Influence of polymerizing agent on structure and spectroscopic properties of nano‐crystalline La0.8Sr0.2MnO3 powders

Strontium‐doped lanthanum manganite (La_1‐xSr_xMnO₃ or LSM) is the material most widely used on solid oxide fuel cells cathode. In this work, nano‐scale La_0.8Sr_0.2MnO₃ powders have been synthesized by polymeric precursor‐based methods using different polymerizing agents with the aim of evaluating the influence of this change in the final powder. The powders calcined at 700 °C for 2 h have been characterized by X‐ray diffraction (XRD), scanning electron microscopy (FE‐SEM) and Fourier transform infrared spectroscopy (FTIR) in order to investigate the quality of both synthesis routes. It is shown that the crystal structure and morphology of the particles are significantly dependent on the preparation conditions. Single phase and La_0.8Sr_0.2MnO₃ nano‐crystalline particles less than 30 nm were obtained using ethylene glycol as polymerizing agent. FTIR results have been indicated that only the powder obtained using gelatin presented small traces of hydroxyl groups on its surface. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Biosurfactant production by Rhodococcus erythropolis grown on glycerol as sole carbon source

The production of biosurfactant by Rhodococcus erythropolis during the growth on glycerol was investigated. The process was carried out at 28 degrees C in a 1.5-L bioreactor using glycerol as carbon source. The bioprocess was monitored through measurements of biosurfactant concentration and glycerol consumption. After 51 h of cultivation, 1.7 g/L of biosurfactant, surface, and interfacial tensions values (with n-hexadecane) of 43 and 15 mN/m, respectively, 67% of Emulsifying Index (E (24)), and 94% of oil removal were obtained. The use of glycerol rather than what happens with hydrophobic carbon source allowed the release of the biosurfactant, originally associated to the cell wall.     

Unusual solvent effect on a SN2 reaction. A quantum-mechanical and kinetic study of the Menshutkin reaction between 2-amino-1-methylbenzimidazole and iodomethane in the gas phase and in acetonitrile

The quaternization reaction between 2-amino-1-methylbenzimidazole and iodomethane was investigated in the gas phase and in liquid acetonitrile. Both experimental and theoretical techniques were used in this study. In the experimental part of this work, accurate second-order rate constants were obtained for this reaction in acetonitrile from conductivity data in the 293-323 K temperature range and at ambient pressure. From two different empirical equations describing the effect of temperature on reaction rates, thermodynamic functions of activation were calculated. In the theoretical part of this work, the mechanism of this reaction was investigated in the gas phase and in acetonitrile. Two different quantum levels (B3LYP/[6-311++G(3df,3pd)/LanL2DZ]//B3LYP/[6-31G(d)/LanL2DZ] and B3LYP/[6-311++G(3df,3pd)/LanL2DZ]//B3LYP/[6-31+G(d)/LanL2DZ]) were used in the calculations, and the acetonitrile environment was modeled using the polarized continuum model (PCM). In addition, an atoms in molecules (AIM) analysis was made aiming to characterize possible hydrogen bonding. The results obtained by both techniques are in excellent agreement and lead to new insight into the mechanism of the reaction under examination. These include the identification and thermodynamic characterization of the relevant stationary species, the rationalization of the mechanistic role played by the solvent and the amine group adjacent to the nucleophile nitrogen atom, the proposal of alternative paths on the modeled potential energy surfaces, and the origin of the marked non-Arrhenius behavior of the kinetic data in solvent acetonitrile. In particular, the AIM analysis confirmed the operation of intermolecular hydrogen bonds between reactants and between products, both in the gas phase and in solution. It is also concluded that the unusual solvent effect on this Menshutkin reaction stems from the conjunction of a nucleophile possessing a relatively complex chemical structure with a dipolar aprotic solvent that is protophobic.     

Mean field linear response within the elimination of the small component formalism to evaluate relativistic effects on magnetic properties

The linear response within the elimination of the small component formalism is aimed at obtaining the leading order relativistic corrections to magnetic molecular properties in the context of the elimination of the small component approximation. In the present work we extend the method in order to include two-body effects in the form of a mean field one-body operator. To this end we consider the four-component Dirac-Hartree-Fock operator as the starting point in the evaluation of the second order relativistic expression of magnetic properties. The approach thus obtained is the fully consistent leading order approximation of the random phase approximation four-component formalism. The mean field effect on the relativistic corrections to both the diamagnetic and paramagnetic terms of magnetic properties taking into account both the Coulomb and Breit two-body interactions is considered.     

A comparison of a gas chromatographic with electron-capture detection and a gas chromatographic with mass spectrometric detection screening methods for the analysis of famoxadone in grapes and wines

Famoxadone is a recent oxazolidinedione fungicide widely used in viticulture and in Integrated Pest Management strategies. In this work, after a simple and fast liquid-liquid extraction (LLE), two new gas chromatographic methods were developed to analyze famoxadone residues in grapes and wines, one with electron-capture detection (GC-ECD) and the other with mass spectrometry (GC-MS). Global uncertainties for validation parameters of both methods were compared. Limits of detection (LODs) were 0.06 and 0.02 mg/L, precision was not above 11.7 and 6.8% and recoveries were, on average, 103%+/-12 and 96%+/-12, respectively, for the GC-ECD and GC-MS methods. Similar expanded uncertainties in the range from 0.25 to 1.00 mg/L were below 35%, with increasing values for lower levels of famoxadone. GC-MS method had a lower LOD and a lower uncertainty if compared with the GC-ECD method.     

