20 resultados para Reactions in Polar Aprotic Media

em Biblioteca Digital da Produção Intelectual da Universidade de São Paulo


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BACKGROUND: In Brazil little is known about adverse reactions during donation and the donor characteristics that may be associated with such events. Donors are offered snacks and fluids before donating and are required to consume a light meal after donation. For these reasons the frequency of reactions may be different than those observed in other countries. STUDY DESIGN AND METHODS: A cross-sectional study was conducted of eligible whole blood donors at three large blood centers located in Brazil between July 2007 and December 2009. Vasovagal reactions (VVRs) along with donor demographic and biometric data were collected. Reactions were defined as any presyncopal or syncopal event during the donation process. Multivariable logistic regression was performed to identify predictors of VVRs. RESULTS: Of 724,861 donor presentations, 16,129 (2.2%) VVRs were recorded. Rates varied substantially between the three centers: 53, 290, and 381 per 10,000 donations in Recife, Sao Paulo, and Belo Horizonte, respectively. Although the reaction rates varied, the donor characteristics associated with VVRs were similar (younger age [18-29 years], replacement donors, first-time donors, low estimated blood volume [EBV]). In multivariable analysis controlling for differences between the donor populations in each city younger age, first-time donor status, and lower EBV were the factors most associated with reactions. CONCLUSION: Factors associated with VVRs in other locations are also evident in Brazil. The difference in VVR rates between the three centers might be due to different procedures for identifying and reporting the reactions. Potential interventions to reduce the risk of reactions in Brazil should be considered.

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A high-performance liquid chromatographic method using polar organic mode was developed to analyze albendazole (ABZ), albendazole sulfone (ABZSO(2)) and the chiral and active metabolite albendazole sulfoxide (ABZSOX, ricobendazole) that was further applied in stereoselective fungal biotransformation studies. The chromatographic separation was performed on a Chiralpak AS column using acetonitrile:ethanol (97:3, v/v) plus 0.2% triethylamine and 0.2% acetic acid as the mobile phase at a flow rate of 0.5 mL min(-1). The present study employed hollow fiber liquid-phase microextraction as sample preparation. The method showed to be linear over the concentration range of 25-5000 ng mL(-1) for each ABZSOX enantiomer, 200-10,000 ng mL(-1) for ABZ and 50-1000 ng mL(-1) for ABZSO(2) metabolite with correlation coefficient (r)> 0.9934. The mean recoveries for ABZ, rac-ABZSOX and ABZSO(2) were, respectively, 9%, 33% and 20% with relative standard deviation below 10%. Within-day and between-day precision and accuracy assays for these analytes were studied at three concentration levels and were lower than 15%. This study opens the door regarding the possibility of using fungi in obtaining of the active metabolite ricobendazole. Nigrospora sphaerica (Sacc.) E. W. Mason (5567), Pestalotiopsis foedans (VR8), Papulaspora immersa Hotson (SS13) and Mucor rouxii were able to stereoselectively metabolize ABZ into its chiral metabolite. Among them, the fungus Mucor rouxii was the most efficient in the production of (+)-ABZSOX. (C) 2011 Elsevier B.V. All rights reserved.

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OBJECTIVE: To analyze discourses on workplace psychological harassment in print media. METHODOLOGICAL PROCEDURES: Documental study on workplace psychological harassment that analyzed news stories published in three major newspapers of the State of Sao Paulo (southeastern Brazil) between 1990 and 2008. Discourse analysis was performed to identify discursive practices that reflect the phenomenon of psychological harassment in today's society, explanations for its occurrence and impact on workers' health. RESULT ANALYSIS: This theme emerged in the media through the dissemination of books, academic research production and laws. It was initially published in general news then in jobs and/or business sections. Discourses on compensation and precautionary business practices and coping strategies are widespread. Health-related aspects are foregone under the prevailing money-based rationale. Corporate cultures are permissive regarding psychological harassment and conflicts are escalated while working to achieve goals and results. Indifference, embarrassment, ridicule and demean were common in the news stories analyzed. CONCLUSIONS: The causal explanations of workplace harassment tend to have a psychological interpretation with emphasis on individual and behavioral characteristics, and minimizing a collective approach. The discourses analyzed trivialized harassment by creating caricatures of the actors involved. People apprehend its psychological content and stigmatization which contributes to making workplace harassment an accepted practice and trivializing work-related violence.

