Solid-state ion exchange of ammonium heptamolybdate tetrahydrate into ZSM-5 zeolite

Journal of Thermal Analysis and Calorimetry - Thermal decomposition (2 K min?1) of ammonium heptamolybdate tetrahydrate, performed between room temperature and...     

Induction theorems on the stable rationality of the center of the ring of generic matrices

Following Procesi and Formanek, the center of the division ring of generic matrices over the complex numbers is stably equivalent to the fixed field under the action of , of the function field of the group algebra of a -lattice, denoted by . We study the question of the stable rationality of the center over the complex numbers when is a prime, in this module theoretic setting. Let be the normalizer of an -sylow subgroup of . Let be a -lattice. We show that under certain conditions on , induction-restriction from to does not affect the stable type of the corresponding field. In particular, and are stably isomorphic and the isomorphism preserves the -action. We further reduce the problem to the study of the localization of at the prime ; all other primes behave well. We also present new simple proofs for the stable rationality of over , in the cases and .

     

Intramolecular Diamination of Alkenes with Palladium(II)/Copper(II) Bromide and IPy2BF4: The Role of Halogenated Intermediates

The oxidative intramolecular diamination of alkenes with tethered ureas and related groups as the nitrogen source has been investigated both with the iodonium reagent IPy₂BF₄ (Py=pyridine) and under palladium catalysis in the presence of copper(II) bromide as a reoxidant. For terminal alkenes, the two procedures enable selective and high‐yielding transformations. Studies with deuterated material led to the conclusion that the reactions proceed through different stereochemical pathways. An advanced protocol for palladium‐catalyzed diamination through six‐membered‐ring annulation was also developed, and the first examples of the intramolecular diamination of internal alkenes are described. In this case, the same stereochemical outcome was observed for the iodonium‐promoted and palladium‐catalyzed transformations. On this basis, it was possible to determine the importance of aminohalogenated intermediates in both diamination reactions. Overall, the disclosed procedures broaden significantly the synthetic applicability of the oxidative intramolecular diamination of alkenes.     

Quantification of fenitrothion and its main metabolites in poplar leaves by isotope dilution gas chromatography-mass spectrometry coupled with solid-phase microextraction

A sensitive and specific method for determining fenitrothion and its main metabolites, 3-methyl-4-nitrophenol and fenitrooxon, in poplar leaves using deuterated isotopes as the internal standard is described. The analytes and the labeled isotopes were extracted from leaves by solid-phase microextraction and subsequently analysed by gas chromatography coupled with mass spectrometry. The method had a chromatographic run time of 17.0 min and good linearity over the range 0.01-10 mg kg(-1). The detection limits ranged between 2.5 and 0.6 microg kg(-1). The isotopic dilution technique allowed improving significantly the repetitivity even using different fibers with the same coating (RSD<5.1%). The method was applied successfully to study the persistence of fenitrothion in forestal matrices in a poplar forest after cannon spray application of the insecticide.     

Molecularly imprinted capillary electrochromatography for selective determination of thiabendazole in citrus samples

In this work, the suitability of the combination of molecular imprinting and capillary electrochromatography (MIP-CEC) to be used as powerful tool in environmental or food analysis has been for the first time studied and successfully demonstrated. A molecularly imprinted monolith (MIM) has been synthesised and evaluated as stationary phase for the selective determination of the fungicide thiabendazole (TBZ) in citrus samples by non-aqueous capillary electrochromatography. The influence of the mobile phase composition, the voltage of the power supply and the separation temperature on the recognition of TBZ by the imprinted polymer has been evaluated, and the imprint effect in the MIM was clearly demonstrated. Once optimum recognition conditions were established, other variables affecting mechanical properties and chromatographic performance of MIM were adjusted using computational approach. The high selectivity achieved by the MIP-CEC developed procedure allowed unambiguous detection and quantification of TBZ in citrus samples by direct injection of the crude sample extracts, without any previous clean-up, in less than 6 min. The developed method was properly validated and the calculated detection limits were below the established maximum residue limits (MRLs), clearly demonstrating the suitability of the method to be used for the control of the selected fungicide.     

