Joint Experimental and Theoretical Analysis of Order Disorder Effects in Cubic BaZrO(3) Assembled Nanoparticles under Decaoctahedral Shape

Periodic first-principles calculations based on density functional theory at the B3LYP level has been carried out to investigate the photoluminescence (PL) emission of BaZrO(3) assembled nanoparticles at room temperature. The defect created in the nanocrystals and their resultant electronic features lead to a diversification of electronic recombination within the BaZrO(3) band gap. Its optical phenomena are discussed in the light of photoluminescence emission at the green-yellow region around 570 nm. The theoretical model for displaced atoms and/or angular changes leads to the breaking of the local symmetry, which is based on the refined structure provided by Rietveld methodology. For each situation a band structure, charge mapping, and density of states were built and analyzed. X-ray diffraction (XRD) patterns, UV-vis measurements, and field emission scanning electron microscopy (FE-SEM) images are essential for a full evaluation of the crystal structure and morphology.

Effect of pH on the production of dispersed Bi4Ge3O12 nanoparticles by combustion synthesis

This paper reports the production of bismuth germanate ceramic scintillator (Bi4Ge3O12) by combustion synthesis (SHS) method, focusing on the influence of the synthesis parameters on the crystalline phases and agglomeration of the nanoparticles. The synthesis and sintering conditions were investigated through thermal analysis, X-ray diffraction as function of temperature, dilatometry and scanning electron microscopy. Well-dispersed Bi4Ge3O12 powder was accomplished by the combustion of the initial solution at pH 9, followed by low temperature calcination and milling. Sintered ceramics presented relative density of 98% and single crystalline Bi4Ge3O12 phase. The luminescent properties of the ceramics were investigated by photo- and radio- luminescence measurements and reproduced the typical Bi4Ge3O12 single-crystal spectra when excited with UV, beta and X-rays. The sintered ceramics presented light output of 4.4 x 10(3) photons/McV. (c) 2008 Published by Elsevier Ltd.

Er : YAB nanoparticles and vitreous thin films by the polymeric precursor method

The synthesis of Y(0.9)Er(0.1)Al(3)(BO(3))(4) crystalline powders and vitreous thin films were studied. Precursor solutions were obtained using a modified polymeric precursor method using D-sorbitol as complexant agent. The chemical reactions were described. Y(0.)9Er(0.1)Al(3)(BO(3))(4) composition presents good thermal stability with regard to crystallization. The Y(0.9)Er(0.1)Al(3)(BO(3))(4) crystallized phase can be obtained at 1,150 degrees C, in agreement with other authors. Crack- and porosity-free films were obtained with very small grain size and low RMS roughness. The films thickness revealed to be linearly dependent on precursor solution viscosity, being the value of 25 mPa s useful to prepare high-quality amorphous multi-layers (up to similar to 800 nm) at 740 degrees C during 2 h onto silica substrates by spin coating with a gyrset technology.

Rhodium-catalyzed carbonylation of allylaminoalcohols: Catalytic synthesis of N-(2-hydroxy-alkyl)-gamma-lactams and bicyclic oxazolidines

Gamma-lactams and bicyclic oxazolidines are important structural frameworks in both synthetic organic chemistry and related pharmacological fields. These heterocycles can be prepared by the rhodium-catalyzed carbonylation of unsaturated amines. In this work, allylaminoalcohols, derived from the aminolysis of cyclohexene oxide, styrene oxide, (R)-(+)-limonene oxide, and ethyl-3-phenyl-glicidate, were employed as substrates. These allylaminoalcohols were carbonylated by employing RhClCO(PPh3)(2) as a precatalyst under varying CO/H-2 mixtures, and moderate to excellent yields were obtained, depending on the substrate used. The results indicated that an increase in the chelating ability of the substrate (-OH and -NHR moieties) decreased the conversion and selectivity of the ensuing reaction. Additionally, the selectivity could be optimized to favor either the gamma-lactams or the oxazolidines by controlling the CO/H-2 ratio. A large excess of CO provided a lactam selectivity of up to 90%, while a H-2-rich gas mixture improved the selectivity for oxazolidines, resulting from hydroformylation/cyclization. Studies of the reaction temperature indicated that an undesirable substrate deallylation reaction occurs at higher temperature (>100 degrees C). Further, kinetic studies have indicated that the oxazolidines and gamma-lactams were formed through parallel routes. Unfortunately, the mechanism for oxazolidines formation is not yet well understood. However, our results have led us to propose a catalytic cycle based on hydroformylation/acetalyzation pathways. The gamma-lactams formation follows a carbonylation route, mediated by a rhodium-carbamoylic intermediate, as previously reported. To this end, we have been able to prepare and isolate the corresponding iridium complex, which could be confirmed by X-ray crystallographic analysis. (C) 2008 Elsevier B.V. All rights reserved.

