979 resultados para Time-resolved methods


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This work demonstrates, for the first time. a time-resolved electron paramagnetic resonance (EPR) monitoring of a chemical reaction occurring in a polymeric structure. The progress of the coupling of a N-alpha-tert-butyloxycarbonyl-2.2.6.6-tetramethylpiperidine-1-oxyl-4-amino-4-carboxylic acid (Boc-TOAC) spin probe to a model peptide-resin was followed through EPR spectra. Progressive line broadening of EPR peaks was observed, indicative of an increased population of immobilized spin probe molecules attached to the solid support. The time for spectral stabilization of this process coincided with that determined in a previous Coupling study. thereby validating this in situ quantitative monitoring of the reaction. In addition, the influence of polymer swelling degree and solvent viscosity, as well as of the steric hindrance within beads. on the rate of coupling reaction was also addressed. A deeper evaluation of the latter effect was possible by determining unusual polymer parameters such as the average site-site distance and site-concentration within resin beads in each solvent system. (c) 2006 Elsevier Ltd. All rights reserved.

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

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Diurea cross-linked bridged silsesquioxanes (BSs) C(10)C(11)C(10) derived from organosilane precursors, including decylene chains as side spacers and alkylene chains with variable length as central spacers (EtO)(3)Si- (CH(2))(10)-Y(CH(2))(n)-Y-(CH(2))(10)-Si(OEt)(3) (n = 7, 9-12; Y = urea group and Et = ethyl), have been synthesized through the combination of self-directed assembly and an acid-catalyzed sol gel route involving the addition of dimethylsulfoxide (DMSO) and a large excess of water. This new family of hybrids has enabled us to conclude that the length of the side spacers plays a unique role in the structuring of alkylene-based BSs, although their morphology remains unaffected. All the samples adopt a lamellar structure. While the alkylene chains are totally disordered in the case of the C(10)C(7)C(10) sample, a variable proportion of all-trans and gauche conformers exists in the materials with longer central spacers. The highest degree of structuring occurs for n = 9. The inclusion of decylene instead of propylene chains as side spacers leads to the formation of a stronger hydrogen-bonded urea-urea array as evidenced by two dimensional correlation Fourier transform infrared spectroscopic analysis. The emission spectra and emission quantum yields of the C(10)C(n)C(10) Cm materials are similar to those reported for diurea cross-linked alkylene-based BSs incorporating propylene chains as side spacers and prepared under different experimental conditions. The emission of the C(10)C(n)C(10) hybrids is ascribed to the overlap of two distinct components that occur within the urea cross-linkages and within the siliceous nanodomains. Time-resolved photoluminescence spectroscopy has provided evidence that the average distance between the siliceous domains and the urea cross-links is similar in the C(10)C(n)C(10) BSs and in oxyethylene-based hybrid analogues incorporating propylene chains as side spacers (diureasils), an indication that the longer side chains in the former materials adopt gauche conformations. It has also allowed us to demonstrate for the first time that the emission features of the urea-related component of the emission of alkylene-based BSs depend critically on the length of the side spacers.

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By simple room temperature broad band time-resolved spectroscopy it was possible to discriminate different Eu3+ spectra in SnO2 monolithic gels obtained by a sol-gel synthetic route. Nanocrystalline domains of the cassiterite-like SnO2:Eu could be easily identified in the transparent medium. From X-ray diffraction profiles a mean particle radius of 2.2 nm was estimated. © 1992.

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Tetrahedral nickel(0) complexes [NiL4], [Ni(dppe)2] and [Ni(CO)2(SbPh3)2] (L=AsPh3, SbPh3, P(OPh)3, dppe=1,2-bis(diphenylphosphino)ethane) were prepared by reduction of NiCl2·6H2O with NaBH4 under N2 or CO atmosphere in the presence of the ligand. The complex [Ni(SbPh3)4] was also obtained by electrolysis at -1.3 V (Ag/Ag+), under a platinum gauze, of the system NiCl2·6H2O/SbPh3 (molar ratio=1:4). These complexes, both in the solid state and in solution, show an orange emission at room temperature, when excited with UV radiation. A qualitative molecular orbital diagram for the [NiL4] complexes is proposed. Electronic absorption spectra of the complexes show bands near 400 nm assigned as MLCT π*2e←d2t2. A 1A1←3T1 transition is suggested for the emission observed in these systems. Lifetimes in microsecond range were estimated from time-resolved emission spectra. Spectroscopic properties of the free ligands have also been investigated.

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Gd2SiO5 is among the interesting and suitable hosts for Er3+ which find extensive applications in the infrared, visible and ultraviolet spectral regions. In order to investigate its potentialities, a prior study of the spectroscopic behaviour of Er3+ substituting for Gd3+ ions in the two crystallographic sites of the host was performed. Absorption, excitation, site-selective emission and time-resolved spectroscopies were employed in the visible spectral region to study transitions between excited 4S3/2 and ground 4I15/2 states. These levels multiplets were attributed to each site separately, and their corresponding 4S3/2 lifetimes (1.8 ± 0.1 μs for site 1 and 3.2 ± 0.1 μs for site 2) were determined.

