In order to elucidate the uranium solution chemistry at the high HNO(3) concentrations typically employed for the reprocessing of spent nuclear fuels, speciation and complex structures of U(IV) and U(VI) are studied in aqueous HNO(3) solutions, as well as in HClO(4) solutions, by means of UV-visible-near-infrared and X-ray absorption spectroscopies and density functional theory calculations. In...

The nitroxyl anion (HNO) is emerging as a novel regulator of cardiovascular function with therapeutic potential in the treatment of diseases such as heart failure. It remains unknown whether tolerance develops to HNO donors, a limitation of currently used nitrovasodilators. The susceptibility of the HNO donor, Angeli's salt (AS), to the development of vascular tolerance was compared with the NO...

The front cover picture shows a prefluorescent phosphine-based probe reacting with nitroxyl (HNO) and S-nitrosothiol (RSNO), nitrogen oxide-derived biological signals. Both species react with the prefluorescent probe, but only the product from the HNO reaction can complete a further chemical ligation pathway that results in fluorescence, indicating the presence of HNO. The product of the probe ...

HNO can interact with numerous heme proteins, but atomic level structures are largely unknown. In this work, various structural models for the first stable HNO heme protein complex, MbHNO (Mb, myoglobin), were examined by quantum chemical calculations. This investigation led to the discovery of two novel structural models that can excellently reproduce numerous experimental spectroscopic proper...

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...

Nitroxyl (HNO) is closely linked with numerous biological processes. Fluorescent probes provide a visual tool for determining HNO. Due to fluorescence quenching by HNO-responsive recognition groups, most of the current fluorescent exhibit an “off-on” response. As such, single signal these easily affected external factors such as microenvironment, sensor concentration, and photobleaching. Herein...

Nitroxyl (HNO), a potential heart failure therapeutic, is known to target cysteine residues to form sulfinamides and/or disulfides. Because HNO-derived modifications may depend on their local environment, we have investigated the reactivity of HNO with cysteine derivatives and C-terminal cysteine-containing peptides at physiological pH and temperature. Our findings indicate that the nature of H...

Recent research has shown that nitroxyl (HNO) has important and unique biological activity, especially as a potential alternative to current treatments of cardiac failure. HNO is a reactive molecule that undergoes efficient dimerization and subsequent dehydration to form nitrous oxide (N(2)O), making its detection in solution or biologically relevant preparations difficult. Due to this limitati...