859 resultados para BORON-CENTERED RADICALS
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A cathodically pretreated boron-doped diamond electrode was used for the simultaneous anodic determination of ascorbic acid (AA) and caffeine (CAF) by differential pulse voltammetry Linear calibration curves (r = 0 999) were obtained from 1 9 x 10(-5) to 2 I x 10(-4) mol L(-1) for AA and from 9 7 x 10(-6) to 1 1 x 10-4 mol L(-1) for CAF. with detection limits of 19 wool L(-1) and 7 0 mu nol L(-1). respectively This method was successfully applied for the determination of AA and CAF in pharmaceutical formulations. with results equal to those obtained using a HPLC reference method
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A simple and highly selective electrochemical method was developed for the single or simultaneous determination of paracetamol (N-acetyl-p-aminophenol, acetaminophen) and caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione) in aqueous media (acetate buffer, pH 4.5) on a boron-doped diamond (BDD) electrode using square wave voltammetry (SWV) or differential Pulse voltammetry (DPV). Using DPV with the cathodically pre-treated BDD electrode, a separation of about 550 mV between the peak oxidation potentials Of paracetamol and caffeine present in binary mixtures was obtained. The calibration curves for the simultaneous determination of paracetamol and caffeine showed an excellent linear response, ranging from 5.0 x 10(-7) mol L(-1) to 8.3 x 10(-7) mol L(-1) for both compounds. The detection limits for the simultaneous determination of paracetamol and caffeine were 4.9 x 10(-7) mol L-1 and 3.5 x 10(-8) mol L(-1), respectively. The proposed method Was Successfully applied in the simultaneous determination of paracetamol and caffeine in several pharmaceutical formulations (tablets), with results similar to those obtained using a high-performance liquid chromatography method (at 95% confidence level). (C) 2008 Elsevier BY. All rights reserved.
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The mechanism of chloroperoxidase (CPO)-catalyzed peroxidatic reactions of several substituted hydroquinones was studied at various hydrogen peroxide concentrations. The pathway was studied using cytochrome c as the radical trapping agent. As the hydroquinones became more hindered there was a difference in the amount of radicals trapped. For hydroquinone, 59.3% radical pathway, and methylhydroquinone, 81.4% radical, the difference in radicals trapped is due to a difference in pathway. For 2,3-dimethylhydroquinone (75.4%), trimethylhydroquinone (44.5%), and t-butylhydroquinone (0%) other non-peroxidatic reactions are noticed. Thus, for the more substituted hydroquinones the difference in radicals trapped can not be assigned to a difference in radical pathway. Also, there were problems drawing conclusions for this system due to the catalytic reaction of hydrogen peroxide. The radical trapping ability of 2,4,6-trimethylphenol was investigated for various other substrates. TMP reacted with the radicals generated in the enzymatic reactions of phenol, resorcinol, and m-methoxyphenol. Thus, this TMP system offers further potential as another radical trapping agent for use in these studies.
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João Bernardo de Sena Esteves Falcão e Cunha
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The purpose of this study was to identify whether activity modeling framework supports problem analysis and provides a traceable and tangible connection from the problem identification up to solution modeling. Methodology validation relied on a real problem from a Portuguese teaching syndicate (ASPE), regarding courses development and management. The study was carried out with a perspective to elaborate a complete tutorial of how to apply activity modeling framework to a real world problem. Within each step of activity modeling, we provided a summary elucidation of the relevant elements required to perform it, pointed out some improvements and applied it to ASPE’s real problem. It was found that activity modeling potentiates well structured problem analysis as well as provides a guiding thread between problem and solution modeling. It was concluded that activity-based task modeling is key to shorten the gap between problem and solution. The results revealed that the solution obtained using activity modeling framework solved the core concerns of our customer and allowed them to enhance the quality of their courses development and management. The principal conclusion was that activity modeling is a properly defined methodology that supports software engineers in problem analysis, keeping a traceable guide among problem and solution.
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A deficiência de B é muito comum nos cafezais brasileiros, mas as respostas do cafeeiro ao B têm sido erráticas, dependendo do ano, do modo e época de aplicação e, ainda, da fonte de B empregada. Um melhor entendimento dos efeitos do B na fisiologia e anatomia do cafeeiro é importante para o desenvolvimento de um programa racional de adubação boratada, uma vez que a anatomia da planta pode influenciar a translocação do nutriente. Neste experimento, plantas de dois cultivares foram cultivadas em soluções nutritivas com 0,0 (deficiente), 5,0 (adequado) e 25,0 µM (alto) de B. Quando os primeiros sintomas de deficiência apareceram, as folhas foram cortadas e tiveram suas paredes celulares isoladas e analisadas quanto aos teores de B e Ca. Cortes foram feitos em folhas novas e no ápice de ponteiros e fotografados em microscópio eletrônico de varredura. A resposta dos dois cultivares ao B foi semelhante, não tendo sido observados sintomas de toxidez. O teor de B nas paredes celulares foi aumentado com o incremento da concentração desse elemento na solução, enquanto o teor de Ca não foi afetado. A relação Ca/B decresceu com o aumento da concentração de B na solução. Com deficiência de B, os tecidos vasculares foram desorganizados e as paredes do xilema ficaram mais finas. Folhas de café com deficiência deste nutriente apresentaram menos estômatos, os quais se encontravam.
