Selective sorption of mercury(II) from aqueous solution with an organically modified clay and its electroanalytical application

The organo-clay used in this work was prepared from a Na-montmorillonite (Wyoming-USA deposit) by treatment with water solution of hexadecyltrimethylammonium cations. As organo-clays exhibit strong sorptive capabilities for organic molecules, 2-mercapto-5-amino-1,3,4-thiadiazole organofunctional groups, with potential usefulness in chemical analysis, were incorporated on its solid surface. The physically adsorbed reagent did not present any restrictions in coordinating with several metal ions on the surface. The resultant organo-clay complex exhibited strong sorptive capability for removing mercury ions from water in which other metals and ions were also present. The purpose of this work is to study the selective separation of mercury(II) from aqueous solution using the organo-clay complex, measured by batch and chromatographic column techniques, and its application as preconcentration agent in a chemically modified carbon paste electrode for determination of mercury(II) in aqueous solution.

Phosphate closes the solution structure of the 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS) from Mycobacterium tuberculosis

The 5-enolpyruvylshikimate-3-phosphate synthase catalyses the sixth step of the shikimate pathway that is responsible for synthesizing aromatic compounds and is absent in mammals, which makes it a potential target for drugs development against microbial diseases. Here, we report the phosphate binding effects at the structure of the 5-enolpyruvyl shikimate-3-phosphate synthase from Mycobacterium tuberculosis. This enzyme is formed by two similar domains that close on each other induced by ligand binding, showing the occurrence of a large conformation change. We have monitored the phosphate binding effects using analytical ultracentrifugation, small angle X-ray scattering and, circular dichroism techniques. The low resolution results showed that the enzyme in the presence of phosphate clearly presented a more compact structure. Thermal-induced unfolding experiments followed by circular dichroism suggested that phosphate rigidified the enzyme. Summarizing, these data suggested that the phosphate itself is able to induce conformational change resulting in the closure movement in the M. tuberculosis 5-enolpyruvylshikimate-3-phosphate synthase. (c) 2006 Elsevier B.V. All rights reserved.

Synthesis, characterization and solution properties of amphiphilic N-isopropylacrylamide-poly(ethylene glycol)-dodecyl methacrylate thermosensitive polymers

Terpolymers of N-isopropylacrylamide, dodecyl methacrylate (DOMA) and poly(ethylene glycol) (PEG) methacrylate, were synthesized by random copolymerization, and the composition was controlled to achieve systems having different thermosensitivities. H-1 NMR spectra and gel permeation chromatography (GPC) were employed to characterize the different samples obtained. The solution properties were studied by employing spectrophotometry, fluorescence, and dynamic light scattering techniques. The chemical compositions in the final terpolymers are close to those in the feed. The polymers exhibited cloud point temperatures (T-es) varying from 17 to 52 degrees C. Micropolarity studies using I-1/I-3 ratio of the vibronic bands of pyrene show the formation of amphiphilic aggregates capable of incorporating hydrophobic drugs as the polymer concentration is increased. The critical aggregation concentration (CAC) increases from 3.6 x 10(-3) to 1 x 10(-2) g/l with the PEG content varying from 5 to 35 mol%. Anisotropy measurements confirm the results obtained by pyrene fluorescence and show that the aggregates resulting from intermolecular interactions present different organizations. The hydrodynamic diameters (Dh) of the aggregates determined by dynamic light scattering (DLS) vary from 40 to 150 nm depending on the terpolymer composition. The T-cs and Dh values decreased with the ionic strength, and this behavior was attributed to the dehydration of the polymeric micelles. The capacity of solubilization of the aggregates was evaluated by employing pyrene, and the obtained results confirm the ability to incorporate hydrophobic molecules. (c) 2005 Elsevier B.V All rights reserved.

