In this study, the dissociative adsorption of NaNO2, NaNO3, HNO2, HNO3 and H2SO4 over (1 1 0) surface of γ-alumina non-spinel model were investigated through the dispersion corrected density functional theory (DFT-D) at PBE-D/DNP level of calculation. It was found that all of the species are dissociated to their ionic forms after...

Here we describe a novel caged form of the highly reactive bioeffector molecule, nitroxyl (HNO). Reacting the labile nitric oxide (NO)- and HNO-generating salt of structure iPrHN-N(O)═NO(-)Na(+) (1, IPA/NO) with BrCH(2)OAc produced a stable derivative of structure iPrHN-N(O)═NO-CH(2)OAc (2, AcOM-IPA/NO), which hydrolyzed an order of magnitude more slowly than 1 at pH 7.4 and 37 °C. Hydrolysis o...

Reduction of cyclic stable nitroxides (RNO) by HNO to the respective hydroxylamines (RNO-H) has been demonstrated using EPR spectrometry. HNO shows low reactivity toward piperidine, pyrrolidine and nitronyl nitroxides with rate constants below 1.4 × 10(5)M(-1)s(-1) at pH 7.0, despite the high driving force for these reactions. The rate constants can be predicted assuming that the reactions take...

Endogenous formation of nitric oxide (NO) and related nitrogen oxides in the vascular system is critical to regulation of multiple physiological functions. An imbalance in the production or availability of these species can result in progression of disease. Nitrogen oxide research in the cardiovascular system has primarily focused on the effects of NO and higher oxidation products. However, nit...

Infrared multiple photon dissociation spectra for the smallest atmospherically relevant anions of sulfuric and nitric acid allow us to characterize structures and distinguish between clusters with a bisulfate or a nitrate core. We find that bisulfate is the main charge carrier for HSO(4)(-)·H(2)SO(4)·HNO(3) but not for NO(3)(-)·H(2)SO(4)·HNO(3). For the mixed dimer anion, we find evidence for t...

Membrane inlet (or introduction) mass spectrometry (MIMS) was used to detect nitroxyl (HNO) in aqueous solution for the first time. The common HNO donors Angeli's salt (AS) and Piloty's acid (PA), along with a newly developed donor, 2-bromo-N-hydroxybenzenesulfonamide (2-bromo-Piloty's acid, 2BrPA), were examined by this technique. MIMS experiments revealed that under physiological conditions 2...

RATIONALE In the myocardium, redox/cysteine modification of proteins regulating Ca(2+) cycling can affect contraction and may have therapeutic value. Nitroxyl (HNO), the one-electron-reduced form of nitric oxide, enhances cardiac function in a manner that suggests reversible cysteine modifications of the contractile machinery. OBJECTIVE To determine the effects of HNO modification in cardiac ...

Nitric oxide (NO) is an important signaling molecule that regulates diverse physiological processes in all domains of life. In many gammaproteobacteria, NO controls behavioral responses through a complex signaling network involving heme-nitric oxide/oxygen binding (H-NOX) domains as selective NO sensors. In Shewanella oneidensis, H-NOX-mediated NO sensing increases biofilm formation, which is t...

We report the first studies on the reaction between an HNO donor compound and vitamin B12 complexes. Kinetic and mechanistic studies have been carried out on the reaction between the vitamin B12 derivative aquacobalamin (H2OCbl(+)/HOCbl; pKa = 7.8) and the HNO donor Angeli's salt. Studies were carried out with aquacobalamin in excess, since nitrite also reacts with aquacobalamin to form nitroco...

In this study, the dissociative adsorption of NaNO2, NaNO3, HNO2, HNO3 and H2SO4 over (1 1 0) surface of γ-alumina non-spinel model were investigated through the dispersion corrected density functional theory (DFT-D) at PBE-D/DNP level of calculation. It was found that all of the species are dissociated to their ionic forms after...