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Increase in the pH medium of aniline polymerization is used for giving products of different morphologies, which are often wrongly attributed to PANI chains. Infrared and Raman spectroscopic data, supported by quantum chemical calculations, show that aniline-1,4-benzoquinone (AnBzq) is a model system for the characterization of the products of aniline oligomerization in low acidic media. The Raman spectra excited at different laser lines reveal the bichromophoric nature of AnBzq, whose absorption bands at 550 nm and 440 nm can be attributed to pi-pi* transitions of the delocalized benzoquinone and amino-phenyl moieties, respectively. (C) 2012 Elsevier B.V. All rights reserved.

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This work describes the synthesis of five O-silyloxy-1,3-thiazoles and their use as fast-response turn-on probes for fluoride ion detection in polar aprotic solvents and in aqueous cetyltrimethylammonium bromide micellar medium. The fluoride-triggered deprotection of these silyl ethers results in ca. 180-nm shifts in the fluorescence emission wavelengths. All compounds are suitable for the detection of fluoride ions with a detection limit in DMSO of 107 mol?L1; derivatives containing a 2-pyridyl moiety in the thiazole system are more efficient than those with a 3- or 4-pyridyl moiety. Typical anionic interferents, such as acetate or chloride, are not detected by O-silyloxy-1,3-thiazoles, making these compounds very specific for fluoride.

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One of the key objectives in fuel cell technology is to reduce Pt loading by the improvement of its catalytic activity towards alcohol oxidation. Here, a sol-gel based method was used to prepare ternary and quaternary carbon supported nanoparticles by combining Pt-Ru with Mo, Ta, Pb, Rh or Ir, which were used as electro-catalysts for the methanol and ethanol oxidation reactions in acid medium. Structural characterization performed by XRD measurements revealed that crystalline structures with crystallites ranging from 2.8 to 4.1 nm in size and with different alloy degrees were produced. Tantalum and lead deposited as a heterogeneous mixture of oxides with different valences resulting in materials with complex structures. The catalysts activities were evaluated by cyclic voltammetry and by Tafel plots and the results showed that the activity towards methanol oxidation was highly dependent of the alloy degree, while for ethanol the presence of a metal capable to promote the break of C-C bond, such as Rh, was necessary for a good performance. Additionally, the catalysts containing of TaOx or PbOx resulted in the best materials due to different effects: the hi-functional mechanism promoted by TaOx and a better dispersion of the catalysts constituents promoted by PbOx. (C) 2012 Elsevier B.V. All rights reserved.

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During sporulation, Bacillus subtilis redeploys the division protein FtsZ from midcell to the cell poles, ultimately generating an asymmetric septum. Here, we describe a sporulation-induced protein, RefZ, that facilitates the switch from a medial to a polar FtsZ ring placement. The artificial expression of RefZ during vegetative growth converts FtsZ rings into FtsZ spirals, arcs, and foci, leading to filamentation and lysis. Mutations in FtsZ specifically suppress RefZ-dependent division inhibition, suggesting that RefZ may target FtsZ. During sporulation, cells lacking RefZ are delayed in polar FtsZ ring formation, spending more time in the medial and transition stages of FtsZ ring assembly. A RefZ-green fluorescent protein (GFP) fusion localizes in weak polar foci at the onset of sporulation and as a brighter midcell focus at the time of polar division. RefZ has a TetR DNA binding motif, and point mutations in the putative recognition helix disrupt focus formation and abrogate cell division inhibition. Finally, chromatin immunoprecipitation assays identified sites of RefZ enrichment in the origin region and near the terminus. Collectively, these data support a model in which RefZ helps promote the switch from medial to polar division and is guided by the organization of the chromosome. Models in which RefZ acts as an activator of FtsZ ring assembly near the cell poles or as an inhibitor of the transient medial ring at midcell are discussed.

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Pt extended surfaces and nanoparticle electrodes are used to understand the origin of anomalous activities for electrocatalytic reactions in alkaline electrolytes as a function of cycling/time. Scanning tunneling microscopy (STM) of the surfaces before and after cycling in alkaline electrolytes was used to understand the morphology of the impurities and their impact on the catalytic sites. The nature of the contaminant species is identified as 3d-transition metal cations, and the formation of hydr(oxy)oxides of these elements is established as the main reason for the observed behavior. We find that, while for the oxygen reduction reaction (ORR) and the hydrogen oxidation reaction (HOR) the blocking of the sites by the undesired 3d-transition metal hydr(oxy)oxide species leads to deactivation of the reaction activities, the CO oxidation reaction and the hydrogen evolution reaction (HER) can have beneficial effects from the same impurities, the latter being dependent on the exact nature of the adsorbing species. These results show the significance of impurities present in real electrolytes and their impact on electrocatalysis.

