammonia from the a7 ions followed by internal amino acid eliminations strongly supports forming the imine-amides structure via cyclization/rearrangement reaction for all studied a(7) ions. This is in agreement with the pioneering study reported by Bythell et al. (2010, 10.1021/ja101556g). A novel rearrangement reaction is detected upon fragmentation of imine-amide structure, which yields a protonated C-terminal amidated hexapeptide excluding the Q residue. A possible fragmentation mechanism was proposed to form the protonated C-terminal amidated hexapeptide, assisted via nucleophilic attack of the side chain amide nitrogen of the Q residue on its N-protonated imine carbon atom of the rearranged imine-amide structure. Highlights The gas-phase fragmentation reactions of a(7) ions obtained from protonated model peptides containing glutamine residue were studied by ESI-MS/MS. A rearranged imine-amide structure is the predominant even for a(7) ions. Novel rearrangement reaction is observed which forms a protonated C-terminal amidated hexapeptide excluding Q residue upon fragmentation of the imine-amide structure.", 
  "author": [
    {
      "family": "Atik", 
      "given": " Ahmet"
    }, 
    {
      "family": "Arslanoglu", 
      "given": " Alper"
    }, 
    {
      "family": "Yalcin", 
      "given": " Talat"
    }
  ], 
  "container_title": "JOURNAL OF MASS SPECTROMETRY", 
  "id": "232554", 
  "issue": "8", 
  "issued": {
    "date-parts": [
      [
        2021, 
        1, 
        1
      ]
    ]
  }, 
  "title": "Gas-phase fragmentation reactions of a(7) ions containing a glutamine residue", 
  "type": "article-journal", 
  "volume": "56"
}
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