943 resultados para Nanoparticles, Thermal Fragmentation, Degradation, Stochastic Processes


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Infrared-to-visible and infrared-to-infrared frequency upconversion processes in Yb3+-Tm3+ doped PbO-GeO2 glasses containing silver nanoparticles (NPs) were investigated. The experiments were performed by exciting the samples with a diode laser operating at 980 nm (in resonance with the Yb3+ transition F-2(7/2)-> F-2(5/2)) and observing the photoluminescence (PL) in the visible and infrared regions due to energy transfer from Yb3+ to Tm3+ ions followed by excited state absorption in the Tm3+ ions. The intensified local field in the vicinity of the metallic NPs contributes for enhancement in the PL intensity at 480 nm (Tm3+ :(1)G(4)-> H-3(6)) and at 800 nm (Tm3+ : H-3(4) -> H-3(6)). (C) 2009 American Institute of Physics. [doi:10.1063/1.3211300]

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

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Transformation of pesticides is directly related to the environmental conditions during application and transport of these compounds in the ecosystem. Rice fields include peculiar conditions, relatively high temperatures and wet conditions, leading to degradation processes, different from that observed in other agricultural systems. This article presents the degradation routes of some characteristic rice insecticides and herbicides under field conditions. A compilation of the pesticides that are usually applied during rice cultivation is included, with their main physico-chemical parameters. The stability of the pesticides by solid phase extraction systems during storage of rice samples is also discussed.

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The thermal behavior of blends of poly(vinylidene fluoride), or PVDF, and poly(o-methoxyaniline) doped with toluene sulfonic acid was studied by thermogravimetic analysis, electrical conductivity measurements, differential scanning calorimetry, X-ray diffraction and scanning electron microscopy. Blends with thermal and electrical conductivity stabler than the conductive polymer alone were obtained. Nevertheless, degradation occurs after a long period of time (500 h) at high temperatures. The possible association of the conductivity decay with dopant loss, degradation and structural and morphological changes of the blend is discussed. (C) 2000 Elsevier Science Ltd.

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

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A combined theoretical and experimental study to elucidate the molecular mechanism for the Grob fragmentation of different (N-halo)-2-amino cyclocarboxylates with the nitrogen atom in exocyclic position: (N-Cl)-2-amino cyclopropanecarboxylate (1), (N-Cl)-2-amino cyclobutanecarboxylate (2), (N-Cl)-2-amino cyclopentanecarboxylate (3) and (N-Cl)-2-amino cyclohexanecarboxylate (4), and the corresponding acyclic compounds, (N-Cl)-2-amino isobutyric acid (A), (N-Cl)-2-amino butyric acid (B), has been carried out. The kinetics of decomposition for these compounds and related bromine derivatives were experimentally determined by conventional and stopped-flow UV spectrophotometry. The reaction products have been analyzed by GC and spectrophotometry. Theoretical analysis is based in the localization of stationary points (reactants and transition structures) on the potential energy surface. Calculations were carried out at B3LYP/6-31+G* and MP2/6-31+G* computing methods in the gas phase, while solvent effects have been included by means the self-consistent reaction field theory, PCM continuum model, at MP2/6-31+G* and MP4/6-31+G*//MP2/6-31+G* calculation levels. Based on both experimental and theoretical results, the different Grob fragmentation processes show a global synchronicity index close to 0.9, corresponding to a nearly concerted process. At the TSs, the N-Cl bond breaking is more advanced than the C-C cleavage process. An antiperiplanar configuration of these bonds is reached at the TSs, and this geometrical arrangement is the key factor governing the decomposition. In the case of 1 and 2 the ring strain prevents this spatial disposition, leading to a larger value of the activation barrier. Natural population analysis shows that the polarization of the N-Cl and C-C bonds along the bond-breaking process can be considered the driving force for the decomposition and that a negative charge flows from the carboxylate group to the chlorine atom to assist the reaction pathway. A comparison of theoretical and experimental results shows the relevance of calculation level and the inclusion of solvent effects for determining accurate unimolecular rate coefficients for the decomposition process. © 2002 Published by Elsevier Science B.V.

