An insight into the beginning stage of the aqueous ring opening metathesis polymerization of exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid with Ru(III) compounds: the consumption of Ru(III) species in the presence of carboxylic acids monitored by ESR spectroscopy

The presence of paramagnetic species in the aqueous ring opening metathesis polymerizations of the exo,exo-7-oxabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid monomer with RuCl(3) and K(2)[RuCl(5)H(2)O] compounds was studied using ESR techniques. It was observed that the intensities of the Ru(III) signals in the ESR spectra decrease on the time scale of the induction period so that the ROMP can take place. The intensity of the Ru(III) signal almost disappeared 50 min after reacting with K(2)[RuCl(5)H(2)O] and after 100 mm in the case of RuCl(3). Reactions of the cis-[Ru(NH(3))(4)(H(2)O)(2)](tfms)(3) and [Ru(NH(3))(5)H(2)O](tfms)(3) complexes with the monomer and different organic compounds representing the organic functions in the monomer (furan, norbornene, but-2-ene-1,4-diol and formic, acetic, oxalic and maleic acids) were also monitored by ESR and UV/vis spectra. It was deduced that the organic acids provide the disappearance of the Ru(III) signal. The proton NMR relaxation times of the residual water in D(2)O for reactions with oxalic acid suggested that the presence of paramagnetic ions in the solution decreases along with

Involvement of free radicals in peroxidatic reactions catalyzed by chloroperoxidase

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.

Nanocatalysts for sustainable industrial processses

In Chapter 1, rhodium nanoparticles were supported on multiwalled carbon nanotubes (MWCNTs) and bound to the magnetic core-shell system Fe3O4@TiO2. The composite Fe3O4@TiO2-Rh-MWCNT and the intermediates were characterized by SEM, EDS and TEM. Their catalytic activity was studied using i) the hydrogenation transfer of nitroarenes and cyclohexene in the presence of hydrazine hydrate; ii) the reduction of 2-nitrophenol with NaBH4; and iii) the decoloration of pigments in the presence of hydrogen peroxide. The results were monitored by gas chromatography (i) and UV Visible (ii and iii). In the second chapter, the catalytic activity of six oxidovanadium(V) aroylhydrazone complexes, viz. [VOL1(OEt)][VOL1(OEt)(EtOH)] (1), [VOL2(OEt)] (2), [Et3NH][VO2L1] (3), [VO2(H2L2)]2·EtOH (4), [VOL1(µ -O)VOL1] (5) and [VOL2(µ -O)VOL2] (6) (H2L1 = 3,5-di-tert-butyl-2-hydroxybenzylidene)-2hydroxybenzohydrazide and H2L2 = 3,5-di-tert-butyl-2-hydroxybenzylidene)-2 aminobenzohydrazide), anchored on nanodiamonds with different treatments, was studied towards the microwave-assisted partial oxidation of 1-phenylethanol to acetophenone in the presence of tert-butyl hydroperoxide (TBHP) as oxidant. A high selectivity for acetophenone was achieved for the optimized conditions. The possibility of recycling and reuse the heterogeneous catalysts was also investigated. In chapter 3, the catalytic activity of gold nanoparticles supported at different metal oxides, such as Fe2O3, Al2O3 ZnO or TiO2, was studied for the above reaction. The effect of the support, quantity of the catalyst and temperature was investigated. The recyclability of the gold catalysts was also studied. In the last chapter, a new copper nanocomposite with functionalized mutiwalled carbon nanotubes (Cu-MWCNT) was synthesized using a microwave assisted polyol method. The characterization was performed using XRD and SEM. The catalytic activity of Cu-MWCNT was studied through the degradation of pigments, such as amaranth, brilliant blue, indigo, tartrazine and methylene blue.