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Abstract Aim Oxidative stress has been implicated in the pathogenesis of Nonalcoholic Fatty Liver Disease (NAFLD). Vitamin C and vitamin E are known to react with reactive oxygen species (ROS) blocking the propagation of radical reactions in a wide range of oxidative stress situations. The potential therapeutic efficacy of antioxidants in NAFLD is unknown. The aim of this study was to evaluate the role of antioxidant drugs (vitamin C or vitamin E) in its prevention. Methods Fatty liver disease was induced in Wistar rats by choline-deficient diet for four weeks. The rats were randomly assigned to receive vitamin E (n = 6) – (200 mg/day), vitamin C (n = 6) (30 mg/Kg/day) or vehicle orally. Results In the vehicle and vitamin E-treated rats, there were moderate macro and microvesicular fatty changes in periportal area without inflammatory infiltrate or fibrosis. Scharlach stain that used for a more precise identification of fatty change was strong positive. With vitamin C, there was marked decrease in histological alterations. Essentially, there was no liver steatosis, only hepatocellular ballooning. Scharlach stain was negative. The lucigenin-enhanced luminescence was reduced with vitamin C (1080 ± 330 cpm/mg/minx103) as compared to those Vitamin E and control (2247 ± 790; 2020 ± 407 cpm/mg/minx103, respectively) (p < 0.05). Serum levels of aminotransferases were unaltered by vitamin C or vitamin E. Conclusions 1) Vitamin C reduced oxidative stress and markedly inhibited the development of experimental liver steatosis induced by choline-deficient diet ; 2)Vitamin E neither prevented the development of fatty liver nor reduced the oxidative stress in this model.

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Purpose: To compare the intravitreal pharmacokinetic profile of a triamcinolone acetonide formulation containing the preservative benzyl alcohol (TA-BA) versus a preservative-free triamcinolone acetonide formulation (TA-PF), and evaluate potential signs of toxicity to the retina. Methods: A total of 60 New Zealand male white rabbits, divided into two groups, were studied. In the TA-BA group, 30 rabbits received an intravitreal injection of TA-BA (4 mg/0.1ml) into the right eye. In the TA-PF group, 30 rabbits received an intravitreal injection of TA-PF (4 mg/0.1ml) into the right eye. The intravitreal drug levels were determined in 25 animals from each group by high-performance liquid chromatography (HPLC). The potential for toxicity associated with the intravitreal triamcinolone injections was evaluated in five randomly selected animals from each group by electroretinography (ERG) and by light microscopy. Results: Median intravitreal concentrations of TA-BA (mu g/ml) were 1903.1, 1213.0, 857.8, 442.0, 248.6 at 3, 7, 14, 21 and 28 days after injection. Intravitreal concentrations of TA-PF (mu g/ml) were 1032.9, 570.1, 516.6, 347.9, 102.8 at 3, 7, 14, 21 and 28 days after injection. The median intravitreal triamcinolone concentration was significantly higher in the TA-BA compared to the TA-PF group at 7 days post-injection (p < 0.05). There was no significant difference between the two groups in median triamcinolone concentration at the other time points evaluated. There was no evidence of toxic effects on the retina in either group based on ERG or histological analyses. Conclusions: Following a single intravitreal injection, the median concentration of triamcinolone acetonide is significantly higher in the TA-BA compared to the TA-PF group at 7 days post-injection. No toxic reactions in the retina were observed in either group.

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Bacterial adhesion to inert surfaces is a complex process influenced by environmental conditions. In this work, the influence of growth medium and temperature on the adhesion of Pseudomonas aeruginosa, Serratia marcescens, Staphylococcus aureus, Micrococcus luteus and Listeria monocytogenes to polystyrene surfaces was studied. Most bacteria demonstrated the highest adhesion when cultured in TSYEA, except S. marcescens, which showed to be positively influenced by the pigment production, favored in poor nutrient media (lactose and peptone agar). P. aeruginosa adhesion to polystyrene increased at low temperatures whatever the medium used. The culture medium influenced the surface properties of the bacteria as assessed by the MATS test.