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O boro (B) tem baixa mobilidade no floema das plantas e é reconhecidamente o micronutriente cuja deficiência é mais comum no algodoeiro. Neste trabalho foi estudada a absorção e mobilidade do B em cultivares de algodão. O experimento foi conduzido em casa de vegetação, e as plantas foram cultivadas em solução nutritiva. Os tratamentos foram constituídos de três cultivares de algodão (FMT 701, DP 604BG e FMX 993) e cinco doses de B (0,0; 2,5; 5,0; 10,0 e 20,0 µmol L-1). As avaliações foram feitas em quatro semanas consecutivas, a partir da primeira semana após emissão do primeiro botão floral. A época de aparecimento e a intensidade de sintomas de deficiência de boro entre cultivares de algodão são diferentes. A cultivar DP604BG é inicialmente menos exigente em B, porém há necessidade de maior disponibilidade desse micronutriente no meio nutritivo para evitar o aparecimento de deficiência. O crescimento do algodoeiro é prejudicado pela carência de B, independentemente das diferenças no aparecimento de sintomas, não havendo diferença entre as cultivares.
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Boron adsorption by soil is the main phenomenon that affects its availability to plants. This, the present study investigated the effect of liming on B adsorption by lowland soils of Parana State, and to correlate these values with the physical and chemical properties of the soils. Surface samples of three lowland soils [Gleissolo Haplico (GX), Plintossolo Haplico (FX) and Cambissolo Haplico (CX)], with different origin material and physicochemical properties were used. Samples with or without liming application were incubated during 60 days. Boron adsorption was accomplished by shaking 4.0g soil samples, for 24 h, with 20 mL of 0.01 mol L-1 CaCl2 solution containing different concentrations of B (0, 1, 2, 4, 8 and 16 mg L-1). Sorption was fitted to non-linear form of the Langmuir adsorption isotherm. The adsorption isotherms indicated that the B adsorption increased with its increasing concentration in the equilibrium solution. Maximum adsorption capacity of B ranged from 3.0 to 13.9 mg kg(-1) (without liming) and 14.7 to 35.7 mg kg(-1) (with liming). Liming increased the amount of adsorbed B in Gleissolo Haplico and Plintossolo Haplico soils, although the bonding energy has decreased. The amount of adsorbed B by Cambissolo Haplico soil was not affected by liming application. The most important soil properties affecting the B adsorption in lowland soils were pH, clay content, exchangeable aluminum and iron oxide contents.
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No Brasil não existem registros de respostas de adubação com boro para a cultura do triticale, sendo a ação deste nutriente uma incógnita, tanto em relação a deficiência quanto a toxidez, causas que levam a redução de produtividade. O objetivo deste trabalho foi avaliar a resposta do triticale a diferentes níveis de boro em comparação com o trigo (Triticum aestivum). Utilizou-se um Latossolo Vermelho distrófico com teor inicial de boro de 0,08 mg dm-3. O delineamento foi um fatorial 4 ´ 4, distribuído em blocos casualizados, com quatro repetições, quatro níveis de boro: 0; 0,62; 1,24 e 1,86 mg dm-3 de B e três cultivares de triticale, IAC 3, BR 4 e BR 53, mais um cultivar de trigo, IAPAR 38, para comparação. Cada cultivar respondeu de forma diferente com relação às variáveis estudadas em função da aplicação de diferentes níveis de boro. O trigo (IAPAR 38) apresenta maior eficiência na absorção de boro. A cultivar de triticale mais responsiva quanto à absorção foi a IAC 3, que apresentou característica semelhante ao trigo, seguida da cultivar BR 4, demonstrando serem cultivares tolerantes a maiores níveis de boro no solo. Para a BR 53, não ocorreu efeito para absorção, com a cultivar apresentando sensibilidade à toxidez de boro. A eficiência de absorção é diferenciada para cada genótipo possibilitando a escolha e utilização de plantas que possuam maior adaptação ao meio.
