IRMPD and DFT study of the loss of water from protonated 2-hydroxynicotinic acid

dc.contributor.author	Van Stipdonk, Michael J.
dc.contributor.author	Kullman, Michael J.
dc.contributor.author	Berden, Giel
dc.contributor.author	Oomens, Jos
dc.date.accessioned	2012-07-19T20:27:23Z
dc.date.available	2012-07-19T20:27:23Z
dc.date.issued	2012-07-06
dc.identifier.citation	Van Stipdonk, Michael J.; Kullman, Michael J.; Berden, Giel & Jos, Oomens.2012. IRMPD and DFT study of the loss of water from protonated 2-hydroxynicotinic acid. International Journal of Mass Spectrometry, Available online 6 July 2012.	en_US
dc.identifier.issn	1387-3806
dc.identifier.uri	http://hdl.handle.net/10057/5247
dc.identifier.uri	http://dx.doi.org/10.1016/j.ijms.2012.06.026
dc.description	Click on the DOI link below to access the article (may not be free).	en_US
dc.description.abstract	Collision-induced dissociation (CID) of protonated 2-hydroxynicotinic acid (2-OHNic) generates a dominant product ion through loss of 18 mass units, presumably the elimination of water. Subsequent isolation and storage of this product ion in the gas-phase environment of an ion trap mass spectrometer, without imposed collisional activation, shows that the species undergoes addition reactions to furnish new products that are higher in mass by 18 and 32 units. Density functional theory (DFT) calculations suggest that an acylium ion (i.e. loss of H2O from the acid group) is energetically more favored than is a species generated by elimination of H2O from the hydroxypyridine ring. Formation of the acylium product is confirmed by comparing the infrared multiple photon dissocation (IRMPD) spectrum to theoretical spectra from (DFT) harmonic calculations for several possible isomers. A thorough DFT study of the reaction dynamics suggests that the acylium ion is generated from the global minimum for the protonated precursor along a pathway that involves proton transfer from the hydroxypyridine ring and elimination of –OH from the acid group.	en_US
dc.language.iso	en_US	en_US
dc.publisher	Elsevier	en_US
dc.relation.ispartofseries	International Journal of Mass Spectrometry;Available online 6 July 2012
dc.subject	IRMPD	en_US
dc.subject	Ion structure	en_US
dc.subject	DFT	en_US
dc.subject	Fragmentation mechanism	en_US
dc.subject	Reaction dynamics	en_US
dc.title	IRMPD and DFT study of the loss of water from protonated 2-hydroxynicotinic acid	en_US
dc.type	Article	en_US
dc.description.version	Peer reviewed
dc.rights.holder	Copyright © 2012, Elsevier