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Grinding process is usually the last finishing process of a precision component in the manufacturing industries. This process is utilized for manufacturing parts of different materials, so it demands results such as low roughness, dimensional and shape error control, optimum tool-life, with minimum cost and time. Damages on the parts are very expensive since the previous processes and the grinding itself are useless when the part is damaged in this stage. This work aims to investigate the efficiency of digital signal processing tools of acoustic emission signals in order to detect thermal damages in grinding process. To accomplish such a goal, an experimental work was carried out for 15 runs in a surface grinding machine operating with an aluminum oxide grinding wheel and ABNT 1045 e VC131 steels. The acoustic emission signals were acquired from a fixed sensor placed on the workpiece holder. A high sampling rate acquisition system at 2.5 MHz was used to collect the raw acoustic emission instead of root mean square value usually employed. In each test AE data was analyzed off-line, with results compared to inspection of each workpiece for burn and other metallurgical anomaly. A number of statistical signal processing tools have been evaluated.

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This paper is concerned with the stability of discrete-time linear systems subject to random jumps in the parameters, described by an underlying finite-state Markov chain. In the model studied, a stopping time τ Δ is associated with the occurrence of a crucial failure after which the system is brought to a halt for maintenance. The usual stochastic stability concepts and associated results are not indicated, since they are tailored to pure infinite horizon problems. Using the concept named stochastic τ-stability, equivalent conditions to ensure the stochastic stability of the system until the occurrence of τ Δ is obtained. In addition, an intermediary and mixed case for which τ represents the minimum between the occurrence of a fix number N of failures and the occurrence of a crucial failure τ Δ is also considered. Necessary and sufficient conditions to ensure the stochastic τ-stability are provided in this setting that are auxiliary to the main result.

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SiO2 (1-x) - TiO2 (x) waveguides, with the mole fraction x in the range 0.07 - 0.20 and thickness of about 0.4 μm, were deposited on silica substrates by a dip-coating technique. The thermal treatments at 700-900°C, used to fully densify the xerogels, produce nucleation of TiO2 nanocrystals even for the lowest TiO2 content. The nucleation of TiO2 nanocrystals and their growth by thermal annealing up to 1300°C were studied by waveguide Raman spectroscopy, for the SiO2 (0.8) - TiO2 (0.2) composition. By increasing the annealing temperature, the Raman spectrum evolves from that typical of the silica-titania glass to that of anatase, but brookite phase is dominant at intermediate temperatures. In the low. frequency region (5-50 cm-1) of the Raman spectra, acoustic vibrations of the nanocrystals are observed. From the measured line shapes, we can deduce the size distribution of the particles. The results are compared with those obtained from the line widths in the X-ray diffraction patterns. Nanocrystals with a mean size in the range 4-20 nm are obtained, by thermal annealing in a corresponding range of 800-1300°C.

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Habitat fragmentation is predicted to restrict gene flow, which can result in the loss of genetic variation and inbreeding depression. The Brazilian Atlantic forest has experienced extensive loss of habitats since European settlement five centuries ago, and many bird populations and species are vanishing. Genetic variability analysis in fragmented populations could be important in determining their long-term viability and for guiding management plans. Here we analyzed genetic diversity of a small understory bird, the Blue-manakins Chiroxiphia caudata (Pipridae), from an Atlantic forest fragment (112 ha) isolated 73 years ago, and from a 10,000 ha continuous forest tract (control), using orthologous microsatellite loci. Three of the nine loci tested were polymorphic. No statistically significant heterozygote loss was detected for the fragment population. Although genetic diversity, which was estimated by expected heterozygosity and allelic richness, has been lower in the fragment population in relation to the control, it was not statistically significant, suggesting that this 112 ha fragment can be sufficient to maintain a blue-manakin population large enough to avoid stochastic effects, such as inbreeding and/or genetic drift. Alternatively, it is possible that 73 years of isolation did not accumulate sufficient generations for these effects to be detected. However, some alleles have been likely lost, specially the rare ones, what is expected from genetic drift for such a small and isolated population. A high genetic differentiation was detected between populations by comparing both allelic and genotypic distributions. Only future studies in continuous areas are likely to answer if such a structure was caused by the isolation resulted from the forest fragmentation or by natural population structure.

