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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorAnbalagan, Victoren_US
dc.contributor.authorSilva, A. T. M.en_US
dc.contributor.authorRajagopalachary, Sen_US
dc.contributor.authorBulleigh, Kellisen_US
dc.contributor.authorTalaty, Erach R.en_US
dc.contributor.authorVan Stipdonk, Michael J.en_US
dc.identifier.citationJournal of mass spectrometry : JMS. 2004 May; 39(5): 495-504.en_US
dc.descriptionClick on the DOI link below to access the article (may not be free).en_US
dc.description.abstractThe aim of this study was to investigate the dissociation patterns, and in particular the relative abundance of [b(3) + 17 + Cat](+), for peptides with C-termini designed to allow transfer of the -OH required to generate the product ion, but not necessarily as the most favored pathway. Working with the hypothesis that formation of a five-membered ring intermediate, including intramolecular nucleophilic attack by a carbonyl oxygen atom, is an important mechanistic step, several model peptides with general sequence AcFGGX were synthesized, metal cationized by electrospray ionization and subjected to collision-induced dissociation (CID). The amino acid at position X was one that either required a larger ring intermediate (beta-alanine, gamma-aminobutyric acid and epsilon-amino-n-caproic acid to generate six-, seven- or nine- membered rings, respectively) to transfer -OH, lacked a structural element required for nucleophilic attack (aminoethanol) or prohibited cyclization because of the inclusion of a rigid ring (p- and m-aminobenzoic acid). For Ag(+), Li(+) and Na(+) cationized peptides, our results show that amino acids requiring the adoption of larger ring intermediates suppressed the formation of [b(3) + 17 + Cat](+), while amino acids that prohibit cyclization eliminated the reaction pathway completely. Formation of [b(3) - 1 + Cat](+) from the alkali metal cationized versions was not a favorable process upon suppression or elimination of the [b(3) + 17 + Cat](+) pathway: the loss of H(2)O to form [M - H(2)O + Cat](+) was instead the dominant dissociation reaction observed. Multiple-stage dissociation experiments suggest that [M - H(2)O + Cat](+) is not [b(4) - 1 + Cat](+) arising from the loss of H(2)O from the C-terminus, but may instead be a species that forms via a mechanism involving the elimination of an oxygen atom from an amide group.en_US
dc.publisherJohn Wiley and Sonsen_US
dc.relation.ispartofseriesJournal of mass spectrometry : JMSen_US
dc.relation.ispartofseriesJ Mass Spectromen_US
dc.subjectResearch Support, Non-U.S. Gov'ten_US
dc.subjectResearch Support, U.S. Gov't, Non-P.H.S.en_US
dc.subject.meshAmino Acids/chemistryen_US
dc.subject.meshMass Spectrometryen_US
dc.subject.meshMolecular Structureen_US
dc.subject.meshOligopeptides/chemical synthesisen_US
dc.titleInfluence of "alternative" C-terminal amino acids on the formation of [b3 + 17 + Cat]+ products from metal cationized synthetic tetrapeptidesen_US
dc.description.versionpeer revieweden_US
dc.rights.holderCopyright © 2004 John Wiley & Sons, Ltd.en_US

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