Structural Refinement and Photoluminescence Properties of MnWO4 Nanorods Obtained by Microwave-Hydrothermal Synthesis

Manganese tungstate (MnWO4) nanorods were prepared at room temperature by the co-precipitation method and synthesized after processing in a microwave-hydrothermal (MH) system at 140 degrees C for 6-96 min. These nanorods were structurally characterized by X-ray diffraction (XRD), Rietveld refinements and Fourier transform (FT)-Raman spectroscopy. The growth direction, shape and average size distribution of nanorods were observed by means of transmission electron microscopy (TEM) and high resolution TEM (HR-TEM). The optical properties of the nanorods were investigated by ultraviolet visible (UV-vis) absorption and photoluminescence (PL) measurements. XRD patterns, Rietveld refinement data and FT-Raman spectroscopy indicate that the MnWO4 precipitate is not a single phase structure while the nanorods synthesized by MH processing have a wolframite-type monoclinic structure without deleterious phases. FT-Raman spectra exhibited the presence of 17 Raman-active modes from 50 to 1,000 cm(-1). TEM and HR-TEM micrographs indicated that the nanorods are aggregated due to surface energy by Van der Waals forces and grow along the [100] direction. UV-vis absorption measurements confirmed non-linear values for the optical band gap (from 3.2 to 2.72 eV), which increased as the MH processing time increased. The structural characterizations indicated that the presence of defects in the MnWO4 precipitate promotes a significant contribution to maximum PL emission, while MnWO4 nanorods obtained by MH processing decrease the PL emission due to the reduction of defects in the lattice.

Local order and electronic structure of Pb1-xLaxZr0.40Ti0.60O3 materials and its relation with ferroelectric properties

The knowledge of electronic and local structures is a fundamental step towards understanding the properties of ferroelectric ceramics. X-ray absorption near-edge structure (XANES) of Pb1-xLaxZr0.40Ti0.60O3 ferroelectric samples was measured in order to know how the local order and electronic structure are related to their ferroelectric property, which was tailored by the substitution of lead by lanthanum atoms. The analysis of XANES spectra collected at Ti K- and L-edges XANES showed that the substitution of Pb by La leads to a decrement of local distortion around Ti atoms on the TiO6 octahedron. The analysis of O K-edge XANES spectra showed that the hybridization between O 2p and Pb 6sp states is related to the displacement of Ti atoms in the TiO6 octahedra. Based on these results, it is possible to determine that the degree of ferroelectricity in these samples and the manifestation of relaxor behavior are directly related to the weakening of O 2p and Pb 6sp hybridization. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4720472]

Electronic and magnetic properties of SnO2/CrO2 thin superlattices

In this article, using first-principles electronic structure calculations within the spin density functional theory, alternated magnetic and non-magnetic layers of rutile-CrO2 and rutile-SnO2 respectively, in a (CrO2) n (SnO2) n superlattice (SL) configuration, with n being the number of monolayers which are considered equal to 1, 2, ..., 10 are studied. A half-metallic behavior is observed for the (CrO2) n (SnO2) n SLs for all values of n. The ground state is found to be FM with a magnetic moment of 2 μB per chromium atom, and this result does not depend on the number of monolayers n. As the FM rutile-CrO2 is unstable at ambient temperature, and known to be stabilized when on top of SnO2, the authors suggest that (CrO2) n (SnO2) n SLs may be applied to spintronic technologies since they provide efficient spin-polarized carriers.

A novel set of ss-N-biaryl ether sulfonamide hydroxamates as potential MMPs inhibitors: Molecular dynamics simulations and molecular properties evaluation

Matrix metalloproteinases (MMPs) constitute a family of zinc-dependent proteases involved in the extracellular matrix degradation. MMP-2 and MMP9 are overexpressed in several human cancer types, including melanoma, thus the development of new compounds to inhibit MMPs' activity is desirable. Molecular dynamic simulation and molecular properties calculations were performed on a set of novel beta-N-biaryl ether sulfonamide-based hydroxamates, reported as MMP-2 and MMP-9 inhibitors, for providing data to develop an exploratory analysis. Thermodynamic, electronic, and steric descriptors have significantly discriminated highly active from moderately and less active inhibitors of MMP-2 whereas apparent partition coefficient at pH 1.5 was also significant for the MMP-9 data set. Compound 47 was considered an outlier in all analysis, indicating the presence of a bulky substituent group in R3 is crucial to this set of inhibitors for the establishment of molecular interactions with the S1 subsite of both enzymes, but there is a limit. (C) 2012 Wiley Periodicals, Inc.