Coordenação entre as respostas da catalase e da ascorbato peroxidade em folhas de feijão caupi submetidas a diferentes fontes de peróxido de hidrogênio

The plants are often exposed to variations in environmental conditions that may trigger metabolic disturbances leading to a consequent loss in productivity of crops. These stressful conditions usually induce an accumulation of reactive oxygen species (ROS) in the cell, a condition known how oxidative stress. Among these species, hydrogen peroxide (H2O2) is an important molecule involved in numerous signaling mechanisms. The present study aimed to understand the relationship between the different enzymatic mechanisms of elimination of H2O2 by catalase (CAT) and ascorbate peroxidase (APX) in leaf tissues of seedlings of the species Vigna unguiculata L. Walp, under conditions of oxidative stress induced by application of CAT inhibitor, 3-amino-1,2,4-triazole (3-AT), and H2O2 itself on the roots. Three experiments were conducted. The first experiment was performed applying the compound 3-AT (5 mM) during the time (hours). In the second experiment, seedlings were exposed to different concentrations of H2O2 (2.5, 5.0, 7.5, 10 mM) for 48 h. The third strategy included the pre-treatment with H2O2 (2.5 mM) for 24 h, followed by subsequent treatment with the inhibitor 3-AT and recovery control condition. Treatment with 3-AT causes a strong inhibition of CAT activity in leaf tissues accompanied by an increase of activity of APX. However a decrease in oxidative damage to lipids is not observed as indicated by TBARS. It was observed that activity of APX is directly linked to the content of peroxide. Inductions in the activities of CAT and APX were observed mainly in the seedlings treated with 2.5 mM H2O2. This can be associated with a decrease in oxidative damage to lipids. In contrast, one same tendency was not observed in treatments with higher concentrations of this ROS. These results suggest that the concentration of 2.5 mM H2O2 can induce responses antioxidants later in seedling cowpea. This concentration when applied as pre-treatment for 24 h promoted an induction systems removers CAT and APX, both in activity and in terms of gene expression. However this increment was not observed in the recovered plants and the plants subsequently subjected to 3-AT. Additionally, the pretreatment was not sufficient to attenuate the inhibition of CAT activity and oxidative damage to lipids caused by the subsequent application of this inhibitor. The results showed that the application of 3-AT and H2O2 in the root systems of seedlings of cowpea promote changes in the parameters analyzed in leaf tissues that indicate a direct response to the presence of these factors or systemic signaling mecanisms. H2O2 appears to activate the responses of two antioxidant systems in this study thar does not promote greater protection in case of additional treatment with 3-AT. This demonstrates the importance of the CAT system. In this work, complete results indicate that there is a difference between the signaling and the effects caused by exposure to H2O2 and by treatment with 3-AT

Potential and costs for the production of electrolytic hydrogen in alcohol and sugar cane plants in the central and south regions of Brazil

This project verified the potential for the production of hydrogen via water electrolysis by using the exceeding electrical energy resultant from alcohol and sugar plants that use sugar cane bagasse as fuel. The studies were carried out in cogeneration plants authorized by the Electrical Energy National Agency (ANEEL). The processing history of sugar cane considered was based on the 2006/2007 harvests. The total bagasse produced, electrical energy generated and exceeding electrical energy in a year were calculated. It was obtained an average energy consumption value of 5.2 kWh Nm(-3) and the hydrogen production costs regarding the amount of sugar cane processed that ranged from US$ 0.50 to US$ 0.75 Nm(-3). The results pointed that the costs for the production of hydrogen via the bagasse exceeding energy are close to the production costs that use other sources of energy. As the energy generated from the bagasse is a renewable one, this alternative for the production of hydrogen is economical and environmentally viable. (C) 2008 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Palma forrageira (Opuntia ficus indica e Nopalea cochenillifera) como matéria-prima para produção de etanol celulósico e enzimas celulolíticas

