<i>Ab Initio</i> and NMR Study of Peroxynitrite and Peroxynitrous Acid:  Important Biological Oxidants

Tsai, Hui Lien; Hamilton, Tracy P.; Tsai, Jyh Hsin M.; Woerd, Mark van der; Harrison, Joseph G.; Jablonsky, Michael J.; Beckman, Joseph S.; Koppenol, Willem H.

doi:10.1021/jp961091i

Cited by 87 publications

(111 citation statements)

References 56 publications

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“…The ground-state structure of cis-cis HOONO was first calculated by McGrath and Rowland at MP2 / 6-311G͑d , p͒, 1 and later by Tsai et al at CCSD/ 6-311+ + G͑d , p͒, 27 by Fry et al at CCSD͑T͒/cc-pVTZ, 6 and by Stanton at CCSD͑T͒ atomic natural orbital ͑ANO͒. 28 This comparison supports the conclusion that high-level CCSD͑T͒ calculations accurately predict the structural parameters of HOONO.…”

Section: Position Of H Atom In Principal Axis Framesupporting

confidence: 54%

Rotational spectroscopy and dipole moment of cis-cis HOONO and DOONO

Fry

Drouin

Miller

2006

The Journal of Chemical Physics

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The rotational spectrum of cis-cis HOONO has been studied over a broad range of frequencies, 13-840 GHz, using pulsed beam Fourier-transform microwave spectroscopy and room-temperature flow cell submillimeter spectroscopy. The rotational spectrum of the deuterated isotopomer, cis-cis DOONO, has been studied over a subset of this range, 84-640 GHz. Improved spectroscopic constants have been determined for HOONO, and the DOONO spectrum is analyzed for the first time. Weak-field Stark effect measurements in the region of 84-110 GHz have been employed to determine the molecular dipole moments of cis-cis HOONO ͓ a = 0.542͑8͒ D, b = 0.918͑15͒ D, = 1.07͑2͒ D͔ and DOONO ͓ a = 0.517͑9͒ D, b = 0.930͑15͒ D, = 1.06͑2͒ D͔. The quadrupole coupling tensor in the principal inertial axis system for the 14 N nucleus has been determined to be aa = 1.4907͑25͒ MHz, bb = −4.5990͑59͒ MHz, ab = 3.17͑147͒ MHz, and cc = 3.1082͑59͒ MHz. Coordinates of the H atom in the center-of-mass frame have been determined with use of the Kraitchman equations, ͉a H ͉ = 0.516 Å and ͉b H ͉ = 1.171 Å. The inertial defects of HOONO and DOONO are consistent with a planar equilibrium structure with significant out-of-plane H atom torsional motion. Comparisons of the present results are made to ab initio calculations.

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Section: Position Of H Atom In Principal Axis Framesupporting

confidence: 54%

Rotational spectroscopy and dipole moment of cis-cis HOONO and DOONO

Fry

Drouin

Miller

2006

The Journal of Chemical Physics

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“…This conformer was first investigated by McGrath and Rowland at the MP2/6-311+G͑3df ,2p͒ ͑MP2-Møller-Plesset perturbation theory truncated at the second order͒ level of theory, 7 and has since been studied by several groups at various levels of theory. 4,[8][9][10][11][12] The calculations of Golden et al at the QCISD͑T͒/cc-pVDZ level 5 ͑QCISD-quadratic configuration interaction with single and double excitation͒ and Bean et al at the CCSD͑T͒/cc-pVTZ level 2 demonstrate that higher levels of theory are required for a good description of HOONO. Attempts to locate a cis-perp HOONO minimum at the CCSD͑T͒ level have been unsuccessful, 5,6,13 calling into question earlier predictions of a cis-perp minimum.…”

Section: -4mentioning

confidence: 99%

“…Furthermore, all of the other modes must be included. Coupling with other modes, notably the low-frequency bending/breathing mode 7 and OONO torsion 8 will alter the frequency shifts. However, if these modes also lead to large shifts in their respective hot bands, then the ratio could be even larger.…”

Section: Implications For the Hoono Yield In The Oh+ No 2 Reactionmentioning

confidence: 99%

Role of OH-stretch/torsion coupling and quantum yield effects in the first OH overtone spectrum of cis-cis HOONO

