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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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{
  "@context": "https://schema.org/", 
  "@id": 232554, 
  "@type": "ScholarlyArticle", 
  "creator": [
    {
      "@type": "Person", 
      "name": "Atik, Ahmet"
    }, 
    {
      "@type": "Person", 
      "affiliation": "Izmir Inst Technol, Dept Mol Biol & Genet, Fac Sci, Izmir, Turkey", 
      "name": "Arslanoglu, Alper"
    }, 
    {
      "@type": "Person", 
      "name": "Yalcin, Talat"
    }
  ], 
  "datePublished": "2021-01-01", 
  "description": "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.", 
  "headline": "Gas-phase fragmentation reactions of a(7) ions containing a glutamine residue", 
  "identifier": 232554, 
  "image": "https://aperta.ulakbim.gov.tr/static/img/logo/aperta_logo_with_icon.svg", 
  "license": "http://www.opendefinition.org/licenses/cc-by", 
  "name": "Gas-phase fragmentation reactions of a(7) ions containing a glutamine residue", 
  "url": "https://aperta.ulakbim.gov.tr/record/232554"
}
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