An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry
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 o...
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2010
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| Acceso en línea: | https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10765174_v45_n5_p536_Butler http://hdl.handle.net/20.500.12110/paper_10765174_v45_n5_p536_Butler |
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paper:paper_10765174_v45_n5_p536_Butler2023-06-08T16:05:23Z An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry 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 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. 2010 https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10765174_v45_n5_p536_Butler http://hdl.handle.net/20.500.12110/paper_10765174_v45_n5_p536_Butler |
| institution |
Universidad de Buenos Aires |
| institution_str |
I-28 |
| repository_str |
R-134 |
| collection |
Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) |
| topic |
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 |
| spellingShingle |
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 An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry |
| topic_facet |
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 |
| description |
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. |
| title |
An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry |
| title_short |
An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry |
| title_full |
An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry |
| title_fullStr |
An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry |
| title_full_unstemmed |
An experimental and computational study on the dissociation behavior of hydroxypyridine N-oxides in atmospheric pressure ionization mass spectrometry |
| title_sort |
experimental and computational study on the dissociation behavior of hydroxypyridine n-oxides in atmospheric pressure ionization mass spectrometry |
| publishDate |
2010 |
| url |
https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_10765174_v45_n5_p536_Butler http://hdl.handle.net/20.500.12110/paper_10765174_v45_n5_p536_Butler |
| _version_ |
1768542375819345920 |