| 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 |