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The problem of assigning cells to switches in a cellular mobile network is an NP-hard optimization problem. So, real size mobile networks could not be solved by using exact methods. The alternative is the use of the heuristic methods, because they allow us to find a good quality solution in a quite satisfactory computational time. This paper proposes a Beam Search method to solve the problem of assignment cell in cellular mobile networks. Some modifications in this algorithm are also presented, which allows its parallel application. Computational results obtained from several tests confirm the effectiveness of this approach to provide good solutions for medium- and large-sized cellular mobile network.

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Purpose: The use of different light sources as an adjunct to in-office bleaching has been questioned. Thus, the aim of this study was to evaluate the color changes of teeth after application of bleaching techniques with different products, with and without activation by a LED-laser system. Methods: Twenty-four bovine teeth surfaces were submitted to three bleaching techniques with two commercially available 35% hydrogen peroxide bleaching agents (n=8). The specimens were immersed in red wine for 48 h at 37°C and submitted to the bleaching techniques. Color changes were measured before and after staining as well as immediately after and 24 h after the bleaching treatments, with two different methods of color evaluation, software ScanWhite V1.1 and intra-oral spectrophotometer (Vita Easyshade). Data were analyzed by ANOVA and Kruskal-Wallis test. Results: The statistical analysis showed that there was no statistically significant difference at 5% of significance level between the different groups, independently of the evaluation time, evaluation methods or the use of LED-laser systems. Conclusion: The results suggested that the use of light in the bleaching techniques did not influence the color changes. Copyright: © 2011 Roberto et al.

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Purpose. To verify the effects of resistance training at the electromyographic fatigue threshold (EMGFT) based on one-repetition maximum strength (1RM), heart rate (HR), rate of perceived exertion (PE) and endurance time (EndT). Methods. Nineteen subjects (training group [TG]: n = 10; control group [CG]: n = 9), performed 1-min bicep curl exercises sets at 25%, 30%, 35% and 40% 1RM. Electromyography (biceps brachii and brachiorradialis), HR and PE were registered. Biceps brachii EMGFT was used to create a load index for an eight-week resistance training programme (three sets until exhaustion/session, two sessions/week) for the TG. The CG only attended one session in the first week and another session in the last week of the eight-week training period for EndT measurement. EndT was determined from the number of repetitions of each of the three sets performed in the first and last training sessions. After training, 1RM, EMGFT, EndT, HR and PE at the different bicep curl load intensities were again measured for both groups. Results. Increases in 1RM (5.9%, p < 0.05) and EndT (> 60%, p < 0.001) after training were found. In addition, PE was reduced at all load intensities (p < 0.05), while no changes were found for HR and EMGFT after training. Conclusions. Strength-endurance training based on the EMGFT improved muscular endurance and also, to a lesser extent, muscular strength. Moreover, the reduced levels of physical exertion after training at the same intensity suggest that endurance training exercises may improve comfort while performing strength exercises.

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Pós-graduação em Ciências Farmacêuticas - FCFAR

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

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

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Neste trabalho, foi realizado um estudo de mapeamento de áreas de incidência e previsões para os casos de dengue na área urbana de Belém. Para as previsões foi utilizada à incidência de dengue com a precipitação pluviométrica a partir de modelos estatísticos, baseados na metodologia de Box e Jenkins de series temporais. O período do estudo foi de 05 anos (2007-2011). Na pesquisa temos métodos multivariados de series temporais, com uso de função de transferência e modelos espaciais, em que se analisou a existência de autocorrelações espaciais na variável em estudo. Os resultados das análises dos dados de incidência de casos de dengue e precipitação mostraram que, o aumento no número de casos de dengue acompanha o aumento na precipitação, demonstrando a relação direta entre o número de casos de dengue e a precipitação nos anos em estudo. O modelo de previsão construído para a incidência de casos de dengue apresentou um bom ajuste com resultados satisfatórios podendo, neste caso, ser utilizado na previsão da dengue. Em relação à análise espacial, foi possível uma visualização da incidência de casos na área urbana de Belém, com as respectivas áreas de incidência, mostrando os níveis de significância em porcentagem. Para o período estudado observou-se o comportamento e as variações dos casos de dengue, com destaque para quatro bairros: Marco, Guamá, Pedreira e Tapanã, com possíveis influências destes bairros nas áreas (bairros) vizinhas. Portanto, o presente estudo evidencia a contribuição para o planejamento das ações de controle da dengue, ao servir de instrumento no apoio às decisões na área de saúde pública.