McCoy

Fry

Francisco

et al. 2005

The Journal of Chemical Physics

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A joint theoretical and experimental investigation is undertaken to study the effects of OH-stretch/ HOON torsion coupling and of quantum yield on the previously reported first overtone action spectrum of cis-cis HOONO ͑peroxynitrous acid͒. The minimum energy path along the HOON dihedral angle is computed at the coupled cluster singles and doubles with perturbative triples level with correlation consistent polarized quadruple basis set, at the structure optimized using the triple basis set ͑CCSD͑T͒/cc-pVQZ//CCSD͑T͒/cc-pVTZ͒. The two-dimensional ab initio potential energy and dipole moment surfaces for cis-cis HOONO are calculated as functions of the HOON torsion and OH bond length about the minimum energy path at the CCSD͑T͒/cc-pVTZ and QCISD/ AUG-cc-pVTZ ͑QCISD-quadratic configuration interaction with single and double excitation and AUG-augmented with diffuse functions͒ level of theory/basis, respectively. The OH-stretch vibration depends strongly on the torsional angle, and the torsional potential possesses a broad shelf at ϳ90°, the cis-perp conformation. The calculated electronic energies and dipoles are fit to simple functional forms and absorption spectra in the region of the OH fundamental and first overtone are calculated from these surfaces. While the experimental and calculated spectra of the OH fundamental band are in good agreement, significant differences in the intensity patterns are observed between the calculated absorption spectrum and the measured action spectrum in the 2 OH region. These differences are attributed to the fact that several of the experimentally accessible states do not have sufficient energy to dissociate to OH+ NO 2 and therefore are not detectable in an action spectrum. Scaling of the intensities of transitions to these states, assuming D 0 = 82.0 kJ/ mol, is shown to produce a spectrum that is in good agreement with the measured action spectrum. Based on this agreement, we assign two of the features in the spectrum to ⌬n = 0 transitions ͑where n is the HOON torsion quantum number͒ that are blue shifted relative to the origin band, while the large peak near 7000 cm −1 is assigned to a series of ⌬n = + 1 transitions, with predominant contributions from torsionally excited states with substantial cis-perp character. The direct absorption spectrum of cis-cis HOONO ͑6300-6850 cm −1 ͒ is recorded by cavity ringdown spectroscopy in a discharge flow cell. A single band of HOONO is observed at 6370 cm −1 and is assigned as the origin of the first OH overtone of cis-cis HOONO. These results imply that the origin band is suppressed by over an order of magnitude in the action spectrum, due to a reduced quantum yield. The striking differences between absorption and action spectra are correctly predicted by the calculations.

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“…Theoretical calculations suggest that the cis-configuration of ONOO Ϫ is favored over the transconfiguration (39). It has been shown recently by x-ray crystallography that peroxynitrite indeed crystallizes in the cis form (40).…”

Section: Discussionmentioning

confidence: 97%

The decomposition of peroxynitrite to nitroxyl anion (NO-) and singlet oxygen in aqueous solution

Khan

Kovacic

Kolbanovskiy

et al. 2000

Proceedings of the National Academy of Sciences

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The mechanism of decomposition of peroxynitrite (OONO ؊ ) in aqueous sodium phosphate buffer solution at neutral pH was investigated. The OONO ؊ was synthesized by directly reacting nitric oxide with superoxide anion at pH 13. The hypothesis was explored that OONO ؊ , after protonation at pH 7.0 to HOONO, decomposes into 1 O2 and HNO according to a spin-conserved unimolecular mechanism. Small aliquots of the concentrated alkaline OONO ؊ solution were added to a buffer solution (final pH 7.0 -7.2), and the formation of 1 O2 and NO ؊ in high yields was observed. The 1 O2 generated was trapped as the transannular peroxide (DPAO2) of 9,10-diphenylanthracene (DPA) dissolved in carbon tetrachloride. The nitroxyl anion (NO ؊ ) formed from HNO (pKa 4.5) was trapped as nitrosylhemoglobin (HbNO) in an aqueous methemoglobin (MetHb) solution. In the presence of 25 mM sodium bicarbonate, which is known to accelerate the rate of decomposition of OONO ؊ , the amount of singlet oxygen trapped was reduced by a factor of Ϸ2 whereas the yield of trapping of NO ؊ by methemoglobin remained unaffected. Because NO3 ؊ is known to be the ultimate decomposition product of OONO ؊ , these results suggest that the nitrate anion is not formed by a direct isomerization of OONO ؊ , but by an indirect route originating from NO ؊ .nitrosylhemoglobin ͉ diphenylanthracene endoperoxide P eroxynitrite is a potent oxidant formed by the near diffusioncontrolled reaction of nitric oxide (NO ⅐ ) and superoxide ion (O 2 Ϫ ) (1). Both nitric oxide and superoxide are produced by activated macrophages (2, 3), neutrophils (4), and endothelial cells (5, 6). There is evidence that peroxynitrite is formed in significant concentrations in vivo (7-9) and may contribute to an increased risk for cancer (10), artherosclerosis (11), stroke (12), and other diseases (13). Peroxynitrite is a stable anion in alkaline solution (pKa of 6.8); however, once protonated, it decomposes rapidly with a half-life of less than 1 s at physiological pH at 37°C (14), generating reactive species that readily react with biomolecules such as lipids (15), amino acids (16), and DNA (17). Central to the question of the biochemistry of peroxynitrite is the mechanism of decomposition and the identity of the reactive species, a subject of intense research and controversy (18-21). Speculations about the decomposition mechanisms are largely based on kinetic and thermodynamic considerations (22). It has been shown that bicarbonate ion enhances the rate of disappearance of peroxynitrite, leading to the proposal of a nitrosoperoxycarbonate anion adduct, with a distinctly different chemistry from that of OONO Ϫ (19).We reported previously that the mere acidification of an aqueous peroxynitrite solution resulted in chemiluminescence at 1,270 nm characteristic of the deactivation of singlet oxygen (23). By comparing the intensity of this emission to that of 1 O 2 generated by the reaction of hydrogen peroxide (H 2 O 2 ) with hypochlorite anion (OCl Ϫ ), which is known to be stoichiometric (24), it was...

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Ab Initio and NMR Study of Peroxynitrite and Peroxynitrous Acid: Important Biological Oxidants

Cited by 87 publications

References 56 publications

Rotational spectroscopy and dipole moment of cis-cis HOONO and DOONO

Rotational spectroscopy and dipole moment of cis-cis HOONO and DOONO

Role of OH-stretch/torsion coupling and quantum yield effects in the first OH overtone spectrum of cis-cis HOONO

The decomposition of peroxynitrite to nitroxyl anion (NO-) and singlet oxygen in aqueous solution

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