Asymmetry and magnetism in bis(oximato)-bridged heterobimetallic compounds: a computational approach

A density functional study of exchange coupling was carried out for a series of heterobinuclear oximato-bridged transition metal complexes. Model calculations were used to examine the influence of the electronic configuration of the metal atoms on the coupling constants. This analysis was complemented by a study of the variation of the coupling constant with the most usual structural distortions within this family of compounds. The influence of the nature of the terminal ligands as well as that of the symmetry on the bridge were also investigated.     

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.     

Molybdenum(VI) and molybdenum(V) mononuclear and dinuclear complexes with 1,3-diphenyl-1,3-propanedione

Summary The synthesis and the dinuclear or mononuclear nature of several molybdenum(VI) and molybdenum(V) oxocomplexes derived from 1,3-diphenyl-1,3-propanedione (HLL) are described. These complexes were identified by i.r. and electronic spectra, magnetic susceptibility and analytical data, and are assigned the following formulae: [MoO₂(LL)₂], [Mo₂O₅(LL)₂], [Mo₂O₄(LL)₂], [MoOCl(LL)₂], [MoCl₂(LL)] and [MoO(OH)(LL)₂)]. The low magnetic moments of the dinuclear complexes are due, in part, to intramolecular interactions. The i.r. data show that the dionate is bound by two oxygen atoms forming a chelate six-membered ring.     

Complexation of the Non-steroidal Anti-inflammatory Drug Nabumetone with Modified and Unmodified Cyclodextrins

The inclusion of the anti-inflammatory drug, Nabumetone, in -, - and hydroxypropyl--cyclodextrin (CDs) is studied using UV-VIS absorption and steady-state fluorescence emission. Binding constants and thermodynamic parameters of complex formation are determined by spectrofluorimetry. The inclusion phenomena of Nabumetone with the three cyclodextrins is compared with that of the well known similar anti-inflammatory drug Naproxen. In the case of Nabumetone pronounced differences are observed in the complexation process with each cyclodextrin whereas the respective Naproxen complexes are nearly identical. ¹H-NMR experiments show that the inclusion process in Nabumetone can occur either through the substituents in the -2 (butanone) or -6 (methoxy) positions in the naphthalene ring.     

Optimization of a microwave-assisted extraction method for the analysis of polychlorinated biphenyls in ash samples

An alternative method for the extraction of polychlorinated biphenyls (PCBs) in ash samples, which is less time and solvent consuming than Soxhlet extraction, is presented. A study was carried out to evaluate the possibilities of microwave-assisted extraction (MAE) to determine exactly which parameters affect the efficiency of the process, since direct extrapolation of extraction conditions for PCBs in other solid matrices, failed when applied to coplanar congeners in ash samples. Influence of the organic solvent on the yield of the extraction was first evaluated using two ash samples with different percentages of carbon. Once the extraction solvent was fixed, the effects of solvent volume, extraction temperature and extraction time were investigated using an experimental design. It was found that the volume of organic solvent played a more important role in the extraction efficiency than the other factors. In the optimal conditions microwave extractions were performed at 110 degrees C. for 10 min and using 30 ml of toluene. Recoveries higher than 80% were obtained for all the highly chlorinated congeners. including coplanar species, in a spiked ash sample containing a relatively high concentration of carbon. The proposed method was also applied to the determination of PCBs in a reference material of urban dust. Recoveries were similar to those obtained for spiked ash samples.     

Micellar solutions of sulfobetaine surfactants in water-ethylene glycol mixtures: surface tension, fluorescence, spectroscopic, conductometric, and kinetic studies

Micellization in water-ethylene glycol (EG) N-dodecyl, N-tetradecyl, and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (SB3-12, SB3-14, and SB3-16, respectively) micellar solutions, with the weight percent of EG changing within the range 0-40, was studied by means of surface tension measurements. Information about the influence of the added EG on the aggregation number of the sulfobetaine micelles and on the polarity of the interfacial region of micelles was obtained through fluorescence and spectroscopic measurements. Surface tension measurements also provide information about the dependence of the surface excess concentration, the minimum area per surfactant molecule, the surface pressure at the cmc, and the standard Gibbs energy of adsorption on the added weight percent of the organic solvent. The Gordon parameter of the water-EG mixtures was also estimated by means of surface tension measurements. The thermodynamic and structural changes originated by the presence of EG control the micellar kinetic effects observed in the reaction methyl 4-nitrobenzenesulfonate + Br(-) occurring in the water-EG sulfobetaine micellar solutions. Information about the distribution of bromide ions between the bulk and micellar pseudophases was obtained through conductivity measurements. The kinetic micellar effects were quantitatively explained by using the pseudophase kinetic model.     

About the calculation of exchange coupling constants in polynuclear transition metal complexes

The application of theoretical methods based on the density functional theory with hybrid functionals provides good estimates of the exchange coupling constants for polynuclear transition metal complexes. The accuracy is similar to that previously obtained for dinuclear compounds. We present test calculations on simple model systems based on H. He and CH(2). He units to compare with Hartree-Fock and multiconfigurational results. Calculations for complete, nonmodeled polynuclear transition metal complexes yield coupling constants in very good agreement with available experimental data.     

Improvements on radiochemical method for the determination of Am and Cm in typical waste streams from nuclear power plants

The determination of Am and Cm in typical waste streams from nuclear power plants using anion exchange chromatography has some drawbacks like the contamination by Pu and Po. This improved procedure solves these problems, and it has been applied with success to the analysis of Am and Cm in nuclear waste samples: ion exchange resins, ion exchange resins solidified with cement and evaporator concentrates.     

Solid-phase extraction of phenols

Sample preparation for phenol analysis using solid-phase extraction (SPE) is reviewed. The scope of the review has been restricted to the literature dealing with the analysis of phenols as the main objective. The use, advantages and disadvantages of silica sorbents, polymeric, functionalized, carbon-based and mixed available sorbents, when applied to the separation and preconcentration of phenols, as well as the available experimental devices, are discussed. Other aspects such as phenol derivatisation prior to SPE, solid-phase microextraction, matrix effects and the storage of phenols in SPE cartridges, have been also discussed.     

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.