Structural Effects of Nanotubes, Nanowires, and Nanoporous Ti/TiO2 Electrodes on Photoelectrocatalytic Oxidation of 4,4-Oxydianiline

The present work illustrates the effect of electrolyte composition on the self-organized TiO2 nanotube arrays electrode preparation. The influence of structural and surface morphology of the TiO2 nanotube-like anode on their photoactivity and photoelectrocatalytic performance was also investigated. TiO2 nanotubular array electrodes are grown by anodization of Ti foil in 0.25wt % NH4F/glycerol/water, but nanowires can be obtained in 4% HF-DMSO as supporting electrolyte, even when both are subjected to electrochemical anodization at 30V during 50 h. The morphological characteristics are analyzed by X-ray diffraction (XRD) and field emission scanning electron microscope (FEG-SEM). The electrodes were successfully applied in photoelectrocatalytic oxidation of 4,4'-oxydianiline (ODAN) in aqueous solution, as a model of a harmful pollutant. Complete removal of the aromatic amine was obtained after 3 hours of photoelectrocatalytic treatment on nanotubular arrays electrodes.

Optical and structural properties of GaAs/GaInP quantum wells grown by Chemical Beam Epitaxy

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Correlation of reactivity with structural factors in a series of Fe(II) substituted cobalt ferrites

A series of powdered cobalt ferrites, CoxFe3-xO4 with 0.66 <= x< 1.00 containing different amounts of Fe-II, were synthesized by a mild procedure, and their Fe and Co site occupancies and structural characteristics were explored using X-ray anomalous scattering and the Rietveld refinement method. The dissolution kinetics, measured in 0.1 M oxalic acid aqueous solution at 70 degrees C, indicate in all cases the operation of a contracting volume rate law. The specific rates increased with the Fell content following approximately a second-order polynomial expression. This result suggests that the transfer of Fe-III controls the dissolution rate, and that the leaching of a first layer of ions Co-II and Fe-II leaves exposed a surface enriched in slower dissolving octahedral Fe-III ions. Within this model, inner vicinal lattice Fe-II accelerates the rate of Fe-III transfer via internal electron hopping. A chain mechanism, involving successive electron transfers, fits the data very well. (C) 2006 Elsevier B.V. All rights reserved.

Phospholipase A(2) - A structural review

Phospholipases A(2) (PLA(2)) are widely distributed in nature and are well characterized proteins with respect to their catalytic and pharmacological activities, A wealth of structural information has recently become available both from X-ray diffraction and NMR studies, and although a detailed model of the catalytic mechanism of PLA(2) has been proposed, the structural bases of other aspects of PLA(2) function, such as interfacial activation and venom PLA(2) pharmacological activities, are still under debate. An appreciation of the PLA(2) protein structure will yield new insights with regard to these activities, the salient structural features of the class I, II and III PLA(2) are discussed with respect to their functional roles. Copyright (C) 1996 Published by Elsevier B.V. Ltd

Structural and functional characterization of neuwiedase, a nonhemorrhagic fibrin(ogen)olytic metalloprotease from Bothrops neuwiedi snake venom

A fibrino(geno)lytic nonhemorrhagic metalloprotease (neuwiedase) was purified from Bothrops neuwiedi snake venom by a single chromatographic step procedure on a CM-Sepharose column, Neuwiedase represented 4.5% (w/w) of the crude desiccated venom, with an approximate Mr of 20,000 and pI 5.9, As regards the amino acid composition, neuwiedase showed similarities with other metalloproteases, with high proportions of Asx, Glx, Leu, and Ser, Atomic absorption spectroscopy showed that one mole of Zn2+ and one mole of Ca2+ were present per mole olf protein. The cDNA encoding neuwiedase was isolated by RT-PCR from venom gland RNA, using oligonucleotides based on the partially determined amino-acid sequences of this metalloprotease. The fall sequence contained approximately 594 bp, which codified the 198 amino acid residues with an estimated molecular weight of 22,375. Comparison of the nucleotide and amino acid sequences of neuwiedase with those of other snake venom metalloproteases showed a high level of sequential similarity, Neuwiedase has two highly conserved characteristics sequences H(142)E(143)XXH(146)XXG(140)XXH(152) and C164I165M166. The three-dimensional structure of neuwiedase was modeled based on the crystal structure of Crotalus adamanteus Adamalysin II. This model revealed that the zinc binding site region showed a I high structural similarity with other metalloproteases,, the proteolyitc specificity, using the B beta-chain of oxidized insulin as substrate, was shown to be directed to the Ala(14)-Leu(15) and Tyr(16)-Leu(17) peptide bonds which were preferentially hydrolyzed. Neuwiedase is a A alpha,B beta fibrinogenase, Its activity upon the A alpha chain of fibrinogen was detected within 15 min of incubation. The optimal temperature and pH for the degradation of both A alpha and B beta chains were 37 degrees C and 7.4-8.0, respectively. This activity was inhibited by EDTA and 1,10-phenantroline, Neuwiedase also showed proteolytic activity upon fibrin and some components of the extracellular matrix. However, it did not show TAME esterase activity and was not able to inhibit platelet aggregation. (C) 2000 Academic Press.