gamma-zein secondary structure in solution by circular dichroism

The proline-rich N-terminal domain of gamma-zein has been reported in relevant process, which include its ability to cross the cell membranes. Evidences indicate that synthetic hexapeptide (PPPVHL), naturally found in N-terminal portion of gamma-zein, can adopt the polyproline II (PPII) conformation in aqueous solution. The secondary structure of gamma-zein in maize protein bodies had been analyzed by solid state Fourier transform infrared and nuclear magnetic resonance spectroscopies. However, it was not possible to measure PPII content in physiological environment since the beta-sheet and PPII signals overlap in both solid state techniques. Here, the secondary structure of gamma-zein has been analyzed by circular dichroism in SDS aqueous solution with and without ditiothreitol (DTT), and in 60% of 2-propanol and water with DTT The results show that gamma-zein has high helical content in all solutions. The PPII conformation was present at about 7% only in water/DTT solution. (c) 2007 Wiley Periodicals, Inc.

Highly Stable, Edible Cellulose Films Incorporating Chitosan Nanoparticles

The need for biodegradable polymers for packaging has fostered the development of novel, biodegradable polymeric materials from natural sources, as an alternative to reduce amount of waste and environmental impacts. The present investigation involves the synthesis of chitosan nanoparticles-carboxymethylcellulose films, in view of their increasing areas of application in packaging industry. The entire process consists of 2-steps including chitosan nanoparticles preparation and their incorporation in carboxymethylcellulose films. Uniform and stable particles were obtained with 3 different chitosan concentrations. The morphology of chitosan nanoparticles was tested by transmission electron microscopy, revealing the nanoparticles size in the range of 80 to 110 nm. The developed film chitosan nanoparticles-carboxymethylcellulose films were characterized by Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis, solubility tests, and mechanical analysis. Improvement of thermal and mechanical properties were observed in films containing nanoparticles, with the best results occurring upon addition of nanoparticles with 110 nm size in carboxymethylcellulose films. Practical Application Carboxymethylcellulose films containing chitosan nanoparticles synthesized and characterized in this article could be a potential material for food and beverage packaging applications products due to the increase mechanical properties and high stability. The potential application of the nanocomposites prepared would be in packaging industry to extend the shelf life of products.

Structural requirement for PPAR gamma binding revealed by a meta analysis of holo-crystal structures

PPAR gamma is a ligand regulated transcriptional factor that modulates the transcription of several genes involved in fat and sugar metabolism. Due to its easy bacterial expression and crystallization, several crystal structures of holo-PPAR gamma have been reported and deposited in the Protein Data Bank. Here, we investigated the three-dimensional electrostatic properties of 55 PPAR gamma ligands and used this information for clustering them through principal component analysis. We found out that, according to their electrostatic potential, these ligands can be separated in three groups, with different binding features. We also observed that non-selective and selective ligands show different 3D electrostatic properties and are separated in different clusters. The relevance of this analysis for the development of new binders is discussed. (C) 2010 Elsevier Masson SAS. All rights reserved.

Footemineite, the Mn-analog of atencioite, from the Foote mine, Kings Mountain, Cleveland County, North Carolina, USA, and its relationship with other roscherite-group minerals

