2002
DOI: 10.1073/pnas.112202099
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Nitroxyl and its anion in aqueous solutions: Spin states, protic equilibria, and reactivities toward oxygen and nitric oxide

Abstract: The thermodynamic properties of aqueous nitroxyl (HNO) and its anion (NO ؊ ) have been revised to show that the ground state of NO ؊ is triplet and that HNO in its singlet ground state has much lower acidity, pKa( 1 HNO͞ 3 NO ؊ ) Ϸ 11.4, than previously believed. These conclusions are in accord with the observed large differences between 1 HNO and 3 NO ؊ in their reactivities toward O2 and NO. Laser flash photolysis was used to generate 1 HNO and 3 NO ؊ by photochemical cleavage of trioxodinitrate (Angeli's an… Show more

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Cited by 410 publications
(561 citation statements)
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“…4 -6 yields: (7) where k 1 [AS] is the rate of Angeli's salt decomposition, and k 2 is the kinetic coefficient of the HNO dimerization reaction (8 × 10 6 M −1 s −1 ). 13 Angeli's salt decomposition rates were determined in PBS by monitoring the decrease in 250 nm absorbance over 60 min and fitting to an exponential decay model (absorbance = Ae −kt + c). 28 For the experimental conditions employed herein (25 °C, pH 7.4, 10 −4 DTPA, aerobic), k 1 was calculated at 8.1 × 10 −4 s −1 .…”
Section: Kinetic Hno Quantificationmentioning
confidence: 99%
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“…4 -6 yields: (7) where k 1 [AS] is the rate of Angeli's salt decomposition, and k 2 is the kinetic coefficient of the HNO dimerization reaction (8 × 10 6 M −1 s −1 ). 13 Angeli's salt decomposition rates were determined in PBS by monitoring the decrease in 250 nm absorbance over 60 min and fitting to an exponential decay model (absorbance = Ae −kt + c). 28 For the experimental conditions employed herein (25 °C, pH 7.4, 10 −4 DTPA, aerobic), k 1 was calculated at 8.1 × 10 −4 s −1 .…”
Section: Kinetic Hno Quantificationmentioning
confidence: 99%
“…Such a trend is consistent with previous reports of decreased metmyoglobin reductive nitrosylation efficiency by equimolar amounts of IPA/NO and Angeli's salt, 25 and may be attributed to the concurrent formation of NO that is both formed competitively with HNO and scavenges existing HNO from solution. 13 …”
Section: Nitroxyl Sensingmentioning
confidence: 99%
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“…The values were expressed as the means Ϯ S.E., and differences between groups were considered to be significant at p Ͻ 0.05 or p Ͻ 0.01. 2 After the submission of this manuscript, a report by Shafirovich and Lymar (61) revealed that the species generated by Angeli's salt in aqueous solutions at neutral pH is HNO rather than NO Ϫ . Although we are aware of these new findings, throughout the text we will refer to the species released by Angeli's salt still as NO Ϫ to simplify the terminology of the distinct redox-activated forms of NO.…”
Section: Methodsmentioning
confidence: 99%
“…Mechanistically, these reactions were suggested to occur with the intermediate formation of [49][50][51][52][53] or (an isomer of) [54] peroxynitrite; [53,55] direct detection of the corresponding oxidizing species, however, has proven to be difficult. Irrespectively of the exact mechanism of these reaction(s), overproduction of HNO in tissues subjected to acidosis may lead to oxidative stress inasmuch as the ability of HNO to act as a pro-oxidant dramatically increases in acidic solutions (ref.…”
Section: Chemical Fate Of No• In Biological Systemsmentioning
confidence: 99%