A rheological analysis of interactions in phenoxy/organoclay nanocomposites

Novel oscillatory flow results of phenoxy/organoclay nanocomposites are analysed considering the blocking effect of nanostructure on polymer chain mobility. The modification provoked by this hindering effect on loss tangent spectrum is investigated. The study of three different systems, involving a pristine montmorillonite and two montmorillonites modified with one alkyl tail and two alkyl tails, respectively, leads to conclude that polymer-alkyl repulsive interactions play the most important role in the chain mobility obstruction process. Our results suggest that polymer-alkyl interactions increase with temperature.     

Lithiation and electrophilic substitution of 8-chlorodibenz[b,f][1,4]-oxazepine-10-tert-butylcarbamate: The preparation of novel fused heterocyclic derivatives of 8-chlorodibenzoxazepine

Lithiation of 8-chlorodibenz[b,f][1,4]oxazepine-10-tert-butylcarbamate ( 1 ) is described. Electrophilic substitution of the resulting N-Boc dibenzoxazepine α- lithioamine 2 with ketones, aldehydes, nitriles, iso-cyanates and imines, followed by an in-situ cyclization, gave fused carbamates 5–26 , fused 2H-imidazol-2-ones 27–29 , fused hydantoins 30–32 , and fused ureas 33–35 , respectively, in 11–66% yield.     

Excess enthalpies of (methyl propanoate or methyl pentanoate + 1-alkanol) at 298.15 K

The excess molar enthalpies H_m^E of methyl propanoate or methyl pentanoate + 1-butanol, + 1-hexanol, + 1-octanol, and + 1-decanol have been determined experimentally at 298.15 K using a Calvet microcalorimeter. For all these mixtures H_m^E > 0; the values increase with the chain length of the alkanol but decrease as the ester chain lengthens.     

The use of the consecutive adsorption of pyridine bases and carbon monoxide in the IR spectroscopic study of the accessibility of acid sites in microporous/mesoporous materials

A new approach to the evaluation of the accessibility of acid sites in microporous/mesoporous materials is developed and tested using a series of dealuminated mordenites. This approach is based on an IR-spectroscopic study of the consecutive adsorption of substituted alkylpyridines (pyridine, 2,4,6-trimethylpyridine, and 2,4,6-triethylpyridine) and carbon monoxide. This method allowed us to determine the strength and number of acid sites with various degrees of accessibility. The adsorption of 2,4,6-triethylpyridine on various types of materials is studied. The extinction coefficients of alkylpyridines are determined using a McBain balance placed in a cell for IR-spectroscopic measurements. Original Russian Text N.S. Nesterenko, F. Thibault-Starzyk, V. Montouilliout, V.V. Yushchenko, C. Fernandez, J.-P. Gilson, F. Fajula, I.I. Ivanova, 2006, published in Kinetika i Kataliz, 2006, Vol. 47, No. 1, pp. 45–53.     

Vapor-particle partitioning of hydrocarbons in Western Mediterranean urban and marine atmospheres

An analytical procedure is described for a comprehensive determination of the composition of hydrocarbons in the atmosphere, based on: (a) aerosol filtration and subsequent adsorption of the vapor phase onto active charcoal and polyurethane foam; (b) GPC and HPLC fractionation of the extracts, and (c) analysis of the fractions by GC-MS under EI and NICI modes. Special emphasis is placed onn-alkanes, PAHs and their oxygenated derivatives.The characterization of samples collected in a coastal urban area (Barcelona city), and far away over the Western Mediterranean, at sea level and at 1100 m of altitude, revealed significant changes in the aerosol composition, mainly attributed to initial vapor-particle partitioning processes, influenced by ambient temperature variations, and to others taking place during long-range atmospheric transport, related with the different compound photoreactivities and with an unexplained source-decoupling phenomenon.     

Studies on the metal-nuclotide (Co-5′IMP,Co-5′GMP) interaction via mössbauer emission spectroscopy and magnetic susceptibility measurements

By means of⁵⁷Co Mössbauer emission spectroscopy and magnetic susceptibility measurements, the local symmetries and electronic structure of the Co(II) ions in the Co-5IMO and Co-5GMP complexes in the hydrated and dehydrated forms have been determined.     

Development of a capillary electrophoretic method for the separation of diastereoisomers of a new human immunodeficiency virus protease inhibitor

A capillary electrophoretic (CE) method was developed for the separation of diastereoisomers of a new human immunodeficiency virus (HIV) protease inhibitor TMC114. In total 16 isomers of this drug have been synthesized (eight pairs of enantiomers). We succeeded in the separation of the eight diastereoisomers, but no enantiomers could be separated. Because of the high similarity and water-insolubility of these isomers, the separation is a real challenge. Different CE modes were tried out: capillary zone electrophoresis (CZE), nonaqueous capillary electrophoresis (NACE), micellar electrokinetic capillary chromatography (MEKC), and microemulsion electrokinetic capillary chromatography (MEEKC). Only MEEKC offered resolution of these compounds.     

Topotactic oxidation of TiGaPO-1, a pyridine-templated titanium gallophosphate with a new octahedral-tetrahedral 3-D framework structure containing Ti(III)/Ti(IV)

The first 3-D open-framework TiGaPO complex, constructed from Ti(III)O(6), Ti(IV)O(6), GaO(4), and PO(4) polyhedra, contains pyridinium cations in a 1-D pore network and can be oxidized in air at 543 K with retention of the original framework structure.