Footemineite, ideally Ca2Mn2+square Mn22+Be4(PO4)(6)(OH)(4)-6H(2)O, triclinic, is a new member of the roscherite group. It occurs on thin fractures crossing quartz-microcline-spodumene pegmatite at the Foote mine, Kings Mountain, Cleveland County, North Carolina, U.S.A. Associated minerals are albite, analcime, eosphorite, siderite/rhodochrosite, fairfieldite, fluorapatite, quartz, milarite, and pyrite. Footemineite forms prismatic to bladed generally rough to barrel-shaped crystals up to about 1.5 mm long and I mm in diameter. Its color is yellow, the streak is white, and the luster is vitreous to slightly pearly. Footemineite is transparent and non-fluorescent. Twinning is simple, by reflection, with twin boundaries across the length of the crystals. Cleavage is good on {0 (1) over bar1}) and {100}. Density (calc.) is 2.873 g/cm(3). Footemineite is biaxial (-), n(alpha) = 1.620(2), n(beta) = 1.627(2), n(gamma) = 1.634(2) (white light). 2V(obs) = 80 degrees, 2V(calc) = 89.6 degrees. Orientation: X boolean AND b similar to 12 degrees, Y boolean AND c similar to 15 degrees, Z boolean AND a similar to 15 degrees. Elongation direction is c, dispersion: r > v or r < v, weak. Pleochroism: beta (brownish yellow) > alpha = gamma (yellow). Mossbauer and IR spectra are given. The chemical composition is (EDS mode electron microprobe, Li and Be by ICP-OES, Fe3+:Fe2+ y Mossbauer, H2O by TG data, wt%): Li2O 0.23, BeO 9.54, CaO 9.43, SrO 0.23, BaO 0.24, MgO 0.18, MnO 26.16, FeO 2.77, Fe2O3 0.62, Al2O3 0.14, P2O5 36.58, SiO2 0.42, H2O 13.1, total 99.64. The empirical formula is (Ca1.89Sr0.03Ba0.02)Sigma(1.94)(Mn-0.90(2+)square(0.10))Sigma(1.00)(square 0.78Li0.17Mg0.05) Sigma(1.00)(Mn3.252+Fe0.432+ Fe0.093+Al0.03)Sigma(3.80) Be-4.30(P5.81Si0.08O24)[(OH)3.64(H2O)0.36]Sigma(4.00)center dot 6.00H(2)O . The strongest reflection peaks of the powder diffraction pattern [d, angstrom (1, %) (hkl)] are 9.575 (53) (010), 5.998 (100) (0 (1) over bar1), 4.848 (26) (021), 3.192 (44) (210), 3.003 (14) (0 (2) over bar2), 2.803 (38) ((1) over bar 03), 2.650 (29) ((2) over bar 02), 2.424 (14) (231). Single-crystal unit-cell parameters are a = 6.788(2), b = 9.972(3), c = 10.014(2) A, (x = 73.84(2), beta = 85.34(2), gamma = 87.44(2)degrees,V = 648.74 angstrom(3), Z = 1. The space group is P (1) over bar. Crystal structure was refined to R = 0.0347 with 1273 independent reflections (F > 2(5). Footemineite is dimorphous with roscherite, and isostructural with atencioite. It is identical with the mineral from Foote mine described as ""triclinic roscherite."" The name is for the Foote mine, type locality for this and several other minerals.

Deviance residuals in generalised log-gamma regression models with censored observations

In this article, we compare three residuals based on the deviance component in generalised log-gamma regression models with censored observations. For different parameter settings, sample sizes and censoring percentages, various simulation studies are performed and the empirical distribution of each residual is displayed and compared with the standard normal distribution. For all cases studied, the empirical distributions of the proposed residuals are in general symmetric around zero, but only a martingale-type residual presented negligible kurtosis for the majority of the cases studied. These studies suggest that the residual analysis usually performed in normal linear regression models can be straightforwardly extended for the martingale-type residual in generalised log-gamma regression models with censored data. A lifetime data set is analysed under log-gamma regression models and a model checking based on the martingale-type residual is performed.

Ric-8B interacts with G alpha olf and G gamma 13 and co-localizes with G alpha olf, G beta 1 and G gamma 13 in the cilia of olfactory sensory neurons

Olfactory sensory neurons are able to detect odorants with high sensitivity and specificity. We have demonstrated that Ric-8B, a guanine nucleotide exchange factor (GEF), interacts with G alpha olf and enhances odorant receptor signaling. Here we show that Ric-8B also interacts with G gamma 13, a divergent member of the G gamma subunit family which has been implicated in taste signal transduction, and is abundantly expressed in the cilia of olfactory sensory neurons. We show that G beta 1 is the predominant GP subunit expressed in the olfactory sensory neurons. Ric-8B and G beta 1, like G alpha olf and G gamma 13, are enriched in the cilia of olfactory sensory neurons. We also show that Ric-8B interacts with G alpha olf in a nucleotide dependent manner, consistent with the role as a GEF. Our results constitute the first example of a GEF protein that interacts with two different olfactory G protein subunits and further implicate Ric-8B as a regulator of odorant signal transduction. (C) 2008 Elsevier Inc. All rights reserved.

