SILICA MORPHOLOGY CHARACTERIZED BY SEM - THE EFFECTS OF THE SOLVENT TREATMENT AND THE DRYING PROCESS

Scanning electron microscopy (SEM) was used to investigated the effects of volatile solvents (such as water, propanone, ethanol, methanol or ethyl ether), treatment and drying processes, microwave ovens, drying ovens, and vacuum desiccators or freeze driers, on silica morphology. Silica gel was obtained from diluted sodium silicate (1:5 w/w SiO2:H2O). The results showed that the drying process based on freeze drying is more efficient for structural conservation of the precipitate. Treatment with volatile solvents does not change the shape of the aggregates, but has an important role in the determination of aggregate surface roughness.

Theoretical and experimental study of the relation between photoluminescence and structural disorder in barium and strontium titanate thin films

Thin films of barium and strontium titanate (BST), synthesized by the polymeric precursor solution and spin coated on [Pt (140nm)/Ti (10 nM)/SiO2(1000 nm)/Si] substrates were found to be photoluminescent at room temperature when heat treated below 973 K, i.e. before their crystallization. First principles quantum mechanical techniques, based on density functional theory (DFT) were employed to study the electronic structure of two periodic models: one is standing for the crystalline BST thin film and the other one for the structurally disordered thin film. The aim is to compare the photoluminescence (PL) spectra of the crystalline and disordered thin films with their UV-vis spectra and with their computed electronic structures. The calculations show that new localized states are created inside the band gap of the crystalline model, as predicted by the UV-vis spectra. The study of the charge repartition in the structure before and after deformation of the periodic model shows that a charge gradient appears among the titanate clusters. This charge gradient, together with the new localized levels, gives favorable conditions for the trapping of holes and electrons in the structure, and thus to a radiative recombination process. Our models are not only consistent with the experimental data, they also allow to explain the relations between structural disorder and photoluminescence at room temperature. (c) 2005 Elsevier Ltd. All rights reserved.

Improvement of the ferroelectric properties of ABO(3) (A= Pb, Ca, Ba; B=Ti, Zr) films

High-quality ABO(3)/LaNiO3 (A = Ph, Ca, Ba; B = Ti, Zr) hetero structures have been grown on LaAlO3 (1 0 0) substrate by the chemical solution deposition method and crystallized by a microwave oven technique. The structural, morphological and electric properties were characterized by means of X-ray diffraction (XRD), atomic force microscope (AFM), and dielectric and ferroelectric measurements. XRD patterns revealed single-phase polycrystalline and oriented thin films whose feature depends on the composition of the films. The AFM surface morphologies showed a smooth and crack-free surface with the average grain size ranging from 116 to 300 nm for both LaNiO3 electrode and the ferroelectric films. Dielectric measurements on these samples revealed dielectric constants as high as 1800 at frequency of 100 KHz. Such results showed that the combination of the chemical solution method with the microwave process provides a promising technique to grow high-quality thin films with good dielectric and ferroelectric properties. (c) 2005 Elsevier Ltd. All rights reserved.

Density improvement of the sol-gel dip-coated SnO2 films by chemical surface modification

We compare the effect of organic (Tiron (R)) and inorganic (Mn(11)) additives on the low temperature (< 600 degrees C) densification of the sol-gel dip-coated SnO2 films. The structural and compositional properties of the samples were investigated by X-ray reflectometry (XRR), X-ray absorption spectroscopy (XAS) and X-ray photoelectron spectroscopy (XPS). The results suggest that the replacement of hydroxyl groups at the particle surface by Tiron (R) reduces the level of agglomeration of the sol, increasing the particles packing and the apparent density of the coatings. Undoped and Mn-doped films drawn from a Tiron (R) containing suspension show after firing at 500 degrees C a porosity reduction of 12 and 8.6%, respectively. The porosity decrease is less pronounced (4.3%) for the film without additives. Both XAS and XPS data show the presence of trivalent manganese. The formation of a non-homogeneous solid solution characterised by the presence of Mn(111) replacing tin atom near to the crystallite surface was evidenced by XAS. Additionally, XPS results reveal the presence of metallic Sn at the surface of films containing Tirono. (c) 2005 Elsevier Ltd. All rights reserved.