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This work involved the development of a smart system dedicated to surface burning detection in the grinding process through constant monitoring of the process by acoustic emission and electrical power signals. A program in Visual Basic® for Windows® was developed, which collects the signals through an analog-digital converter and further processes them using burning detection algorithms already known. Three other parameters are proposed here and a comparative study carried out. When burning occurs, the newly developed software program sends a control signal warning the operator or interrupting the process, and delivers process information via the Internet. Parallel to this, the user can also interfere in the process via Internet, changing parameters and/or monitoring the grinding process. The findings of a comparative study of the various parameters are also discussed here. Copyright © 2006 by ABCM.

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The use of the nasal route for drug delivery has attracted much interest in recent years in the pharmaceutical field. Local and principally systemic drug delivery can be achieved by this route of administration. But the nasal route of delivery is not applicable to all drugs. Polar drugs and some macromolecules are not absorbed in sufficient concentration due to poor membrane permeability, rapid clearance and enzymatic degradation into the nasal cavity. Thus, alternative means that help overcome these nasal barriers are currently in development. Absorption enhancers such as phospholipids and surfactants are constantly used, but care must be taken in relation to their concentration. Drug delivery systems including liposomes, cyclodextrins, micro- and nanoparticles are being investigated to increase the bioavailability of drugs delivered intranasally. This review article discusses recent progress and specific development issues relating to colloidal drug delivery systems in nasal drug delivery. © 2006 Bentham Science Publishers Ltd.

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Polymeric nanoparticles have received great attention as potential controlled drug delivery systems. Biodegradable polymers has been extensively used in the development of these drug carriers, and the polyesters such as polylactic acid, polyglycolic acid and their copolymers as poly-lactide-co- glycolide are the most used, considering its biocompatibility and biodegradability. Thermal analysis techniques have been used for pharmaceutical substances for more than 30 years and are routine methods for screening drug-excipient interactions. The aim of this work is to use thermal analysis to characterize PLGA nanoparticles containing a hydrophobic drug, praziquantel. The results show that the drug is in an amorphous state or in disordered crystalline phase of molecular dispersion in the PLGA polymeric matrix and that the microencapsulation process did not interfere with the chemical structure of the polymer, mantaining the structural drug integrity.

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The cationic polysaccharide chitosan has been widely used for non-viral transfection in vitro and in vivo and has many advantages over other polycations. Chitosan is biocompatible and biodegradable and protects DNA against DNase degradation. However following administration the ChitosanDNA polyplexes must overcome a series of barriers before DNA is delivered to the cell nucleus. This paper describes the most important parameters involved in the chitosan-DNA interaction and their effects of on the condensation, shape, size and protection of DNA. Strategies developed for chitosanDNA polyplexes to avoid non-specific interaction with blood components and to overcome intracellular obstacles as the crossing of die cell membrane, endosomal escape and nuclear import are presented. © 2006 American Chemical Society.

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This paper presents a methodology and a specialist tool for failure probability analysis of induction type watt-hour meters, considering the main variables related to their measurement degradation processes. The database of the metering park of a distribution company, named Elektro Electricity and Services Co., was used for determining the most relevant variables and to feed the data in the software. The modeling developed to calculate the watt-hour meters probability of failure was implemented in a tool through a user friendly platform, written in Delphi language. Among the main features of this tool are: analysis of probability of failure by risk range; geographical localization of the meters in the metering park, and automatic sampling of induction type watt-hour meters, based on a risk classification expert system, in order to obtain information to aid the management of these meters. The main goals of the specialist tool are following and managing the measurement degradation, maintenance and replacement processes for induction watt-hour meters. © 2011 IEEE.