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Molecular modeling is growing as a research tool in Chemical Engineering studies, as can be seen by a simple research on the latest publications in the field. Molecular investigations retrieve information on properties often accessible only by expensive and time-consuming experimental techniques, such as those involved in the study of radical-based chain reactions. In this work, different quantum chemical techniques were used to study phenol oxidation by hydroxyl radicals in Advanced Oxidation Processes used for wastewater treatment. The results obtained by applying a DFT-based model showed good agreement with experimental values available, as well as qualitative insights into the mechanism of the overall reaction chain. Solvation models were also tried, but were found to be limited for this reaction system within the considered theoretical level without further parameterization.

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This paper reports on results obtained from experiments carried out in an acidogenic anaerobic reactor aiming at the optimization of hydrogen production by altering the degree of back-mixing. It was hypothesized that there is an optimum operating point that maximizes the hydrogen yield. Experiments were performed in a packed-bed bioreactor by covering a broad range of recycle ratios (R) and the optimum point was obtained for an R value of 0.6. In this operating condition the reactor behaved as 8 continuous stirred-tank reactors in series and the maximum yield was 4.22 mol H-2 mol sucrose(-1). Such optimum point was estimated by deriving a polynomial function fitted to experimental data and it was obtained as the conjugation of three factors related to the various degrees of back-mixing applied to the reactor: mass transfer from the bulk liquid to the biocatalyst, liquid-to-gas mass transfer and the kinetic behavior of irreversible reactions in series. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

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Determination of organic acids in intracellular extracts and in the cultivation media of marine microalgae aid investigations about metabolic routes related to assimilation of atmospheric carbon by these organisms, which are known by their role in the carbon dioxide sink. The separation of these acids was investigated by hydrophilic interaction liquid chromatography (HILIC) using isocratic elution with a mobile phase composed of 70: 30 v/v acetonitrile/20 mmol/L ammonium acetate buffer (pH 6.8) and detection at 220 nm. HILIC allowed the determinations of glycolic acid, the most important metabolite for the evaluation of the photorespiration process in algae, to be made with better selectivity than that achieved by reversed phase liquid chromatography, but with less detectability. The concentration of glycolic acid was determined in the cultivation media and in intracellular extracts of the algae Tetraselmis gracilis and Phaeodactylum tricornutum submitted to different conditions of aeration: (i) without forced aeration, (ii) aeration with atmospheric air, and (iii) bubbling with N(2). The concentration of glycolic acid had a higher increase as the cultures were aerated with nitrogen, showing higher photorespiratory flux than that occurring in the cultures aerated with atmospheric air.

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Calcium (Ca) and boron (B) have been reported as the major macro-and micronutrient required for castor bean plant yield. The objective of this study was to determine the Ca: B ratios (in the growth media and plant tissue) for fruit yield and shoot dry weight of the castor bean (Ricinus communis L.), grown in a nutrient solution, and to evaluate Ca and B supply on concentration and total uptake of Ca, potassium (K), magnesium (Mg), and B, as well on the seed oil content. The treatments were arranged in a 3 x 3 factorial fashion, consisting of three rates of Ca (40, 80, and 160 mg L-1) and three of B (0.32, 0.96, and 1.60 mg L-1). Calcium and B rates increased the shoot and root dry weight and fruit yield at a Ca: B ratio in the nutrient solution of 166 and 100, respectively. Symptoms of B deficiency were observed in plants supplied with 0.32 mg B L-1, regardless of the Ca concentration in the nutrient solution. Plants which showed visual symptoms of Ca deficiency cultivated with 40 mg Ca L-1 presented concentration of Ca in plant tissue up to 10 g kg(-1). The concentration and total Ca and B uptake increased with the rates of them. Notwithstanding, the shoot Ca accumulation was improved by B rates. In addition, there were no decreases in K and Mg uptake due to Ca rates. Furthermore, addition of 80 mg L-1 of Ca and 1.60 mg L-1 of B in the growth media increased the seed oil content. The Ca: B ratio in the diagnostic leaf associated with the highest plant dry weight (shoot and root) and fruit yield, was 500 (16 to 20 g kg(-1) of Ca, and for 30 to 40 mg kg(-1) of B).