Structural biology of membrane-acting peptides: Conformational plasticity of anticoccidial peptide PW2 probed by solution NMR

The bottleneck for the complete understanding of the structure-function relationship of flexible membrane-acting peptides is its dynamics. At the same time, not only the structure but also the dynamics are the key points for their mechanism of action. Our model is PW2, a TRP-rich, cationic peptide selected from phage display libraries that shows anticoccidial activity against Eimeria acervulina. In this manuscript we used a combination of several NMR techniques to tackle these difficulties. The structural features of the membrane-acting peptide PW2 was studied in several membrane mimetic environments: we compared the structural features of PW2 in SDS and DPC micelles, that were reported earlier, with the structure properties in different lipid vesicles and the peptide free in water. We were able to unify the structural information obtained in each of these systems. The structural constraints of the peptide free in water were fundamental for the understanding of plasticity necessary for the membrane interaction. Our data suggested that the WWR sequence is the region responsible for anchoring the peptide to the interfaces, and that this same region displays some degree of conformational order in solution. For PW2, we found that affinity is related to the aromatic region, by anchoring the peptide to the membrane, and specificity is related to the N- and C-termini, which are able to accommodate in the membrane due to its plasticity. (C) 2007 Elsevier B.V. All rights reserved.

Structural organization and thermal properties of the Sb2O3-SbPO4 glass system

The structural organization of Sb2O3-SbPO4 glasses has been studied by FTIR, Raman, P-31 MAS and spin echo NMR, Mossbauer and X-ray absorption spectroscopy (EXAFS and XANES at K and L-3,L-1-Sb edges). The combined results can be explained in terms of two potential mechanisms describing the change of the Sb(m) local environment upon incorporation of Q((4))-type phosphate. The formation of the latter species requires anionic compensation that may be adjusted by (a) formation of non bridging oxygen or (b) formation of SbO4E- groups (E = non-bonding electron pair). The second model is favored.

A probabilistic model for elastic-plastic fracture analysis of plane and axisymmetric structures

This work presents a methodology for elastic-plastic fracture reliability analysis of plane and axisymmetric structures. The structural reliability analysis is accomplished by means of the FORM analytical method. The virtual crack extension technique based on a direct minimization of potencial energy is utililized for the calculation of the energy release rate. Results are presented to illustrate the performance of the adopted methodology.

Molecular model for the binary complex of uropepsin and pepstatin

The three-dimensional structure of human uropepsin complexed with pepstatin has been modelled using human pepsin as a template. Uropepsin is an aspartic proteinase from the urine, produced in the form of pepsinogen A in the gastric mucosa. The structure is bilobal, consisting of two predominantly beta -sheet lobes which, as observed in other aspartic proteinases, are related by a pseudo twofold axis. A structural comparison between binary complexes of pepsin:pepstatin and uropepsin:pepstatin is discussed. (C) 2001 Academic Press.

Elasto-plastic structural stability of arches

The elastic-plastic structural stability behaviour of arches is analysed in the present work.The application of the developed mathematical model, allows to determine the elastic-plastic equilibrium paths, looking for critical points, bifurcation or limit, along those paths, associated to the critical load, in case it comes to happen.The equilibrium paths in the elastic-plastic behaviour when compared with the paths in the linear elastic behaviour, may show that, due to influence of the material plasticity, modifications paths appear and consequently alterations in the values of its critical loads.

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.

Structural and functional characterization of myotoxin I, a Lys49 phospholipase A(2) homologue from Bothrops moojeni (Caissaca) snake venom