Stability regions around the components of the triple system 2001 SN263

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Kinetics and mechanism of the forward and reverse reactions between N,N′-dimethyl-4,4′-bipyridinium and hexacyanoferrate(II)

The kinetics of the hexacyanoferrate(III)-N,N′-dimethyl-4,4′-bipyridinium radical (MV+) reaction was studied by a laser flash photolysis technique. The radical was generated, in the presence of Fe(CN)6 3-, by quenching the excited state *Ru(bpy)3 2+ with MV2+. The second-order rate constant for the Fe(CN)6 3--MV+ reaction is (7.6 ± 0.5) × 109 M-1 s-1 at 23°C and ionic strength 0.10 M. Comparison with the rate constants calculated for the diffusion-controlled reaction (4.7 × 109 M-1 s-1) and the activation-controlled reaction (5.2 × 1012 M-1 s-1, on the basis of self-exchange rate constants of 8.0 × 105 M-1 s-1 and 1.9 × 104 M-1 s-1 for the MV2+/+ and Fe(CN)6 3-/4- couples, respectively) leads to the conclusion that the Fe(CN)6 3--MV+ reaction is diffusion controlled. The rate constant for the Fe(CN)6-MV2+ reaction, calculated from the rate constant for the Fe(CN)6 3--MV+ reaction and the appropriate equilibrium constant, is 2.4 × 10-5 M-1 s-1 at 23°C and ionic strength 0.10 M. Microscopic reversibility considerations require that the Fe(CN)6 4--MV2+ reaction be controlled by the dissociation of the successor complex Fe(CN)6 3-|MV+. The thermal and optical electron transfers in the ion pair Fe(CN)6 4-|MV2+ and in related systems are analyzed and discussed. © 1982 American Chemical Society.

Interference competition and scavenging by Crematogaster ants (Hymenoptera: Formicidae) associated with the webs of the social spider Anelosimus eximius (Araneae: Theridiidae) in the central Amazon

Crematogaster cf. victima is a common inhabitant in the sheet web nests of the social spider Anelosimus eximius in the central Amazon basin near Manaus. A number of other ant species were found foraging on the non-sticky webs of A. eximius, but none of these reached the web occupation frequency found in C. cf. victima, nor, with the exception of an unidentified species of Pheidole, did they form satellite nests in the web, as did this species. Many prey which escaped the knock-down threads of the sheet web of A. eximius colonies were captured by ants in the lower web portions which they dominated. Furthermore, prey which were rejected by A. eximius, especially large, heavily sclerotized beetles, were also consumed by this ant. Repeated observations and experiments suggest that C. cf. victima is able to deter A. eximius activity through aerial venom release. Resources lost by A. eximius colonies to ants, especially C. cf. victima, in colonial web area and prey, may pose significant costs and may reduce colony growth.

Study of the binding of Eu3+ and Tb3+ to L-phenylalanine and L-tryptophan

Trivalent europium and terbium ions have ionic radii similar to that of Ca2+. So they are employed as probes of calcium binding sites in biological molecules. These ions exhibit very useful spectroscopic characteristics, chiefly a pronounced luminescence. In protein bound lanthanide, visible light emission from the lanthanide excited states can be observed when UV light is absorbed by aromatic amino acids. Subsequently, the energy is transferred to the lanthanide ion. The present work was carried out to define the binding sites of Eu3+ and Tb3+ in complexes with the aromatic amino acids L-phenylalanine and L-tryptophan. The techniques utilized were infrared and C nuclear magnetic resonance spectroscopies. It was found that trivalent europium and terbium interact with the carboxylate group of both amino acids. With L-tryptophan, the imino group of the indole ring is also involved representing another coordination site.

Synthesis, characterization and molecular structures of the pyridinium trans-bis(pyridine)tetrachlororuthenate(III) and pyridinium trans-(carbonyl)(pyridine)tetrachlororuthenate(III)

The pyH[trans-RuCl4(py)2](1) and pyH[trans-RuCl4(CO)(py)](2) complexes were synthesized and found to crystallize in space group P21/n, Z = 4 with a = 8.080(7), b = 22.503(7), c = 10.125(6) Å, β = 93.19(6)° for (1) and a = 7.821(1), b = 10.337(3), c = 19.763(3) Å, β = 93.07(1)° for (2). The structures were solved by Patterson and difference Fourier techniques and refined to R = 0.062 for (1) and R = 0.038 for (2). In both cases the Ru(III) ion is octahedrally coordinated to four co-planar chlorine atoms, the nitrogen of the pyridine rings or carbon from the carbon monoxide. Another protonated pyridine group, which forms the counter-cation completes the crystal structures. The UV-Vis absorption spectra show three bands: (1) 360 (ε = 1180 M-1 cm-1), 441 (ε = 3200 M-1 cm-1) and 532 nm (ε = 400 M-1 cm-1); (2) 315(ε = 1150 M-1 cm-1), 442 (ε = 3170 M-1 cm-1) and 530 nm (ε = 390 M-1 cm-1). The two higher energy bands were associated with ligand-to-metal charge transfer transitions and a third band at lower energy was assigned to a d-d transition. Low temperature EPR data confirmed the presence of the paramagnetically active Ru(III) and it is consistent with axial symmetry of the complexes. The position of the stretching CO band in complex (2) is discussed in terms of metal-CO backbonding.