The need for new sources of energy and the concern about the environment have pushed the search for renewable energy sources such as ethanol. The use of lignocellulosic biomass as substrate appears as an important alternative because of the abundance of this raw material and for it does not compete with food production. However, the process still meets difficulties of implementation, including the cost for production of enzymes that degrade cellulose to fermentable sugars. The aim of this study was to evaluate the behavior of the species of cactus pear Opuntia ficus indica and Nopalea cochenillifera, commonly found in northeastern Brazil, as raw materials for the production of: 1) cellulosic ethanol by simultaneous saccharification and fermentation (SSF) process, using two different strains of Saccharomyces cerevisiae (PE-2 and LNF CA-11), and 2) cellulolytic enzymes by semi-solid state fermentation (SSSF) using the filamentous fungus Penicillium chrysogenum. Before alcoholic fermentation process, the material was conditioned and pretreated by three different strategies: alkaline hydrogen peroxide, alkaline using NaOH and acid using H2SO4 followed by alkaline delignification with NaOH. Analysis of composition, crystallinity and enzymatic digestibility were carried out with the material before and after pretreatment. In addition, scanning electron microscopy images were used to compare qualitatively the material and observe the effects of pretreatments. An experimental design 2² with triplicate at the central point was used to evaluate the influence of temperature (30, 40 and 45 °C) and the initial charge of substrate (3, 4 and 5% cellulose) in the SSF process using the material obtained through the best condition and testing both strains of S. cerevisiae, one of them flocculent (LNF CA-11). For cellulase production, the filamentous fungus P. chrysogenum was tested with N. cochenillifera in the raw condition (without pretreatment) and pretrated hydrothermically, varying the pH of the fermentative medium (3, 5 and 7). The characterization of cactus pear resulted in 31.55% cellulose, 17.12% hemicellulose and 10.25% lignin for N. cochenillifera and 34.86% cellulose, 19.97% hemicellulose and 15.72% lignin for O. ficus indica. It has also been determined, to N. cochenillifera and O. ficus indica, the content of pectin (5.44% and 5.55% of calcium pectate, respectively), extractives (26.90% and 9.69%, respectively) and ashes (5.40% and 5.95%). Pretreatment using alkaline hydrogen peroxide resulted in the best cellulose recovery results (86.16% for N. cochenillifera and 93.59% for O. ficus indica) and delignification (48.79% and 23.84% for N. cochenillifera and O. ficus indica, respectively). This pretreatment was also the only one which did not increase the crystallinity index of the samples, in the case of O. ficus indica. However, when analyzing the enzymatic digestibility of cellulose, alkali pretreatment was the one which showed the best yields and therefore it was chosen for the tests in SSF. The experiments showed higher yield of conversion of cellulose to ethanol by PE-2 strain using the pretreated N. cochenillifera (93.81%) at 40 °C using 4% initial charge of cellulose. N. cochenillifera gave better yields than O. ficus indica and PE-2 strain showed better performance than CA-11. N. cochenillifera proved to be a substrate that can be used in the SSSF for enzymes production, reaching values of 1.00 U/g of CMCase and 0.85 FPU/g. The pretreatment was not effective to increase the enzymatic activity values

Integração dos processos de flotação e foto-fenton para redução de óleos e graxas de água produzida em campos de petróleo

During production of oil and gas, there is also the production of an aqueous effluent called produced water. This byproduct has in its composition salts, organic compounds, gases and heavy metals. This research aimed to evaluate the integration of processes Induced Air Flotation (IAF) and photo-Fenton for reducing the Total Oils and Greases (TOG) present in produced water. Experiments were performed with synthetic wastewater prepared from the dispersion of crude oil in saline solution. The system was stirred for 25 min at 33,000 rpm and then allowed to stand for 50 min to allow free oil separation. The initial oil concentration in synthetic wastewater was 300 ppm and 35 ppm for the flotation and the photo-Fenton steps, respectively. These values of initial oil concentration were established based on average values of primary processing units in Potiguar Basin. The processes were studied individually and then the integration was performed considering the best experimental conditions found in each individual step. The separation by flotation showed high removal rate of oil with first-order kinetic behavior. The flotation kinetics was dependent on both the concentration and the hydrophilic-lipophilic balance (HLB) of the surfactant. The best result was obtained for the concentration of 4.06.10-3 mM (k = 0.7719 min-1) of surfactant EO 2, which represents 86% of reduction in TOG after 4 min. For series of surfactants evaluated, the separation efficiency was found to be improved by the use of surfactants with low HLB. Regarding the TOG reduction step by photo-Fenton, the largest oil removal reached was 84% after 45 min of reaction, using 0.44 mM and 10 mM of ferrous ions and hydrogen peroxide, respectively. The best experimental conditions encountered in the integrated process was 10 min of flotation followed by 45 min of photo-Fenton with overall TOG reduction of 99%, which represents 5 ppm of TOG in the treated effluent. The integration of processes flotation and photo-Fenton proved to be highly effective in reducing TOG of produced water in oilfields

