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dc.contributorWichita State University. Department of Chemistryen_US
dc.contributor.authorTalaty, Erach R.en_US
dc.contributor.authorYoung, Sarah M.en_US
dc.contributor.authorDain, Ryan P.en_US
dc.contributor.authorVan Stipdonk, Michael J.en_US
dc.date.accessioned2012-02-06T17:17:31Z
dc.date.available2012-02-06T17:17:31Z
dc.date.issued2011-05-15en_US
dc.identifier21488111en_US
dc.identifier8802365en_US
dc.identifier.citationRapid communications in mass spectrometry : RCM. 2011 May 15; 25(9): 1119-29.en_US
dc.identifier.issn1097-0231en_US
dc.identifier.issn0951-4198en_US
dc.identifier.urihttp://dx.doi.org/10.1002/rcm.4965en_US
dc.identifier.urihttp://hdl.handle.net/10057/4433
dc.descriptionClick on the DOI link below to access the article (may not be free).en_US
dc.description.abstractA tandem mass spectrometric study of a series of secondary amides of acetylglycine and hippuric acid utilizing electrospray ionization (ESI) was conducted. Among the fragment ions observed was an unusual one, which we have determined to be a nitrilium ion having the structure  or by loss of the full mass of glycine as a neutral fragment. A mechanism that we propose involves an initial protonation of the oxygen atom at the N-terminus, followed by cyclization to a five-membered imidazolium ring, and its subsequent collapse to the nitrilium ion. This mechanism is supported by extensive isotopic labels and considerable variation of substituents. A similar study of the amides of acyl β-alanine and acyl γ-aminobutyric acid revealed that the former furnishes the same nitrilium ion, but not the latter. Thus, a six-membered intermediate is also possible and capable of losing the full mass of β-alanine as a neutral fragment. When the size of the ring is forced to be seven-membered, this pathway is blocked. When this study was expanded to include a variety of N-acylproline amides, the nitrilium ion was observed in 100% abundance only when the acyl group was acetyl. Thus a proline effect (involvement of a strained bicyclic [3.3.0] structure) is being observed.en_US
dc.format.extent1119-29en_US
dc.language.isoengen_US
dc.publisherJohn Wiley and Sonsen_US
dc.relation.ispartofseriesRapid communications in mass spectrometry : RCMen_US
dc.relation.ispartofseriesRapid Commun. Mass Spectrom.en_US
dc.sourceNLMen_US
dc.subject.meshAcylationen_US
dc.subject.meshAmides/chemistryen_US
dc.subject.meshAmino Acids/chemistryen_US
dc.subject.meshDeuterium Exchange Measurementen_US
dc.subject.meshNitriles/chemistryen_US
dc.subject.meshPhysicochemical Phenomenaen_US
dc.subject.meshPhysicochemical Processesen_US
dc.subject.meshSpectrometry, Mass, Electrospray Ionizationen_US
dc.subject.meshTandem Mass Spectrometry/methods*en_US
dc.titleA study of fragmentation of protonated amides of some acylated amino acids by tandem mass spectrometry: observation of an unusual nitrilium ionen_US
dc.typeArticleen_US
dc.coverage.spacialEnglanden_US
dc.description.versionPeer reviewed
dc.rights.holderCopyright © 2011 John Wiley & Sons, Ltd.en_US


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