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A tandem mass spectrometric study of protonated isomeric hydroxypyridine N-oxides was carried out with a hybrid quadrupole/time-of-flight mass spectrometer coupled with different atmospheric pressure ionization sources. The behavior observed in the collision-induced dissociation (CID) mass spectra of the parent cations, was similar irrespective of the source employed. However, there were intrinsic differences in the intensities of the two fragments observed for each isomer. The major fragment becauseof elimination of a hydroxyl radical, dominated the CID spectra (in contrast with weaker water loss) at different energy thresholds. Therefore, it was possible to differentiate both isomers at collision energies above 13 eV by comparing the ratio of intensities of the major fragment relative to the precursor cation. In addition, quantum chemical calculations at the B3LYP/6-31++G(d,p) level of theory were performed for the protonated isomers of hydroxypyridine N-oxide and their radical cation products in order to gain insight into the major routes of dissociation. The results suggest that dissociation from the lowest triplet excited state of the protonated species would provide a reasonable rationalization for the difference in behavior of both isomers. Copyright © 2010 John Wiley & Sons, Ltd.


Documento: Artículo
Título:An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry
Autor:Butler, M.; Mañez, P.A.; Cabrera, G.M.
Filiación:Departamento de Química Orgánica, UMYMFOR-CONICET, Universidad de Buenos Aires, Buenos Aires, Argentina
Departamento de Química Inorgánica, Analítica Y Química Fisica, INQUIMAE-CONICET, Universidad de Buenos Aires, Buenos Aires, Argentina
Palabras clave:Ab initio calculations; API MS; CID fragmentation; Isomer differentiation; Pyridine N-oxides; Ab initio calculations; API MS; Atmospheric pressure ionization; Atmospheric pressure ionization mass spectrometries; Collision energies; Collision-induced dissociation; Computational studies; Energy thresholds; Gain insight; Hydroxyl radicals; Hydroxypyridine; Intrinsic differences; Mass spectra; N-Oxides; Protonated; Protonated species; Quadrupole/time of flights; Quantum chemical calculations; Radical cations; Tandem mass spectrometric; Water loss; Atmospheric chemistry; Atmospheric ionization; Atmospheric pressure; Calculations; Dissociation; Ionization of liquids; Mass spectrometers; Mass spectrometry; Oxides; Particle detectors; Positive ions; Protonation; Pyridine; Quantum chemistry; Isomers; pyridinol; article; atmospheric pressure; collisionally activated dissociation; controlled study; isomer; priority journal; proton transport; quantum chemistry; tandem mass spectrometry; time of flight mass spectrometry; water loss; Atmospheric Pressure; Cyclic N-Oxides; Models, Molecular; Molecular Conformation; Pyridines; Spectrometry, Mass, Electrospray Ionization; Tandem Mass Spectrometry; Temperature; Thermodynamics
Página de inicio:536
Página de fin:544
Título revista:Journal of Mass Spectrometry
Título revista abreviado:J. Mass Spectrom.
CAS:pyridinol, 27341-45-3; Cyclic N-Oxides; Pyridines; hydroxypyridines


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---------- APA ----------
Butler, M., Mañez, P.A. & Cabrera, G.M. (2010) . An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry. Journal of Mass Spectrometry, 45(5), 536-544.
---------- CHICAGO ----------
Butler, M., Mañez, P.A., Cabrera, G.M. "An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry" . Journal of Mass Spectrometry 45, no. 5 (2010) : 536-544.
---------- MLA ----------
Butler, M., Mañez, P.A., Cabrera, G.M. "An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry" . Journal of Mass Spectrometry, vol. 45, no. 5, 2010, pp. 536-544.
---------- VANCOUVER ----------
Butler, M., Mañez, P.A., Cabrera, G.M. An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry. J. Mass Spectrom. 2010;45(5):536-544.