TNF-alpha, H2O2 and NO response of peritoneal macrophages to Yersinia enterocolitica O : 3 derivatives

In this study, the effect of Yersinia derivatives on nitric oxide (NO), hydrogen peroxide (H2O2) and tumor necrosis factor-alpha (TNF-alpha) production by murine peritoneal macrophages was investigated. Addition of lipopolysaccharide (LPS) to the macrophage culture resulted in NO production that was dose dependent. on the other hand, bacterial cellular extract (CE) and Yersinia outer proteins (Yops) had no effect on NO production. The possible inhibitory effect of Yops on macrophage cultures stimulated with LPS was investigated. Yops partially inhibited NO production (67.4%) when compared with aminoguanidine. The effects of Yersinia derivatives on H2O2 production by macrophages were similar to those on NO production. LPS was the only derivative that stimulated H2O2 release in a dose-dependent manner. All Yersinia derivatives provoked the production of TNF-alpha, but LPS had the strongest effect, as observed for NO production. CE and Yops stimulated TNF-alpha production to a lesser extent than LPS. The results indicate the possibility that in vivo Yops may aid the evasion of the bacteria from the host defense mechanism by impairing the secretion of NO by macrophages. (C) 2003 Elsevier SAS. All rights reserved.

Prevalência e fatores de risco à persistência de hábitos bucais de sucção não nutritiva em crianças de 3 a 5 anos de idade

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Serotonin as a physiological substrate for myeloperoxidase and its superoxide-dependent oxidation to cytotoxic tryptamine-4,5-dione

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Degradação de compostos orgânicos voláteis usando o catalisador SBA-15 contendo titânio

The groundwater pollution arising due to fuel leaks gas stations has presented a problem aggravating. Increasingly studies related to environmental problems such accidents and seek to propose some solutions for the treatment of groundwater and soils that are contaminated by gasoline. This study evaluated the use of molecular sieve TiSBA-15 as a catalyst for the reaction of removing of volatile organic compounds, particularly benzene, toluene, ethylbenzene and xylenes, known as BTEX, one of the main pollutants found in groundwater. The catalyst was synthesized by the method post-synthesis techniques and characterized by XSD, TG/DTG, adsorption/desorption of N2, XRF-EDX, for checking the incorporation of titanium and formation of the structure of the catalyst. The reaction occurred with the presence of hydrogen peroxide, H2O2, in aqueous medium to form hydroxyl radicals, which are needed in the process of removal of BTEX compounds. The catalytic reaction was carried out for 5 hours at 60 °C, pH to 3.0, and analyzes of the compounds were made in a gas chromatograph with a flame detection means photoionization static headspace (HS-GC-PID). The catalytic tests have shown the efficacy of using this type of catalyst for the removal of these volatile organic compounds, having a removal rate of 90.60% in the range where the catalyst was studied TiSBA-15(5,0)

Lack of effect of prior treatment with fluoride on genotoxicity of two chemical agents in vitro

The goal of this study was to investigate the ability of fluoride to modulate the genotoxic effects induced by the oxidative agent hydrogen peroxide (H2O2) and the alkylating agent methyl methanesulfonate (MMS) in vitro by the single-cell gel ( comet) assay. Chinese hamster ovary cells were exposed in culture for 1 h at 37 degrees C to sodium fluoride at 7-100 mu g/ml. NaF-treated and control cells were then incubated with 0-10 mu M MMS in phosphate-buffered saline (PBS) for 15 min at 37 degrees C, or 7-100 mu M H2O2 in distilled water for 5 min on ice. Negative control cells were treated with PBS for 1 h at 37 degrees C. Clear concentration-related effects were observed for the two genotoxins. Increase of DNA damage induced by either MMS or H2O2 was not significantly altered by pretreatment with NaF. The data indicate that NaF does not modulate alkylation-induced genotoxicity or oxidative DNA damage as measured by the single-cell gel ( comet) assay. Copyright (c) 2007 S. Karger AG, Basel

Genotoxicity in primary human peripheral lymphocytes after exposure to radiopacifiers in vitro