Synthesis, crystal structure and magnetic properties of the helical oxalate-bridged copper(II) chain {[(CH3)(4)N](2)[Cu(C2O4)(2)] center dot H2O}(n)

The preparation, crystal structure and magnetic properties of a new oxalate-containing copper(II) chain of formula {[(CH3)(4)N](2)]Cu(C2O4)(2)] center dot H2O}(n) (1) [(CH3)(4)N+ = tetramethylammonium cation] are reported. The structure of 1 consists of anionic oxalate-bridged copper(II) chains, tetramethylammoniun cations and crystallization water molecules. Each copper(II) ion in 1 is surrounded by three oxalate ligands, one being bidentate and the other two exhibiting bis-bidenate coordination modes. Although all the tris-chelated copper(H) units from a given chain exhibit the same helicity, adjacent chains have opposite helicities and then an achiral structure results. Variable-temperature magnetic susceptibility measurements of 1 show the occurrence of a weak ferromagnetic interaction through the oxalate bridge [J = +1.14(1)cm(-1), the Hamiltonian being defined as H = -J Sigma nm S-i . S-j]. This value is analyzed and discussed in the light of available magnetostructural data for oxalate-bridged copper(H) complexes with the same out-of-plane exchange pathway. (C) 2012 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

Processing and mechanical properties evaluation of glass fiber-reinforced PTFE laminates

A specific manufacturing process to obtain continuous glass fiber-reinforced RIFE laminates was studied and some of their mechanical properties were evaluated. Young's modulus and maximum strength were measured by three-point bending test and tensile test using the Digital Image Correlation (DIC) technique. Adhesion tests, thermal analysis and microscopy were used to evaluate the fiber-matrix adhesion, which is very dependent on the sintering time. The composite material obtained had a Young's modulus of 14.2 GPa and ultimate strength of 165 MPa, which corresponds to approximately 24 times the modulus and six times the ultimate strength of pure RIFE. These results show that the RIFE composite, manufactured under specific conditions, has great potential to provide structural parts with a performance suitable for application in structural components. (C) 2012 Elsevier Ltd. All rights reserved.

Interaction between bradykinin potentiating nonapeptide (BPP9a) and beta-cyclodextrin: A structural and thermodynamic study

Herein, we demonstrate the physical and chemical characterizations of the supramolecular complex formed between beta-cyclodextrin (beta CD) and bradykinin potentiating nonapeptide (BPP9a), an endogenous toxin found in Bothrops jararaca. Circular dichroism results indicate a conformational change in the BPP9a secondary structure upon its complexation with beta CD. Nuclear magnetic resonance results, mainly from NOESY experiments, and theoretical calculations showed a favorable interaction between the tryptophan residue of BPP9a and the beta CD cavity. Thermodynamic inclusion parameters were investigated by isothermal titration calorimetry, demonstrating that beta CD/BPP9a complex formation is an exothermic process that results in a reduction in entropy. Additionally, in vitro degradation study of BPP9a against trypsin (37 degrees C, pH 7.2) showed higher stability of peptide in presence of beta CD. This beta CD/BPP9a complex, which presents new chemical properties arising from the peptide inclusion process, may be useful as an antihypertensive drug in oral pharmaceutical formulations. (C) 2011 Elsevier B.V. All rights reserved.

Effects of the Compaction Pressure on the Magnetic Properties of a Sintered Fe-Based Alloy

The structural and magnetic properties of a Fe-based alloy before and after sintering have been analyzed. X ray diffraction measurements confirm the deformation of the magnetic particles in the compacted samples. After sintering, hysteresis energy dissipation, remanence and intrinsic coercivity differ by less than 10% as porosity changes from 15 to 7%.

Electronic Properties of Water in Liquid Environment. A Sequential QM/MM Study Using the Free Energy Gradient Method

There is a continuous search for theoretical methods that are able to describe the effects of the liquid environment on molecular systems. Different methods emphasize different aspects, and the treatment of both the local and bulk properties is still a great challenge. In this work, the electronic properties of a water molecule in liquid environment is studied by performing a relaxation of the geometry and electronic distribution using the free energy gradient method. This is made using a series of steps in each of which we run a purely molecular mechanical (MM) Monte Carlo Metropolis simulation of liquid water and subsequently perform a quantum mechanical/molecular mechanical (QM/MM) calculation of the ensemble averages of the charge distribution, atomic forces, and second derivatives. The MP2/aug-cc-pV5Z level is used to describe the electronic properties of the QM water. B3LYP with specially designed basis functions are used for the magnetic properties. Very good agreement is found for the local properties of water, such as geometry, vibrational frequencies, dipole moment, dipole polarizability, chemical shift, and spin-spin coupling constants. The very good performance of the free energy method combined with a QM/MM approach along with the possible limitations are briefly discussed.

