Hydrogen-shift isomers of ionic and neutral hydroxypyridines: a combined experimental and computational investigation

Trikoupis, Moschoula A.; Gerbaux, Pascal; Lavorato, David J.; Flammang, Robert; Terlouw, Johan K.

doi:10.1016/s1387-3806(02)00531-6

Cited by 25 publications

(20 citation statements)

References 56 publications

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“…In 2002, Trikoupis et al [125] performed combined B3LYP/CBSB7 computations and mass spectrometric experiments on 2-HP + . They showed that the fragmentation pathways of the cationic species are very complex.…”

Section: -Pyridonementioning

confidence: 99%

Photoionization Spectroscopy of Nucleobases and Analogues in the Gas Phase Using Synchrotron Radiation as Excitation Light Source

Schwell

Hochlaf

2014

Topics in Current Chemistry

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We review here the photoionization and photoelectron spectroscopy of the gas phase nucleic acid bases adenine, thymine, uracil, cytosine, and guanine, as well as the three base analogues 2-hydroxyisoquinoline, 2-pyridone, and δ-valerolactam in the vacuum ultraviolet (VUV) spectral regime. The chapter focuses on experimental work performed with VUV synchrotron radiation and related ab initio quantum chemical calculations of higher excited states beyond the ionization energy. After a general part, where experimental and theoretical techniques are described in detail, key results are presented by order of growing complexity in the spectra of the molecules. Here we concentrate on (1) the accurate determination of ionization energies of isolated gas phase NABs and investigation of the vibrational structure of involved ionic states, including their mutual vibronic couplings, (2) the treatment of tautomerism after photoionization, in competition with other intramolecular processes, (3) the study of fragmentation of these molecular systems at low and high internal energies, and (4) the study of the evolution of the covalent character of hydrogen bonding upon substitution, i.e., examination of electronic effects (acceptor, donor, etc.).

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Section: -Pyridonementioning

confidence: 99%

Photoionization Spectroscopy of Nucleobases and Analogues in the Gas Phase Using Synchrotron Radiation as Excitation Light Source

Schwell

Hochlaf

2014

Topics in Current Chemistry

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“…[5] Therefore, a detailed understanding of the ionization and fragmentation of heterocyclic N-oxides would be very valuable. [6] While the hydroxypyridines have been extensively studied by mass spectrometry, [7,8] to our knowledge their N-oxides have thus far escaped examination.…”

Section: Introductionmentioning

confidence: 99%

An experimental and computational study on the dissociation behavior of hydroxypyridine N‐oxides in atmospheric pressure ionization mass spectrometry

2010

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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 because of 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.

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“…The relative stability of this form of 3-hydroxypyridine is uncertain but it is expected to be significantly less stable than the hydroxy form [46,47]. As a result, the pathway involving ion-neutral complexes may be associated with a relatively high critical energy and allow other processes to be able to compete with this reaction pathway.…”

Section: Discussionmentioning

confidence: 99%

A chemical ionization study of deuteron transfer initiated propene loss from propoxypyridines

Beelen

Molenaar-Langeveld

Ingemann

2003

J. Am. Soc. Mass Spectrom.

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The mechanism of propene loss from the metastable [M ϩ D] ϩ ions of isomeric 2-, 3-, and 4-n-propoxypyridines and the related isopropoxypyridines has been examined by chemical ionization (CI) and tandem mass spectrometry in combination with deuterium labeling. The (1) The loss of propene by ion-neutral complex formation and the occurrence of a substantial isotope effect in the subsequent proton/deuteron transfer within the complex, and/or (2) the loss of propene by a 1,2-elimination type reaction.

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Hydrogen-shift isomers of ionic and neutral hydroxypyridines: a combined experimental and computational investigation

Cited by 25 publications

References 56 publications

Photoionization Spectroscopy of Nucleobases and Analogues in the Gas Phase Using Synchrotron Radiation as Excitation Light Source

Photoionization Spectroscopy of Nucleobases and Analogues in the Gas Phase Using Synchrotron Radiation as Excitation Light Source

An experimental and computational study on the dissociation behavior of hydroxypyridine N‐oxides in atmospheric pressure ionization mass spectrometry

A chemical ionization study of deuteron transfer initiated propene loss from propoxypyridines

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