Search results for "Radical"

First tetrathiafulvalene (TTF) cation-radical salt containing the inorganic polyoxometalate β-[Mo8O26]4⊖

1993

Antioxidant activity of cerium dioxide nanoparticles and nanorods in scavenging hydroxyl radicals

2019

Cerium oxide nanoparticles (CeNPs) have been shown to exhibit antioxidant capabilities, but their efficiency in scavenging reactive oxygen species (ROS) and the underlying mechanisms are not yet well understood. In this study, cerium dioxide nanoparticles (CeNPs) and nanorods (CeNRs) were found to exhibit much stronger scavenging activity than ·OH generation in phosphate buffered saline (PBS) and surrogate lung fluid (SLF). The larger surface area and higher defect density of CeNRs may lead to higher ·OH scavenging activity than for CeNPs. These insights are important to understand the redox activity of cerium nanomaterials and provide clues to the role of CeNPs in biological and environmen…

Further insight into the photostability of the pyrene fluorophore in halogenated solvents.

2012

Pyrene fluorophores of pyrene-functionalized CdSe quantum dots (QD@Py), as well as alkylpyrene and pyrene itself (Py), undergo fast degradation in aerated chloroform under ultraviolet-A (UV-A, 316<λ<400 nm) illumination. Steady-state fluorescence studies of irradiated chloroform solutions of QD@Py show formation of new bands, red-shifted compared to that of the pyrene moiety. Similar behaviour is observed for pyrene and the alkylpyrene system. Column chromatography of the pyrene photolysate in chloroform allowed us to isolate photoproducts arising from pyrene degradation, and to obtain information on the structure of the photoproducts responsible for the emission bands. The most predominant…

1‑Phenyl-3-(pyrid-2-yl)benzo[e][1,2,4]triazinyl: The First "Blatter Radical" for Coordination Chemistry

2014

A neutral air- and moisture-stable N,N′-chelating radical ligand, 1-phenyl-3-(pyrid-2-yl)benzo[e][1,2,4]triazinyl (1) was synthesized and characterized by electron paramagnetic resonance spectroscopy, X-ray crystallography, and magnetic measurements. Subsequent reaction of 1 with Cu(hfac)2·2H2O (hfac = hexafluoroacetylacetonate) under ambient conditions afforded the coordination complex Cu(1)(hfac)2 in which the radical binds to the metal in a bidentate fashion. Magnetic susceptibility data collected from 1.8 to 300 K indicate a strong ferromagnetic metal-radical interaction in the complex and weak antiferromagnetic radical···radical interactions between the Cu(1)(hfac)2 units. Detailed com…

A continuous reaction system to investigate dispersion polymerization of vinyl monomers in supercritical carbon dioxide

2006

A laboratory-scale continuous reaction system using a stirred tank reac- tor was assembled in our laboratory to study the dispersion polymerization of vinyl monomers in supercritical carbon dioxide (scCO2). The apparatus was equipped with a suitable downstream separation section to collect solid particles entrained in the effluent stream from the reactor, whose monomer concentration could be measured online with a gas chromatograph. The dispersion polymerization of methyl methacry- late in scCO2 was selected as a model process to be investigated in the apparatus. The experiments were performed at 65 8C and 25 MPa with 2,2 0 -azobisisobutyroni- trile as the initiator and a reactive polysilox…

Polymerization of vinylidene fluoride with perfluoropolyether surfactants in supercritical carbon dioxide as a dispersing medium

2006

The heterogeneous polymerization of vinylidene fluoride (VDF) was investigated at 50 °C with supercritical carbon dioxide (scCO 2 ) as a dispersing medium and diethylperoxidicarbonate as an initiator in the presence of different perfluoropolyether surfactants. When FLK 7004A ammonium carboxylate salts were used at a 5% (w/w) concentration with respect to VDF, with an initial pressure of 31-45 MPa and with an olefin concentration of about 5.5 mol/L, monomer conversions up to 63% were obtained, corresponding to a final solid content higher than 200 g/L, and the polymer was collected at the end of the process in the form of a white powder completely composed of microspheres. The effects of the…

Pressure dependence in the methyl vinyl ketone + OH and methacrolein + OH oxidation reactions: an electronic structure study.

2005

High-level electronic structure calculations were carried out for the study of the reaction pathways in the OH-initiated oxidations of methyl vinyl ketone (MVK) and methacrolein (MACR). For the two conformers of MVK (called synperiplanar and antiperiplanar), the addition channels of OH to the terminal and central carbon atom of the double bond dominate the overall rate constant, whereas the abstraction of the methyl hydrogen atoms has no significant kinetic role. In the case of MACR, only the antiperiplanar conformer is important in its reactivity. In addition, the lower Gibbs free energy barrier for MACR corresponds to the aldehydic hydrogen abstraction reaction, which will be somewhat mor…

Redox-induced coordination isomerization of a phosphoniobenzophospholide.

2003

1-Triphenylphosphoniobenzo[c]phospholide 1 reacts with [M(CO)(5)Br] (M = Mn, Re) and [Mn(CO)(3)(naphthalene)][BF(4)] to give complexes cis-[M(CO)(4)(1)Br] (5 a,b) and [Mn(CO)(3)(1)][BF(4)] (6 a[BF(4)]), respectively, featuring eta(1)(P)- and eta(5)(pi)-coordination of the phosphole ring. The corresponding reactions with [M(2)(CO)(10)] proceed with conservation of the metal-metal bond and yield, depending on the reaction temperature, dinuclear complexes [M(2)(CO)(8)(1)] (M=Mn, 7 a) or [M(2)(CO)(6)(1)(2)] (M=Mn, Re, 8 a,b) with mu(2)-bridging eta(1)(P):eta(2)(Pdbond;C) coordination of the phosphole moiety. All complexes formed were characterized by spectroscopic data; 5 b, 6 a[BF(4)], and 8 a…

The transformation of aromatic molecules into the subspace of their double bonds

1975

A model of new submolecules is presented. As an application some absorptions of aromatic radicals are interpreted in UV and visible spectra. Extension of the model to biological systems is prejudged.

Heterogeneous photocatalytic degradation of nitrophenols

2003

The photocatalytic degradation of 2-, 3- and 4-nitrophenol has been investigated in oxygenated aqueous suspensions containing TiO2. The organic reaction intermediates have been determined by high performance liquid chromatography. The results indicate the complete mineralisation of the substrates and the formation of both nitrate and ammonium ions. The degradation pathways involve a rapid opening of the aromatic ring followed by a slower oxidation of the aliphatic compounds. The hydroxyl radicals are responsible for the primary attack of the nitrophenols with formation of dihydroxynitrobenzenes. The ring hydroxylation occurs in the positions activated by the contemporaneous presence of phen…