Efficient Oxidation of Cysteine and Glutathione Catalyzed by a Dinuclear Areneruthenium Trithiolato Anticancer Complex

The highly cytotoxic diruthenium complex [(p-MeC(6)H(4)Pr(1))(2)Ru(2)(SC(6)H(4)-p-Me)(3)](+) (1), water-soluble as the chloride salt, is shown to efficiently catalyze oxidation of the thiols cysteine and glutathione to give the corresponding disulfides, which may explain its high in vitro anticancer activity.

“Sweating meteorites”-Water-soluble salts and temperature variation in ordinary chondrites and soil from the hot desert of Oman

The common appearance of hygroscopic brine (“sweating”) on ordinary chondrites (OCs) from Oman during storage under room conditions initiated a study on the role of water-soluble salts on the weathering of OCs. Analyses of leachates from OCs and soils, combined with petrography of alteration features and a 11-month record of in situ meteorite and soil temperatures, are used to evaluate the role of salts in OC weathering. Main soluble ions in soils are Ca2+, SO42−, HCO3−, Na+, and Cl−, while OC leachates are dominated by Mg2+ (from meteoritic olivine), Ca2+ (from soil), Cl− (from soil), SO42− (from meteoritic troilite and soil), and iron (meteoritic). “Sweating meteorites” mainly contain Mg2+ and Cl−. The median Na/Cl mass ratio of leachates changes from 0.65 in soils to 0.07 in meteorites, indicating the precipitation of a Na-rich phase or loss of an efflorescent Na-salt. The total concentrations of water-soluble ions in bulk OCs ranges from 600 to 9000 μg g−1 (median 2500 μg g−1) as compared to 187–14140 μg g−1 in soils (median 1148 μg g−1). Soil salts dissolved by rain water are soaked up by meteorites by capillary forces. Daily heating (up to 66.3 °C) and cooling of the meteorites cause a pumping effect, resulting in a strong concentration of soluble ions in meteorites over time. The concentrations of water-soluble ions in meteorites, which are complex mixtures of ions from the soil and from oxidation and hydrolysis of meteoritic material, depend on the degree of weathering and are highest at W3. Input of soil contaminants generally dominates over the ions mobilized from meteorites. Silicate hydrolysis preferentially affects olivine and is enhanced by sulfide oxidation, producing local acidic conditions as evidenced by jarosite. Plagioclase weathering is negligible. After completion of troilite oxidation, the rate of chemical weathering slows down with continuing Ca-sulfate contamination.

Synthesis and Structural Elucidation of Triazolylmolybdenum(VI) Oxide Hybrids and Their Behavior as Oxidation Catalysts

A large family of bifunctional 1,2,4-triazole molecular tectons (tr) has been explored for engineering molybdenum(VI) oxide hybrid solids. Specifically, tr ligands bearing auxiliary basic or acidic groups were of the type amine, pyrazole, 1H-tetrazole, and 1,2,4-triazole. The organically templated molybdenum(VI) oxide solids with the general compositions [MoO3(tr)], [Mo2O6(tr)], and [Mo2O6(tr)(H2O)2] were prepared under mild hydrothermal conditions or by refluxing in water. Their crystal structures consist of zigzag chains, ribbons, or helixes of alternating cis-{MoO4N2} or {MoO5N} polyhedra stapled by short [N–N]-tr bridges that for bitriazole ligands convert the motifs into 2D or 3D frameworks. The high thermal (235–350 °C) and chemical stability observed for the materials makes them promising for catalytic applications. The molybdenum(VI) oxide hybrids were successfully explored as versatile oxidation catalysts with tert-butyl hydroperoxide (TBHP) or aqueous H2O2 as an oxygen source, at 70 °C. Catalytic performances were influenced by the different acidic–basic properties and steric hindrances of coordinating organic ligands as well as the structural dimensionality of the hybrid.

Seasonal variation of high-molecular-weight compounds in the water-soluble fraction of organic urban aerosols

Aerosol samples were collected in Zurich, Switzerland, at an urban background site and were analyzed with size exclusion chromatography (SEC) and laser/desorption ionization mass spectrometry (LDI-MS) for water-soluble organic compounds with high molecular weight. Daily samples were collected during two campaigns in winter and summer, for 1 month each. The concentration of high-molecular-weight compounds (humic-like substances (HULIS)) was between 0.4 and 4 μg/m3 in winter and summer. The most intense signals in the LDI-MS mass spectra were measured between m/z150 and 500, comparing well with the mode of the two main high mass peaks determined with SEC corresponding to masses between 200 and 600 Da. For the maximum molecular weight, however, different results were obtained by the two techniques: whereas a maximum molecular weight between 1300 and 3300 Da was found with SEC, hardly any peaks above m/z700 were measured with LDI-MS. During summer the maximum molecular weight of HULIS (determined with SEC) correlates positively with several parameters such as ozone and increased temperature indicative of enhanced atmospheric photo-oxidation. The HULIS concentration also correlates positively with the oxalic acid concentration in the particles. This suggests that HULIS are generated by secondary processes in summer. The lack of such correlations during winter suggests that other sources and processes might be important during colder seasons.