Synthesis and Characterization of the Europium(III) Pentakis(picrate) Complexes with Imidazolium Countercations: Structural and Photoluminescence Study

Six new lanthanide complexes of stoichiometric formula (C)(2)[Ln(Pic)(5)]-where (C) is a imidazolium cation coming from the ionic liquids 1-butyl-3-methylimidazolium picrate (BMIm-Pic), 1-butyl-3-ethylimidazolium picrate (BEIm-Pic), and 1,3-dibutylimidazolium picrate (BBIm-Pic), and Ln is Eu(III) or Gd(III) ions-have been prepared and characterized. To the best of our knowledge, these are the first cases of Ln(III) pentakis(picrate) complexes. The crystal structures of (BEIm)(2)[Eu(Pic)(5)] and (BBIm)(2)[Eu(Pic)(5)] compounds were determined by single-crystal X-ray diffraction. The [Eu(Pic)(5)](2-) polyhedra have nine oxygen atoms coordinated to the Eu(III) ion, four oxygen atoms from bidentate picrate, and one oxygen atom from monodentate picrate. The structures of the Eu complexes were also calculated using the sparkle model for lanthanide complexes, allowing an analysis of intramolecular energy transfer processes in the coordination compounds. The photoluminescence properties of the Eu(III) complexes were then studied experimentally and theoretically, leading to a rationalization of their emission quantum yields.

Cluster Coordination and Photoluminescence Properties of alpha-Ag2WO4 Microcrystals

In this paper, we report our initial research to obtain hexagonal rod-like elongated silver tungstate (alpha-Ag2WO4) microcrystals by different methods [sonochemistry (SC), coprecipitation (CP), and conventional hydrothermal (CH)] and to study their cluster coordination and optical properties. These microcrystals were structurally characterized by X-ray diffraction (XRD), Rietveld refinements, Fourier transform infrared (FT-IR), X-ray absorption near-edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) spectroscopies. The shape and average size of these alpha-Ag2WO4 microcrystals were observed by field-emission scanning electron microscopy (FE-SEM). The optical properties of these microcrystals were investigated by ultraviolet-visible (UV-vis) spectroscopy and photoluminescence (PL) measurements. XRD patterns and Rietveld refinement data confirmed that alpha-Ag2WO4 microcrystals have an orthorhombic structure. FT-IR spectra exhibited four IR-active modes in a range from 250 to 1000 cm(-1). XANES spectra at the W L-3-edge showed distorted octahedral [WO6] clusters in the lattice, while EXAFS analyses confirmed that W atoms are coordinated by six O atoms. FE-SEM images suggest that the alpha-Ag2WO4 microcrystals grow by aggregation and the Ostwald ripening process. PL properties of alpha-Ag2WO4 microcrystals decrease with an increase in the optical band-gap values (3.19-3.23 eV). Finally, we observed that large hexagonal rod-like alpha-Ag2WO4 microcrystals prepared by the SC method exhibited a major PL emission intensity relative to alpha-Ag2WO4 microcrystals prepared by the CP and CH methods.

Structural and mechanical analysis for the optimization of PVD oxide coatings for protection against metal dusting

The evolution of the structure and properties of Cr/Cr oxide thin films deposited on HK40 steel substrates by reactive magnetron sputtering (RMS) was investigated and linked to their potential protective behavior against metal dusting. Deposition time, mode of oxygen feeding, and application of bias voltage were varied to assess their effect on the density, adhesion, and integrity of the films. All the films showed a very fine columnar microstructure and the presence of amorphous Cr oxide. Both, an increasing time and a constant oxygen flow during deposition led to the development of relatively low density films and mud-like cracking patterns. A graded oxygen flow resulted in films with fewer cracks, but a careful control of the oxygen flow is required to obtain films with a truly graded structure. The effect of the bias voltage was much more significant and beneficial. An increasing negative bias voltage resulted in the development of denser films with a transition to an almost crack-free structure and better adhesion. The amorphous oxide resulted in low values of hardness and Young's modulus. (C) 2012 Elsevier B.V. All rights reserved.