Vacuum-UV-photolysis of aqueous solutions of citric and gallic acids

The vacuum-UV- (VUV-) photolysis of water is one of the advanced oxidation processes (AOP) based on the production of hydroxyl radicals (HO) that can be applied to the degradation of organic pollutants in aqueous systems. The kinetics of the VUV-photolyses of aqueous solutions of citric acid (1) or gallic acid (2) were investigated in the presence or absence of dissolved molecular oxygen (O₂) and under different pH conditions. In the case of 1, the rate of consumption of the substrate was faster at pH 3.4 than in alkaline solution (pH 11), whereas, in the case of 2, the variation of pH (2.5–7.5) did not affect the course of the reaction. Unexpectedly, the rates of depletion of both 1 and 2 decreased in the absence of O₂, this effect being much more pronounced in the case of 2. In order to explain these results, possible reaction pathways for the degradation of 1 and 2 are proposed, and the roles of the oxidizing (HO) and reducing (H and e_aq⁻) species produced by the VUV-photolysis of water are discussed.     

On realistic terrains

We study worst-case complexities of visibility and distance structures on terrains under realistic assumptions on edge length ratios and the angles of the triangles, and a more general low-density assumption. We show that the visibility map of a point for a realistic terrain with n triangles has complexity . We also prove that the shortest path between two points p and q on a realistic terrain passes through triangles, and that the bisector of p and q has complexity . We use these results to show that the shortest path map for any point on a realistic terrain has complexity , and that the Voronoi diagram for any set of m points on a realistic terrain has complexity and . Our results immediately imply more efficient algorithms for computing the various structures on realistic terrains.     

Role of superheated water in the dissolution and perturbation of hydrogen bonding in the crystalline lattice of polyamide 4,6

Here, we demonstrate that water, in the superheated state, is a solvent for polyamide 4,6 (PA4,6) and that the water molecules can strongly influence hydrogen bonding. In the presence of superheated water, the melting temperature of PA4,6 can be suppressed by nearly 100 degrees C. The depression in the melting temperature follows the Flory-Huggins principle. The instantaneous dissolution of the polymer hardly influences the molar mass of the polymer. However, if the polymer is retained in solution above the dissolution temperature for more than 10 min, hydrolysis occurs. These findings suggest that the dissolution of the aliphatic polymer in superheated water is mainly a physical process as opposed to a chemical process. Time resolved X-ray studies show that the dissolution occurs prior to the Brill transition temperature, as reported earlier. Crystals grown from the water solution show a lath-like morphology with interchain and intersheet distances that are similar to the distances obtained for crystals grown from other known solvents. Electron diffraction further confirmed that the crystals grown from superheated water are single crystals, where the chains are perpendicular to the ab-plane. SAXS performed on dried sedimented water grown single crystals showed a lamellar thickness of 6 nm. The lamellar thickness is in accordance with other reported studies on PA4,6, confirming that the single crystals incorporate four repeat units between re-entrant folds with an amide group incorporated in the tight fold. Solid state NMR studies performed on mats of these single crystals showed two different mobilities of the proton associated with the amide groups: a higher mobility linked to the amide protons in the fold and a reduced mobility of the hydrogen bonded amide protons within the crystal. Additionally, the solid state NMR studies on the dried water crystallized single crystals show the presence of water molecule(s) in the vicinity of the amide groups. This was confirmed by infrared studies that conclusively demonstrated the appearance of two new bands arising due to the binding of a water molecule in the vicinity of the amide group (i.e., NH3(+) and COO(-) bands that disappear upon heating at approximately 200 degrees C). Additionally, DSC traces of the water crystallized PA4,6 show an exothermic event in the same temperature region (i.e., in the vicinity of the Brill transition temperature, where the bound water exits from the lattice). Furthermore, this event was corroborated by TGA data.     

Direct time-resolved detection of singlet oxygen in zeolite-based photocatalysts

Singlet oxygen has been characterized spectroscopically as a product of the exposure of suspensions of zeolites containing oxidation catalysts. Spectroscopic and lifetime studies show that a part of the singlet oxygen formed reacts within the zeolite porous structure, while a significant fraction escapes and becomes available for reaction in the bulk media. The liquid phase plays a key role in determining intra- and extracavity dynamics.