A selective phosphine-based fluorescent probe for nitroxyl in living cells

[Display omitted] A novel fluorescein-based fluorescent probe for nitroxyl (HNO) based on the reductive Staudinger ligation of HNO with an aromatic phosphine was prepared. This probe reacts with HNO derived from Angeli’s salt and 4-bromo Piloty’s acid under physiological conditions without interference by other biological redox species. Confocal microscopy demonstrates this probe detects HNO by fluorescence in HeLa cells and mass spectrometric analysis of cell lysates confirms this probe detects HNO following the proposed mechanism

Direct and Nitroxyl (HNO)-Mediated Reactions of Acyloxy Nitroso Compounds with the Thiol-Containing Proteins Glyceraldehyde 3‑Phosphate Dehydrogenase and Alkyl Hydroperoxide Reductase Subunit C

Nitroxyl (HNO) reacts with thiols, and this reactivity requires the use of donors with 1-nitrosocyclohexyl acetate, pivalate, and trifluoroacetate, forming a new group. These acyloxy nitroso compounds inhibit glyceraldehyde 3-phosphate dehydrogenase (GAPDH) by forming a reduction reversible active site disulfide and a reduction irreversible sulfinic acid or sulfinamide modification at Cys244. Addition of these acyloxy nitroso compounds to AhpC C165S yields a sulfinic acid and sulfinamide modification. A potential mechanism for these transformations includes nucleophilic addition of the protein thiol to a nitroso compound to yield an <i>N</i>-hydroxysulfenamide, which reacts with thiol to give disulfide or rearranges to sulfinamides. Known HNO donors produce the unsubstituted protein sulfinamide as the major product, while the acetate and pivalate give substituted sulfinamides that hydrolyze to sulfinic acids. These results suggest that nitroso compounds form a general class of thiol-modifying compounds, allowing their further exploration

A selective phosphine-based fluorescent probe for nitroxyl in living cells

A novel fluorescein-based fluorescent probe for nitroxyl (HNO) based on the reductive Staudinger ligation of HNO with an aromatic phosphine was prepared. This probe reacts with HNO derived from Angeli’s salt and 4-bromo Piloty’s acid under physiological conditions without interference by other biological redox species. Confocal microscopy demonstrates this probe detects HNO by fluorescence in HeLa cells and mass spectrometric analysis of cell lysates confirms this probe detects HNO following the proposed mechanism

Enhanced photocatalytic degradation of methylene blue and methyl orange by ZnO:Eu nanoparticles

ZnO nanoparticles doped with different Eu3+ percentages were synthesized in water (ZnO: Eu(chi%)-W) and other solvents (methanol ZnO:Eu(chi%)-M and ethanol ZnO:Eu(chi%)-E). X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), optical absorption and photoluminescence (PL) spectroscopy were used for characterization of the nanoparticles. Our results showed influence of europium doping and solvents on size, particles agglomeration, light absorption and photo catalytic activity. Improvement in photocatalytical activity with addition of Eu3+ doping was detected. Particle size increased with Eu3+ doping in water samples, while it decreased in methanol. Agglomeration was more prominent in ZnO:Eu(chi%)-W samples. Greater amount of surface OH groups in case of ZnO:Eu(chi%)-M samples was detected by PL, XPS and FTIR measurements. Influence of europium doping, as an electron trap, and surface OH groups, as a hole trap, was studied in sunlight photocatalytic degradation of cationic methylene blue (MB) and anionic methyl orange (MO). Improved photocatalytic behavior was discussed and influence of active species was further investigated using hole and hydroxyle radical scavengers. The degradation pathway of MB and MO, using high performance liquid chromatohraphy (HPLC), is also examined. (C) 2016 Elsevier B.V. All rights reserved