Aerobic oxidation of monoterpenic alcohols catalyzed by ruthenium hydroxide supported on silica-coated magnetic nanoparticles

Ruthenium hydroxide supported on silica-coated magnetic nanoparticles was shown to be an efficient heterogeneous catalyst for the liquid-phase oxidation of a wide range of alcohols using molecular oxygen as a sole oxidant in the absence of co-catalysts or additives. The material was prepared through the loading of the amino modified support with ruthenium(III) ions from an aqueous solution of ruthenium(III) chloride followed by treatment with sodium hydroxide to form ruthenium hydroxide species. Characterizations suggest that ruthenium hydroxide is highly dispersed on the support surface, with no ruthenium containing crystalline phases being detected. Various carbonylic monoterpenoids important for fragrance and pharmaceutical industries can be obtained in good to excellent yields starting from biomass-based monoterpenic alcohols, such as isobomeol, perillyl alcohol, carveol, and citronellol. The catalyst undergoes no metal leaching and can be easily recovered by the application of an external magnet and re-used. (C) 2011 Elsevier Inc. All rights reserved.

Kinetic resolution of a drug precursor by Burkholderia cepacia lipase immobilized by different methodologies on superparamagnetic nanoparticles

Burkholderia cepacia lipase was immobilized on superparamagnetic nanoparticles using three different methodologies (adsorption, chemisorption with carboxibenzaldehyde and chemisorption with glutaraldehyde) and employed in the kinetic resolution of a chiral drug precursor, (RS)-2-bromo-1-(phenyl)ethanol, via enantioselective acetylation reaction. An excellent improvement of lipase catalytical performance was observed. Free B. cepacia lipase gave the ester (S)-2 with poor E-value <30, and after its immobilization to magnetic nanoparticles the E-value was up to >200. The effect of several reaction parameters in the kinetic resolution was studied. The best results for kinetic resolution were obtained using vinyl acetate as acetyl donor and toluene as solvent, typically yielding the ester in high enantiomeric excess (>99%) and E-value (E > 200). Of the three tested immobilization methods, chemisorption with glutaraldehyde was the best one in terms of temperature stability and yield product. (C) 2010 Elsevier B.V. All rights reserved.

Adsorption of anionic amphiphilic polyelectrolytes onto amino-terminated solid surfaces

The adsorption behavior of several amphiphilic polyelectrolytes of poly(maleic anhydride-alt-styrene) functionalized with naphthyl and phenyl groups, onto amino-terminated silicon wafer has been studied by means of null- ellipsometry, atomic force microscopy (AFM) and contact angle measurements. The maximum of adsorption, Gamma(plateau), varies with the ionic strength, the polyelectrolyte structure and the chain length. Values of Gamma(plateau) obtained at low and high ionic strengths indicate that the adsorption follows the ""screening-reduced adsorption"" regime. Large aggregates were detected in solution by means of dynamic light scattering and fluorescence measurements. However. AFM indicated the formation of smooth layers and the absence of aggregates. A model based on a two-step adsorption behavior was proposed. In the first one, isolated chains in equilibrium with the aggregates in solution adsorbed onto amino-terminated surface. The adsorption is driven by electrostatic interaction between protonated surface and carboxylate groups. This first layer exposes naphtyl or phenyl groups to the solution. The second layer adsorption is now driven by hydrophobic interaction between surface and chains and exposes carboxylate groups to the medium, which repel the forthcoming chain by electrostatic repulsion. Upon drying some hydrophobic naphtyl or phenyl groups might be oriented to the air, as revealed by contact angle measurements. Such amphiphilic polyelectrolyte layers worked well for the building-up of multilayers with chitosan. (C) 2010 Elsevier Ltd. All rights reserved.

Effects of gamma radiation on the photoluminescence properties of polycarbonate matrices doped with terbium complex

Luminescent films containing terbium complex [Tb(acac)(3)(H(2)O)(3)] (acac = acetylacetonate) doped into a polycarbonate (PC) matrix were prepared and irradiated at low-dose gamma radiation with ratio of 5 and 10 kGy. The PC polymer was doped with 5% (w/w) of the Tb(3+) complex. The thermal behavior was investigated by utilization of differential scanning calorimetry (DSC) and thermogravimetry analysis (TGA). Changes in thermal stability due to the addition of doping agent into the polycarbonate matrix. Based on the emission spectra of PC:5% Tb(acac)(3) film were observed the characteristic bands arising from the (5)D(4) -> (7)F(J) transitions of Tb(3+) ion (J = 0-6), indicating the ability to obtain the luminescent films. Doped samples irradiated at low dose of gamma irradiation showed a decrease in luminescence intensity with increasing of the dose. (C) 2009 Elsevier Ltd. All rights reserved.

A large-scale synthesis of enantiomerically pure gamma-hydroxy-organochalcogenides

Enantiomerically pure (R)- and (S)-gamma-hydroxy-organochalcogenides are prepared using poly-[R]-3-hydroxybutanoate (PHB) as the starting material. (C) 2009 Elsevier Ltd. All rights reserved.