Taking into consideration that DNA damage plays an important role in carcinogenesis, the purpose of this study was to evaluate whether some radiopacifiers widely used in clinical practice are able to induce genetic damage in primary human cells in vitro. Human peripheral lymphocytes obtained from 10 healthy volunteers were exposed to barium sulphate (BaSO(4)), zirconium oxide (ZnO(2)) and bismuth oxide (Bi(2)O(3)) at final concentrations ranging from 1 to 1000 mu g/mL for 1 h at 37 degrees C. The negative control group was treated with vehicle control (phosphate buffer solution) for 1 h at 37 degrees C and the positive control group was treated with hydrogen peroxide (at 100 mu M) for 5 min on ice. Results were analyzed by the Friedman non-parametric test. The results pointed all compounds tested out did not induce DNA breakage in human peripheral lymphocytes as depicted by the mean tail moment and tail intensity in all concentrations tested. In summary, our results indicate that exposure to these radiopacifiers may not be a factor that increases the level of DNA lesions in human peripheral lymphocytes as detected by single cell gel (comet) assay.

Cytotoxic Effects of Different Concentrations of a Carbamide Peroxide Bleaching Gel on Odontoblast-Like Cells MDPC-23

This study evaluated the cytotoxic effects of a carbamide peroxide (CP) bleaching gel at different concentrations on odontoblast-like cells. Immortalized cells of the MDPC-23 cell line (30,000 cells/cm(2)) were incubated for 48 h. The bleaching gel was diluted in DMEM culture medium originating extracts with different CP concentrations. The amount (mu g/mL) of hydrogen peroxide (H(2)O(2)) released from each extract was measured by the leukocrystal violet/horseradish peroxidase enzyme assay. Five groups (n = 10) were formed according to the CP concentration in the extracts: G1-DMEM (control); G2-0.0001 % CP (0.025 mu g/mL H(2)O(2)); G3-0.001% CP (0.43 mu g/mL H(2)O(2)); G4-0.01% CP (2.21 mu g/mL H(2)O(2)); and G5-0.1 % CP (29.74 mu g/mL H(2)O(2)). MDPC-23 cells were exposed to the bleaching gel extracts for 60 min and cell metabolism was evaluated by the NITT assay. Data were analyzed statistically by one-way ANOVA and Tukey's test (alpha = 0.05). Cell morphology was examined by scanning electron microscopy. The percentages of viable cells were as follows: G1, 100%; G2, 89.41%; G3, 82.4%; G4, 61.5%; and G5, 23.0%. G2 and G3 did not differ significantly (p > 0.05) from G1. The most severe cytotoxic effects were observed in G3 and G4. In conclusion, even at low concentrations, the CP gel extracts presented cytotoxic effects. This cytotoxicity was dose-dependent, and the 0.1% CP concentration caused the most intense cytopathic effects to the MDPC-23 cells. (C) 2009 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater 9013: 907-912, 2009

Fracture strength of incisor crowns after intracoronal bleaching with sodium percarbonate

Objectives: To compare the fracture resistance of bovine teeth after intracoronal bleaching with sodium percarbonate (SPC) or sodium perborate (SP) mixed with water or 20% hydrogen peroxide (HP). Materials and methods: Fifty extracted bovine teeth were divided into four experimental groups (G1G4) and one control (n = 10) after endodontic treatment. Following root canal obturation, a glass ionomer barrier was placed at the cementoenamel junction. After that, the pulp chambers were filled with: G1 SP with water; G2 SP with 20% HP; G3 SPC with water; and G4 SPC with 20% HP. No bleaching agent was used in the control group. Coronal access cavities were sealed with glass ionomer and specimens were immersed in artificial saliva. The bleaching agents were replaced after 7 days, and teeth were kept in artificial saliva for an additional 7 days, after which the pastes were removed and the coronal access cavities were restored with glass ionomer. Crowns were subjected to compressive load at a cross head speed of 0.5 mm min-1 applied at 135 degrees to the long axis of the root by an EMIC DL2000 testing machine, until coronal fracture. Data were statistically analysed by anova and Tukey test. Results: No differences in fracture resistance were observed between the experimental groups (P > 0.05). However, all experimental groups presented lower fracture resistance than the control group (P < 0.05). Conclusion: SPC and SP led to equal reduction on fracture resistance of dental crowns, regardless of being mixed with water or 20% HP.