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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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  <dc:creator>Atik, Ahmet</dc:creator>
  <dc:creator>Arslanoglu, Alper</dc:creator>
  <dc:creator>Yalcin, Talat</dc:creator>
  <dc:date>2021-01-01</dc:date>
  <dc: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.</dc:description>
  <dc:identifier>https://aperta.ulakbim.gov.trrecord/232554</dc:identifier>
  <dc:identifier>oai:aperta.ulakbim.gov.tr:232554</dc:identifier>
  <dc:rights>info:eu-repo/semantics/openAccess</dc:rights>
  <dc:rights>http://www.opendefinition.org/licenses/cc-by</dc:rights>
  <dc:source>JOURNAL OF MASS SPECTROMETRY 56(8)</dc:source>
  <dc:title>Gas-phase fragmentation reactions of a(7) ions containing a glutamine residue</dc:title>
  <dc:type>info:eu-repo/semantics/article</dc:type>
  <dc:type>publication-article</dc:type>
</oai_dc:dc>
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