Structural XANES characterization of Ca0.99Sm0.01TiO3 perovskite and correlation with photoluminescence emission

In this work, CaTiO3:Sm (CT:Sm) were prepared by a soft chemical processing at different annealing temperatures starting with a disordered structure and reaching an ordered one, with the propose to understand the relationship between structural order-disorder and photoluminescence emission. The samples were characterized by titanium K-edge, Titanium L-II and L-III-edge XANES, electron paramagnetic resonance (EPR) and photoluminescence (PL) measurements. XANES results clearly point the presence of local distortion in [TiO6] octahedral clusters until the crystallization was completed. The interactions of the network clusters that form the CT:Sm structures provides favorable structural and electronic conditions for the appearance of PL phenomena. (C) 2012 Published by Elsevier B.V.

Effect of the vanadium(V) concentration on the spectroscopic properties of nanosized europium-doped yttrium phosphates

Nanosized rare earth phosphovanadate phosphors (Y(P,V)O-4:Eu3+) have been prepared by applying the organic-inorganic polymeric precursors methodology. Luminescent powders with tetragonal structure and different vanadate concentrations (0%, 1%, 5%, 10%, 20%, 50%, and 100%, with regard to the phosphate content) were then obtained for evaluation of their structural and spectroscopic properties. The solids were characterized by scanning electron microscopy, X-ray diffractometry, vibrational spectroscopy (Raman and infrared), and electronic spectroscopy (emission, excitation, luminescence lifetimes, chromaticity, quantum efficiencies, and Judd-Ofelt intensity parameters). The solids exhibited very intense D-5(0) -> F-7(J) Eu3+ transitions, and it was possible to control the luminescent characteristics, such as excitation maximum, lifetime and emission colour, through the vanadium(V) concentration. The observed luminescent properties correlated to the characteristics of the chemical environments around the Eu3+ ions with respect to the composition of the phosphovanadates. The Eu3+ luminescence spectroscopy results indicated that the presence of larger vanadium(V) amounts in the phosphate host lattice led to more covalent and polarizable chemical environments. So, besides allowing for control of the luminescent properties of the solids, the variation in the vanadate concentration in the obtained YPO4:Eu3+ phosphors enabled the establishment of a strict correlation between the observable spectroscopic features and the chemical characteristics of the powders.

X-ray absorption spectroscopy study on La0.6Sr0.4CoO3 and La0.6Sr0.4Co1¡yFeyO3 nanotubes and nanorods for IT-SOFC cathodes.

In the last years, extensive research has been devoted to develop novel materials and structures with high electrochemical performance for intermediate-temperatures solid-oxide fuel cells (IT-SOFCs) electrodes. In recent works, we have investigated the structural and electrochemical properties of La0:6Sr0:4CoO3 (LSCO) and La0:6Sr0:4Co1¡yFeyO3 (LSCFO) nanostructured cathodes, finding that they exhibit excellent electrocatalytic properties for the oxygen reduction reaction [1,2]. These materials were prepared by a pore-wetting technique using polycarbonate porous membranes as templates. Two average pore sizes were used: 200 nm and 800 nm. Our scanning electronic microscopy (SEM) study showed that the lower pore size yielded nanorods, while nanotubes were obtained with the bigger pore size. All the samples were calcined at 1000oC in order to produce materials with the desired perovskite-type crystal structure. In this work, we analyze the oxidation states of Co and Fe and the local atomic order of LSCO and LSCFO nanotubes and nanowires for various compositions. For this pur- pose we performed XANES and EXAFS studies on both Co and Fe K edges. These measurements were carried out at the D08B-XAFS2 beamline of the Brazilian Synchrotron Light Laboratory (LNLS). XANES spectroscopy showed that Co and Fe only change slightly their oxidation state upon Fe addition. Surprisingly, XANES results indicated that the content of oxygen vacancies is low, even though it is well-known that these materials are mixed ionic-electronic conductors. EXAFS results were consistent with those expected according to the rhombohedral crystal structure determined in previous X-ray powder dffraction investigations. [1] M.G. Bellino et al, J. Am. Chem. Soc. 129 (2007) 3066 [2] J.G. Sacanell et al., J. Power Sources 195 (2010) 1786