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A study of fragmentation of protonated amides of some acylated amino acids by tandem mass spectrometry: observation of an unusual nitrilium ion

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dc.contributor Wichita State University. Department of Chemistry en_US
dc.contributor.author Talaty, Erach R. en_US
dc.contributor.author Young, Sarah M. en_US
dc.contributor.author Dain, Ryan P. en_US
dc.contributor.author Van Stipdonk, Michael J. en_US
dc.date.accessioned 2012-02-06T17:17:31Z
dc.date.available 2012-02-06T17:17:31Z
dc.date.issued 2011-05-15 en_US
dc.identifier 21488111 en_US
dc.identifier 8802365 en_US
dc.identifier.citation Rapid communications in mass spectrometry : RCM. 2011 May 15; 25(9): 1119-29. en_US
dc.identifier.issn 1097-0231 en_US
dc.identifier.issn 0951-4198 en_US
dc.identifier.uri http://dx.doi.org/10.1002/rcm.4965 en_US
dc.identifier.uri http://hdl.handle.net/10057/4433
dc.description Click on the DOI link below to access the article (may not be free). en_US
dc.description.abstract A 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.extent 1119-29 en_US
dc.language.iso eng en_US
dc.publisher John Wiley and Sons en_US
dc.relation.ispartofseries Rapid communications in mass spectrometry : RCM en_US
dc.relation.ispartofseries Rapid Commun. Mass Spectrom. en_US
dc.source NLM en_US
dc.subject.mesh Acylation en_US
dc.subject.mesh Amides/chemistry en_US
dc.subject.mesh Amino Acids/chemistry en_US
dc.subject.mesh Deuterium Exchange Measurement en_US
dc.subject.mesh Nitriles/chemistry en_US
dc.subject.mesh Physicochemical Phenomena en_US
dc.subject.mesh Physicochemical Processes en_US
dc.subject.mesh Spectrometry, Mass, Electrospray Ionization en_US
dc.subject.mesh Tandem Mass Spectrometry/methods* en_US
dc.title A study of fragmentation of protonated amides of some acylated amino acids by tandem mass spectrometry: observation of an unusual nitrilium ion en_US
dc.type Article en_US
dc.coverage.spacial England en_US
dc.description.version Peer reviewed
dc.rights.holder Copyright © 2011 John Wiley & Sons, Ltd. en_US

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