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O presente estudo foi desenvolvido na UNESP/Botucatu, São Paulo, Brasil, num solo identificado como Oxisol, onde foram plantadas mudas de limoeiro Siciliano (C. limon) enxertadas em laranjeira Azeda (C. aurantium) e em limoeiro Cravo (C. limonia). O experimento consistiu em três níveis de saturação por bases (50%, 70% e 90%) e três doses de boro (0,5; 1,5 e 4,5 mg dm-3) no plantio em esquema fatorial de 3x3x2, com quatro repetições. Houve diferentes comportamentos entre os porta-enxertos no que se refere à composição mineral de folhas de limoeiro Siciliano , bem como, no desenvolvimento do sistema radicular, sendo maior na laranjeira azeda em relação ao limoeiro cravo. Não houve nenhum efeito na interação de níveis de saturação por bases e doses de boro para nenhum dos parâmetros avaliados.
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Redox processes are involved in the mechanism of action of NADPH oxidase inhibitors such as diphenyleneiodonium and apocynin. Here, we studied the structure-activity relationship for apocynin and analogous ortho-methoxy-substituted catechols as inhibitors of the NADPH oxidase in neutrophils and their reactivity with peroxidase. Aiming to alter the reduction potential, the ortho-methoxy-catechol moiety was kept constant and the substituents at para position related to the hydroxyl group were varied. Two series of compounds were employed: methoxy-catechols bearing electron-withdrawing groups (MC-W) such as apocynin, vanillin, 4-nitroguaiacol, 4-cyanoguaiacol, and methoxy-catechol bearing electron-donating groups (MC-D) such as 4-methylguaiacol and 4-ethylguaiacol. We found that MC-D were weaker inhibitors compared to MD-W. Furthermore, the radicals generated by oxidation of MC-W via MPO/H(2)O(2), but not for MC-D, were able to oxidize glutathione (GSH) as verified by the formation of thiyl radicals, depletion of GSH, and recycling of the ortho-methoxy-catechols during their oxidations. The capacity of oxidizing sulfhydryl (SH) groups was also verified when ovalbumin was incubated with MC-W, but not for MC-D. Since the effect of apocynin has been correlated with inactivation of the cytosolic fractions of the NADPH oxidase complex and its oxidation during the inhibitory process develops a special role in this process, we suggest that the close relationship between the reactivity of the radicals of MC-W compounds with thiol groups and their efficacy as NADPH oxidase inhibitor could be the chemical pathway behind the mechanism of action of apocynin and should be taken into account in the design of new and specific NADPH oxidase inhibitors. (c) 2007 Elsevier B.V. All rights reserved.
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Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)
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Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)
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The Capacitated Centered Clustering Problem (CCCP) consists of defining a set of p groups with minimum dissimilarity on a network with n points. Demand values are associated with each point and each group has a demand capacity. The problem is well known to be NP-hard and has many practical applications. In this paper, the hybrid method Clustering Search (CS) is implemented to solve the CCCP. This method identifies promising regions of the search space by generating solutions with a metaheuristic, such as Genetic Algorithm, and clustering them into clusters that are then explored further with local search heuristics. Computational results considering instances available in the literature are presented to demonstrate the efficacy of CS. (C) 2010 Elsevier Ltd. All rights reserved.
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Many pollutants dumped in waterways, such as dyes and pesticides, have become so ubiquitous that they represent a serious threat to human health. The electrochemical oxidation is presented as an alternative clean, efficient and economic degradation of wastewater containing organic compounds and a number of advantages of this technique is to just not make use of chemical reagents, since only electrical energy is consumed during the removal of pollutants organic. However, despite being a promising alternative, still needs some tweaking in order to obtain better efficiency in the elimination of persistent pollutants. Thus, this study sought a relationship between a recently discovered phenomenon that reflects the participation of dissolved oxygen in solution in the electrochemical oxidation process, as an anomaly, present a kinetic model that shows instantaneous current efficiency (ICE) above 100% limited by theory, manifested for some experiments with phenolic compounds with H2SO4 or HClO4 as supporting electrolyte with electrodes under anodic oxidation on boron doped diamond (BDD). Therefore it was necessary to reproduce the data ICE exposes the fault model, and thus the 2-naphthol was used as phenolic compound to be oxidised at concentrations of 9, 12 and 15 mmol L-1, and H2SO4 and HClO4 to 1 mol L-1 as a supporting electrolyte under a current density of 30 mA cm-2 in an electrochemical reactor for continuous flow disk configuration, and equipped with anodes DDB at room temperature (25 oC). Experiments were performed using N2 like as purge gas for eliminate oxygen dissolved in solution so that its influence in the system was studied. After exposure of the anomaly of the ICE model and investigation of its relationship with dissolved O2, the data could be treated, making it possible for confirmation. But not only that, the data obtained from eletranálise and spectroscopic analysis suggest the involvement of other strongly oxidizing species (O3 (ozone) and O radicals and O2 -), since the dissolved O2 can be consumed during the formation of new strong oxidizing species, not considered until now, something that needs to be investigated by more accurate methods that we may know a little more of this system. Currently the performance of the electrocatalytic process is established by a complex interaction between different parameters that can be optimized, so it is necessary to the implementation of theoretical models, which are the conceptual lens with which researchers see