Thermodynamic characterization of the prevailing molecular interactions in mixed floating monolayers of phospholipids and usnic acid

The investigation of the characteristics of mixed floating monolayers of phospholipids and usnic acid (UA), an active metabolite from lichens, can provide valuable information on how to prepare stable liposomes that could serve as carriers of UA for therapeutic proposes. The present paper is concerned with the thermodynamic analysis of the behavior of Langmuir monolayers formed by mixing different phospholipids (dibehenoylphosphatidylcholine, DBPC, dipalmitoylphosphatidylcholine, DPPC, and dioleoylphosphatidylcholine, DOPC) and UA at varied molar fractions. Relevant thermodynamic parameters such as excess areas, excess free energies and free energy of mixing were derived from the surface pressure data obtained from compression measurements performed in a Langmuir trough. For the largest lateral pressure examined (25 mN/m), negative values of the excess free energy were found only for the DOPC/UA monolayer, which should be the most stable of them. Based on the calculated values of the free energy of mixing, we note that the DBPC/UA and DPPC/UA systems present the best mixed character at low pressures and when the molar fraction of the UA is 0.5; at that relative concentration and at low values of the external pressure, the UA molecules can better mix and interact with the phospholipid molecules. The compression isotherms for mixed monolayers show no visible transitions, exhibiting a more organized phase that corresponds to a negative free energy of mixing. We have established that the most stable monolayers were those corresponding to DOPC/UA mixtures with a UA molar fraction of 0.75.     

Aggregation of methyl orange probed by electrical impedance spectroscopy

We present results of an electrical impedance spectroscopy investigation of the evolution of the aggregation of methyl orange (MO) in pure aqueous solutions as the concentration of the dye is varied. By applying the constant phase element (CPE) approximation to model the electrical response of the MO solutions, we have verified that the formation of dimers and oligomers can be recognized by specific signatures in the loss and capacitive components of the dielectric response of the system. We interpret these well-defined changes in the dielectric properties of the solutions as a result of molecular rearrangements caused by the aggregation process that alter the current circulation pathways and the electric dipole distribution. The fact that these specific changes in the dielectric behavior coincide with critical concentrations where dimer and oligomer formation in pure aqueous MO solutions are known to occur suggests that electrical impedance spectroscopy can be a competitive technique for the investigation of aggregation behavior in dyes and surfactants.     

Linear stability analysis of transverse dunes

Sand-moving winds blowing from a constant direction in an area of high sand availability form transverse dunes, which have a fixed profile in the direction orthogonal to the wind. Here we show, by means of a linear stability analysis, that transverse dunes are intrinsically unstable. Any perturbation in the cross-wind profile of a transverse dune amplifies in the course of dune migration due to the combined effect of two main factors, namely: the lateral transport through avalanches along the dune’s slip-face, and the scaling of dune migration velocity with the inverse of the dune height. Our calculations provide a quantitative explanation for recent observations from experiments and numerical simulations, which showed that transverse dunes moving on the bedrock (or “transverse sand ridges”) cannot exist in a stable form and decay into a chain of crescent-shaped barchans.     

Singlet Oxygen Generation Enhanced by Silver-Pectin Nanoparticles

We demonstrate the potential application of silver-pectin nanoparticles on photodynamic therapy, on a solution-base platform. Photodynamic therapy is a medical technique which uses a combination of photosensitizing drugs and light to induce selective damage on the target tissue, by electronically excited and highly reactive singlet state of oxygen. Metal enhanced singlet oxygen generation in riboflavin water solution with silver-pectin nanoparticles was observed and quantified. Here 13 nm silver nanospheres enclosed by a pectin layer were synthesized and it interaction with riboflavin molecule was analyzed. Pectin, a complex carbohydrate found in plants primary cell walls, was used to increase the biocompatibility of the silver nanoparticles and to improve metal enhanced singlet oxygen generation (28.5 %) and metal-enhanced fluorescence (30.7 %) processes at room temperature. The singlet oxygen sensor fluorescent green reagent was used to quantify the enhancement of the riboflavin singlet oxygen production induced by the silver colloid. We report a 1.7-fold increase of riboflavin emission and a 1.8-fold enhancement of singlet oxygen production.     

On the isothermal closed space sublimation growth of CdSe using a mixed source for selenium

The use of a selenium–tellurium (SeTe) mixed source in the isothermal close space sublimation growth of CdSe epilayers is considered. The epitaxial growth was performed in flowing helium by sequential exposures of the substrate to vapors of the mixed SeTe source and elemental cadmium at temperatures within 350–410 °C. In spite of the mixed source (proposed to decrease the partial pressure of Se), tellurium incorporation was small and CdSe_xTe_(1−x) (x∼0.98) epilayers were obtained. X-ray diffraction reciprocal space mapping shows the existence of hexagonal inclusions mainly on the (1 1 1) facets of the cubic phase. Material deposition on areas of the graphite crucible exposed to the sources, contamination of the Cd source and large growth rates suggest the existence of a selenium transport process via graphite. This transport might be the result of the combination of selenium deposition on graphite with a subsequent activated desorption of selenium under cadmium exposure. It affects Cd source purity and growth kinetic bringing on a modification of the usual atomic layer deposition regimen; however, a reproducible growth rate of the epilayers was obtained.