Myotoxin-I (MjTX-I) was purified to homogeneity from the venom of Bothrops moojeni by ion-exchange chromatography on CM-Sepharose. Its molecular weight, estimated by SDS-PAGE, was 13,400 (reduced) or 26,000 (unreduced). The extinction coefficient (E-1.0 cm(1.0 mg/ml)) of MjTX-I was 1.145 at lambda = 278 nm, pH 7.0, and its isoelectric point was 8.2 at ionic strength mu = 0.1. When lyophilized and stored at 4 degrees C, dimeric, trimeric, and pentameric forms of the protein were identified by SDS-PAGE. This heterogeneous sample could be separated into three fractions by gel filtration on Sephadex 6-50. The fractions were analyzed by isoelectric focusing, immunoelectrophoresis, and amino acid composition, which indicated that heterogeneity was the result of different levels of self-association. Protein sequencing indicated that MjTX-I is a Lys49 myotoxin and consists of 121 amino acids (M-r = 13,669), containing a high proportion of basic and hydrophobic residues. It shares a high degree of sequence identity with other Lys49 PLA(2)-like myotoxins, but shows a significantly lower identity with catalytically active Asp49 PLA(2)s. The three-dimensional structure of MjTX-I was modeled based on the crystal structures of three highly homologous Lys49 PLA(2)-like myotoxins. This model showed that the amino acid substitutions are conservative, and mainly the beta-wing region, and the C-terminal extended random coil. MjTX-I displays local myotoxic and edema-inducing activities in mice, and is lethal by intraperitoneal injection, with an LD50 value of 8.5 +/- 0.8 mg/kg, In addition, it is cytotoxic to myoblasts/ myotubes in culture, and disrupts negatively charged liposomes. In comparison with the freshly prepared dimeric sample, the more aggregated forms showed significantly reduced myotoxic activity. However, the edema-inducing activity of MjTX-I was independent of molecular association. Phospholipase A(2) activity on egg yolk, as well as anticoagulant activity, were undetectable both in the native and in the more associated forms. His, Tyr, and Trp residues of the toxin were chemically modified by specific reagents. Although the myotoxic and lethal activities of the modified toxins were reduced by these treatments, neither its edema-inducing or Liposome-disrupting activities were significantly altered. Rabbit antibodies to native MjTX-I cross-reacted with the chemically modified forms, and both the native and modified MjTX-I preparations were recognized by antibodies against the C-terminal region 115-129 of myotoxin II from B. asper, a highly Lys49 PLA(2)-homologue with high sequencial similarity. (C) 2000 Academic Press.

Structural health evaluation by optimization techinique and artificial neural network

This paper presents two different approaches to detect, locate, and characterize structural damage. Both techniques utilize electrical impedance in a first stage to locate the damaged area. In the second stage, to quantify the damage severity, one can use neural network, or optimization technique. The electrical impedance-based, which utilizes the electromechanical coupling property of piezoelectric materials, has shown engineering feasibility in a variety of practical field applications. Relying on high frequency structural excitations, this technique is very sensitive to minor structural changes in the near field of the piezoelectric sensors, and therefore, it is able to detect the damage in its early stage. Optimization approaches must be used for the case where a good condensed model is known, while neural network can be also used to estimate the nature of damage without prior knowledge of the model of the structure. The paper concludes with an experimental example in a welded cubic aluminum structure, in order to verify the performance of these two proposed methodologies.

Structural behaviour of three-pile caps subjected to axial compressive loading

This work presents a comparative analysis about the behaviour of pile caps supported by 3 piles subjected to axial loading. Piles with 20 cm and 30 cm diameters were analysed. The main reinforcement was maintained in all the specimens, however, the arrangement of the secondary reinforcement varied. The main reinforcement consisted of steel bars connecting the piles. The secondary reinforcement was made up of: (a) bars going through the piles and through the projection of the column, (b) bars forming a network, and (c) vertical and horizontal stirrups. The main objective was the observation of the pile cap behaviour regarding the cracks and the modes of rupture. The real scale specimens were subjected to experimental tests until failure by rupture. Instruments were placed with the aim to obtain the displacement of the bases, the strains in the main and secondary reinforcement bars, in the compression struts, in the lower and upper nodal zones and in the sides of the caps. None of the caps reached failure by rupture with a load less than 1.12 times the theoretical load. The specimens ruptured due to the cracking of the compression strut and/or the yielding of the reinforcement bars in one direction.

Effects of biofertilizer rates on the structural, morphogenetic and productive characteristics of Piata grass

The objective of this study was to investigate the influence of different levels of biofertilizers from cattle and swine manure on the structural, morphogenetic and productive characteristics of Brachiaria brizantha cv. Piata. The experiment was arranged in a completely randomized factorial design with split plots. The plots were defined by eight treatments: two biofertilizers (cattle and swine), four levels (0, 100, 200 and 300 kg N.ha(-1)) and subplots by four different cutting periods. The cutting for plant uniformity was performed at 45 days after sowing at 15 cm above the soil surface. The biofertilizeres were applied in a single level, after the cutting of plants, in rates of 0, 0.23 and 0.19, 0.45 and 0.38, 0.68 and 0.57 liters pot(-1) for the biofertilizers from cattle and swine manure, respectively. These rates were also equivalent to levels of 0, 100, 200 and 300 kg N.ha(-1). There was no significant difference between the types of biofertilizers as there was no interaction between them and the different levels, hence both biofertilizers could be applied without any loss of nutrient intake by the plants used in this experiment. There was a significant difference between the production of green and dry matter, the leaf appearance rate, phyllochron, leaf and pseudostem elongation rates, number of green leaves, final leaf length, number and weight of tillers, according to the increase of nitrogen rates, following linear prediction model. Effect of the cutting periods was also observed, once the plants harvested during the summer presented greater performance of structural and morphogenetic characteristics.