Electrochemical behavior of thermally sprayed stainless steel coatings in 3.4% NaCl solution

Four types of stainless steel coatings prepared by a high velocity oxy-fuel spraying system (HVOF) were studied. Differences among coated steels were related to the spraying parameters, which influenced the behavior of the samples against the corrosion. The electrochemical behavior of the stainless steel coatings was strongly influenced by porosity, the presence of micro- and macro-cracks, and also of un-melted particles. Once the electrolyte reached the steel substrate via these defects, the galvanic pair formed between the coating and substrate-accelerated corrosion, leading to the depletion of the coating. (C) 2004 Elsevier Ltd. All rights reserved.

Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < PH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbOx (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at PH 2.2 and potential of +2.4 V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 K PH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1 h of electrolysis the results indicated total color removal and 37% of mineralization. (c) 2004 Elsevier Ltd. All rights reserved.

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.

The application of preprocessing and cutting plane techniques for a class of production planning problems

This paper investigates properties of integer programming models for a class of production planning problems. The models are developed within a decision support system to advise a sales team of the products on which to focus their efforts in gaining new orders in the short term. The products generally require processing on several manufacturing cells and involve precedence relationships. The cells are already (partially) committed with products for stock and to satisfy existing orders and therefore only the residual capacities of each cell in each time period of the planning horizon are considered. The determination of production recommendations to the sales team that make use of residual capacities is a nontrivial optimization problem. Solving such models is computationally demanding and techniques for speeding up solution times are highly desirable. An integer programming model is developed and various preprocessing techniques are investigated and evaluated. In addition, a number of cutting plane approaches have been applied. The performance of these approaches which are both general and application specific is examined.

Crystallization, preliminary X-ray analysis and molecular-replacement solution of the carboxy form of haemoglobin I from the fish Brycon cephalus

Haemoglobin, the 'honorary enzyme' [Brunori (1999), Trends Biochem. Sci. 24, 158-161], constitutes a prime prototype for allosteric models. Here, the crystallization and preliminary X-ray analysis of haemoglobin I from the South American fish Brycon cephalus are reported. X-ray diffraction data have been collected to 2.5 Angstrom resolution using synchrotron radiation (LNLS). Crystals were determined to belong to the space group P6(1)22 and preliminary structural analysis revealed the presence of one dimer (alpha beta) in the asymmetric unit. The structure was determined using standard molecular-replacement techniques.

Changes on iron electrode surface during hydrogen permeation in borate buffer solution

Hydrogen interaction with oxide films grown on iron electrodes at open circuit potential (E-oc) and in the passive region (+0.30 V-ECS) was studied by chronopotentiometry, chronoamperometry and electrochemical impedance spectroscopy techniques. The results were obtained in deaerated 0.3 mol L-1 H3BO3 + 0.075 mol L-1 Na2B4O7 (BB, pH 8.4) solution before, during and after hydrogen permeation. The iron oxide film modification was also investigated by means of in situ X-ray absorption near-edge spectroscopy (XANES) and scanning electrochemical microscopy (SECM) before and during hydrogen permeation. The main conclusion was that the passive film is reduced during the hydrogen diffusion. The hydrogen permeation stabilizes the iron surface at a potential close to the thermodynamic water stability line where hydrogen evolution can occur. The stationary condition required for the determination of the permeation parameters cannot be easily attained on iron surface during hydrogen permeation. Moreover, additional attention must be paid when obtaining the transport parameters using the classical permeation cell. (c) 2007 Elsevier Ltd. All rights reserved.

Zirconia foams prepared by integration of the sol-gel method and dual soft template techniques

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

In vivo antimicrobial activity of 2% chlorhexidine used as a root canal irrigating solution

The aim of the present study was to evaluate the in vivo antimicrobial activity of 2% chlorhexidine gluconate (FCFRP-USP) used as a root canal irrigating solution in teeth with pulp necrosis and radiographically visible chronic periapical reactions. Culture techniques and measurement of the inhibition zone were used. Twenty-two root canals of incisors and molars of 12 patients were used. After accessing the canal, the first root canal sample was collected with two sterile paper points that were transferred to a tube containing reduced transport fluid. The root canal was instrumented using chlorhexidine solution. A small sterile cotton pellet was placed at the root canal entrance, and the cavity was sealed with zinc oxide-eugenol cement. The canals were maintained empty for 48 h. Three sterile paper points were then introduced to absorb the root canal fluid (second sample). One paper point was placed on an agar plate inoculated with Micrococcus luteus ATCC 9341 and incubated for 24 h at 37°C, and the other two were submitted to microbiological evaluation. Present in 10 cases at baseline, mutans streptococci was reduced by 100% at the second assessment. Treatment showed an efficiency of 77.78% for anaerobic microorganisms at the second assessment. These data suggest that chlorhexidine prevents microbial activity in vivo with residual effects in the root canal system up to 48 h. Copyright © 1999 by The American Association of Endodontists.