Two new species of the cricket genus Eidmanacris and a new combination name for a third species (Orthoptera, Grylloidea, Phalangopsidae)

Two new species of the genus Eidmanacris are described (E. bidentata and E. corumbatai) and a new combination name ( E. alboannulata) is assigned for the species Arachnomimus alboannulatus Piza, 1960 (= E. bicornis Mesa & Mello, 1985). Morphological and karyologycal information are provided, and the structure of the genital sclerites is discussed. [KEY WORDS: Orthoptera, Grylloidea, Phalangopsidae, Eidmanacris, cricket, phallic sclerites, chromosomes].

A refinement of the gauss-lucas theorem

The classical Gauss-Lucas Theorem states that all the critical points (zeros of the derivative) of a nonconstant polynomial p lie in the convex hull H of the zeros of p. It is proved that, actually, a subdomain of H contains the critical points of p. ©1998 American Mathematical Society.

Comparison of artificial and natural, new and reused, brackish water for the larviculture of the freshwater prawn Macrobrachium rosenbergii in a recirculating system

Differences in culture duration, metamorphosis rate and the productivity in hatchery culture of M. rosenbergii using a closed system with natural and artificial brackish water were evaluated. Reuse of brackish water in more than one hatchery cycle was also evaluated. Natural and artificial brackish water constituted the two tested treatments, which were distributed in four independent recirculating systems (tank and respective biofilter). Four batches of cultures were conducted and the 2nd and 4th reused the water from the 1st and 3rd, respectively. Mean duration of the hatchery period was 28 d in natural brackish water and 31 d in artificial brackish water. The metamorphosis rate and the average productivity for the natural brackish water treatment were 74% and 60 postlarvae/ L. respectively, and values obtained with artificial brackish water were 55% and 44 postlarvae/L. The successful hatchery culture of M. rosenbergii in this specific artificial brackish water suggests its potential use in enterprises located far from the coast. Brackish water can be used in two consecutive cultures without a negative effect on productivity.

Spectroscopic study of the interaction of Nd3+ with amino acids: Phenomenological 4f-4f intensity parameters

We have studied the bevahior of the phenomenological 4f-4f intensity parameters in compounds of the Nd ion with glycine, L-aspartic acid, L-glutamic acid, L-histidine, DL-malic acid and Aspartame™ in aqueous solution, as a function of the pK values and partial charges on the oxygens of the carboxylate groups of these molecules. The results are discussed and qualitatively interpreted in terms of the forced electric dipole and dynamic coupling mechanisms of the 4f-4f intensities, thus indicating that the forced electric dipole mechanism is dominant.

Characterization of bornite (Cu5FeS4) electrodes in the presence of the bacterium Acidithiobacillus ferrooxidans

Bornite electrodes were characterized in the absence or in the presence of Acidithiobacillus ferrooxidans, which is an important microorganism involved in metal bioleaching processes. The presence of the bacterium modified the mineral/electrolyte interface, increasing the corrosion rate, as revealed by interferometric, AEM, ICP and EIS analyses. As a consequence of bacterial activity the electrode became porous, increasing its surface heterogeneity. This behavior was correlated with the evolution of impedance diagrams obtained during the time course of experiments. The main difference in these diagrams was the presence of an inductive feature (up to 44 h), which was related to bacterial action on the mineral dissolution, better than to its adhesion on the bornite. The total real impedance measured in presence of the bacterium was about 10 times lower than in its absence, due to the acceleration of the mineral dissolution, because an oxidant environment was maintained.

Determination of the phthalocyanine textile dye, reactive turquoise blue, by electrochemical techniques

Turquoise blue 15 (AT15) is a reactive dye widely used in the textile industry to color natural fibers. The presence of these dyes in effluent and industrial wastewater is of considerable interest due ecotoxicological and environmental problems. The electrochemical reduction of this dye has been investigated in aqueous solution using cyclic voltammetry, controlled potential electrolysis and cathodic stripping voltammetry. Optimum conditions for dye discoloration by controlled potential electrolysis use an alkaline medium. Using cathodic stripping voltammetry a linear calibration graph was obtained from 5.00×10-8 mol L-1 to 1.00×10 -6 mol L-1 of AT15 at pH 4.0, using accumulation times of 180 and 240 s and an accumulation potential of 0.0 V. The proposed method was applied in direct determination of the dye in tap water and in textile industry effluent.