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

SOAR Repository

Show simple item record

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

Files in this item

Files Size Format View

There are no files associated with this item.

This item appears in the following Collection(s)

Show simple item record

Search SOAR

Advanced Search


My Account