Local structure and charge distribution in the UO(2)-U(4)O(9) system

Analysis of X-ray absorption fine structure spectra of UO(2+x) for x = 0-0.20 (UO(2)--U(4)O(9)) reveals that the adventitious O atoms are incorporated as oxo groups with U--O distances of 1.74 A, most likely associated with U(VI), that occur in clusters so that the UO(2) fraction of the material largely remains intact. In addition to the formation of some additional longer U--O bonds, the U sublattice consists of an ordered portion that displays the original U--U distance and a spectroscopically silent, glassy part. This is very different from previous models derived from neutron diffraction that maintained long U--O distances and high U--O coordination numbers. UO(2+x) also differs from PuO(2+x) in its substantially shorter An-oxo distances and no sign of stable coordination with H(2)O and its hydrolysis products.     

Critical flocculation density of dilute water-in-CO2 emulsions stabilized with block copolymers

The critical flocculation density (CFD), that is, the CO(2) density below which flocculation occurs, was studied for dilute water-in-CO(2) (W/C) miniemulsions stabilized with poly(1,1-dihydroperfluorooctyl methacrylate)-b-poly(ethylene oxide) (PFOMA-b-PEO) surfactants. The CFD, which was measured by turbidimetry, decreased as the PFOMA molecular weight was increased, the average droplet size was decreased, the surfactant loading was increased, and the temperature was increased. A simple model, which addressed both the van der Waals attraction between droplets and osmotic solvent-tail interactions, was in good qualitative agreement with the experimentally observed trends for the CFD and predicted a decrease in emulsion stability as the CO(2) density was lowered toward the theta density for PFOMA in bulk CO(2).     

The regiospecific Fischer indole reaction in choline chloride.2ZnCl2 with product isolation by direct sublimation from the ionic liquid

The Fischer indole synthesis occurs in high yield with one equivalent of the ionic liquid choline chloride[middle dot]2ZnCl(2); exclusive formation of 2,3-disubstituted indoles is observed in the reaction of alkyl methyl ketones, and the products readily sublime directly from the ionic liquid.     

A novel azulene synthesis from the Ramirez ylide involving two different modes of its reaction with activated alkynes

The Ramirez ylide undergoes electrophilic substitution with acetylenedicarboxylates to form Z and E adducts. The latter can react by cycloaddition with another equivalent of the alkyne to provide a new route to novel tetra-substituted azulenes, which show interesting bond localisation and crystal packing effects.     

Enhanced photoluminescence from poly(phenylene vinylene):dendrimer polyelectrolyte assemblies in solution

Poly(2,5-methoxy-propyloxy sulfonate phenylene vinylene)(MPS-PPV) and DAB-Am-16, a generation 3.0 polypropylenimine hexadecamine dendrimer (DAB), are shown to form a tunable photoresponsive polyelectrolyte assembly in aqueous solution with an enhanced emission signal of up to 18-times that of MPS-PPV alone.     

Redox inactivation of human 15-lipoxygenase by marine-derived meroditerpenes and synthetic chromanes: archetypes for a unique class of selective and recyclable inhibitors

The selective inhibition of human 15-lipoxygenase (15-hLO) could serve as a promising therapeutic target for the prevention of atherosclerosis. A screening of marine sponges revealed that crude extracts of Psammocinia sp. exhibited potent 15-hLO inhibitory activity. Bioassay-guided fractionation led to the isolation of chromarols A-E (8-12) as potent and selective inhibitors of 15-hLO. An additional 22 structurally related compounds, including meroditerpenes from the same Psammocinia sp. (3, 4, 13-16) and our pure compound repository (17, 18), commercially available tocopherols (19-24), and synthetic chromanes (25-32), were evaluated for their ability to inhibit human lipoxygenases. The 6-hydroxychromane moiety found in chromarols A-D was identified as essential for the selective redox inhibition of 15-hLO. Furthermore, the oxidized form of the 6-hydroxychromane could be reduced by ascorbate, suggesting a potential regeneration pathway for these inhibitors in the body. This pharmacophore represents a promising paradigm for the development of a unique class of recyclable 15-hLO redox inhibitors for the treatment of atherosclerosis.     

Chalcogen-chalcogen bonds in edge-sharing square-planar d8 complexes. Are they possible?

A theoretical study of the formation of X-X bonds in complexes with the general formula [M(2)(mu-X)(2)L(4)] (M = group 10 and X = group 16 elements) having d(8) transition-metal atoms is presented. The existence of two energy minima for some complexes, with short and long X-X distances, is shown by density functional theory calculations, and the factors responsible for it are analyzed, including a strong influence of the nature of the metals and ligands on the relative stability of the two isomers. The influence of the bite angle of chelating terminal ligands and the nature of the donor atom on the relative stabilities of the two isomers are also discussed.