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.

In vitro susceptibility of oral Candida albicans strains to different pH levels and calcium hydroxide saturated aqueous solution

Candida albicans is present in the oral cavity and in the whole digestive tract of humans and other animals, being frequently related to endodontic treatment failure. The present study determined the incidence of C. albicans in the oral cavity and the susceptibility of isolates to different pH values and saturated calcium hydroxide aqueous solution at pH 12.5. Sixty-five patients attending the Endodontic Clinic at the Sagrado Coração University participated in the study. The collected samples were cultivated in selective media for C. albicans and the isolates were tested in terms of resistance to both alkaline pH and saturated aqueous solution of calcium hydroxide. In relation to time variables, yeast viability was assessed by the Sabouraud's agar culture and fluorescein diacetate and ethidium bromide fluorescent staining method. Results from the different pHs and experimental times, including those from different techniques measuring fungal viability, were compared using the chi-square and Fisher's exact tests (α=0.05). The yeasts became completely inviable after 48 h of contact with the calcium hydroxide solution. On the other hand, when exposed to the alkaline culture broth, the yeasts were found to be viable at pHs 9.5 and 10.5 for up to 7 days. In conclusion, C. albicans can only be completely inhibited by direct contact with saturated calcium hydroxide aqueous solution after 48 h of exposure.

An exact series solution for the vibration analysis of cylindrical shells with arbitrary boundary conditions

In this paper, an exact series solution for the vibration analysis of circular cylindrical shells with arbitrary boundary conditions is obtained, using the elastic equations based on Flügge's theory. Each of the three displacements is represented by a Fourier series and auxiliary functions and sought in a strong form by letting the solution exactly satisfy both the governing differential equations and the boundary conditions on a point-wise basis. Since the series solution has to be truncated for numerical implementation, the term exactly satisfying should be understood as a satisfaction with arbitrary precision. One of the important advantages of this approach is that it can be universally applied to shells with a variety of different boundary conditions, without the need of making any corresponding modifications to the solution algorithms and implementation procedures as typically required in other techniques. Furthermore, the current method can be easily used to deal with more complicated boundary conditions such as point supports, partial supports, and non-uniform elastic restraints. Numerical examples are presented regarding the modal parameters of shells with various boundary conditions. The capacity and reliability of this solution method are demonstrated through these examples. © 2012 Elsevier Ltd. All rights reserved.

An approach to implement data fusion techniques in wireless sensor networks using genetic machine learning algorithms

Wireless Sensor Networks (WSNs) can be used to monitor hazardous and inaccessible areas. In these situations, the power supply (e.g. battery) of each node cannot be easily replaced. One solution to deal with the limited capacity of current power supplies is to deploy a large number of sensor nodes, since the lifetime and dependability of the network will increase through cooperation among nodes. Applications on WSN may also have other concerns, such as meeting temporal deadlines on message transmissions and maximizing the quality of information. Data fusion is a well-known technique that can be useful for the enhancement of data quality and for the maximization of WSN lifetime. In this paper, we propose an approach that allows the implementation of parallel data fusion techniques in IEEE 802.15.4 networks. One of the main advantages of the proposed approach is that it enables a trade-off between different user-defined metrics through the use of a genetic machine learning algorithm. Simulations and field experiments performed in different communication scenarios highlight significant improvements when compared with, for instance, the Gur Game approach or the implementation of conventional periodic communication techniques over IEEE 802.15.4 networks. © 2013 Elsevier B.V. All rights reserved.