Síntese enzimática de ésteres de açúcar: surfactantes e polímeros como novos materiais ambientalmente seguros

Sugar esters are substances which possess surfactant, antifungical and bactericidal actions and can be obtained through two renewable sources of raw materials: sugars and vegetable oils. Their excellent biodegradability, allied to lhe fact that they are non toxic, insipid, inodorous, biocompatible, no-ionic, digestible and because they can resist to adverse conditions of temperature, pH and salinity, explain lhe crescent use of these substances in several sections of lhe industry. The objective of this thesis was to synthesize and characterize surfactants and polymers containing sugar branched in their structures, through enzymatic transesterification of vinyl esters and sugars, using alkaline protease from Bacillus subtilis as catalyst, in organic medium (DMF).Three types of sugars were used: L-arabinose, D-glucose and sucrose and two types of vinyl esters: vinyl laurate and vinyl adipate. Aiming to reach high conversions from substrates to products for a possible future large scale industrial production, a serie of variables was optimized, through Design of Experiments (DOE), using Response Surface Methodology (RSM).The investigated variables were: (1) enzyme concentration; (2) molar reason of substrates; (3) water/solvent rale; (4) temperature and (5) time. We obtained six distinct sugar esters: 5-0-lauroyl L-arabinose, 6-0-lauroyl D-glucose, 1'-O-lauroyl sucrose, 5-0-vinyladipoyl L-arabinose, 6-0-vinyladipoyl D-glucose and 1 '-O-vinyladipoyl sucrose, being lhe last three polymerizable. The progress of lhe reaction was monitored by HPLC analysis, through lhe decrease of sugar concentration in comparison to lhe blank. Qualitative analysis by TLC confirmed lhe formation of lhe products. In lhe purification step, two methodologies were adopted: (1) chromatographic column and (2) extraction with hot acetone. The acylation position and lhe chemical structure were determined by 13C-RMN. The polymerization of lhe three vinyl sugar esters was possible, through chemical catalysis, using H2O2 and K2S2O8 as initiators, at 60°C, for 24 hours. IR spectra of lhe monomers and respective polymers were compared revealing lhe disappearance of lhe vinyl group in lhe polymer spectra. The molar weights of lhe polymers were determined by GPC and presented lhe following results: poly (5-0-vinyladipoyl L-arabinose): Mw = 7.2 X 104; PD = 2.48; poly (6-0-vinyladipoyl D-glucose): Mw = 2.7 X 103; PD = 1.75 and poly (1'-O-vinyladipoyl sucrose): Mw = 4.2 X 104; PD = 6.57. The six sugar esters were submitted to superficial tension tests for determination of the critical micelle concentrations (CMC), which varied from 122 to 167 ppm. Finally, a study of applicability of these sugar esters, as lubricants for completion fluids of petroleum wells was' accomplished through comparative analysis of lhe efficiency of these sugar esters, in relation to three commercial lubricants. The products synthesized in this thesis presented equivalent or superior action to lhe tested commercial products

Influência da substituição de areia natural por pó de pedra no comportamento mecânico, microestrutural e eletroquímico de concretos

The construction industry is one of the largest consumers of natural raw materials, and concrete is considered today the most used material wide. This accentuated consumption of natural resources has generated concern with the preservation of the environment, and has motivated various studies related to the use of resid ues, which can partially or entirely substitute, with satisfactory performance, some materials such as the aggregate, and in so doing, decrease the impact on the environment caused by the produced residues. Research has been done to better understand and improve the microstructure of concrete, as well as to understand the mechanism of corrosion in reinforced steel. In this context, this work was developed aiming at discovering the influence of the substitution of natural sand by artificial sand, with rega rd to mechanical resistance, microstructure, and durability. To obtain the electrochemical parameters, an adaptation was made to the galvanostatic electrochemical method to study the corrosion in reinforced steel. Concretes of categories 20 MPa and 40 MPa were produced, containing natural sand, and concretes of the same categories were produced with artificial sand substituting the natural sand, and with the addition of sodium nitrate and sodium chloride. Due to the use of rock dust reject (artificial sand), an evaluation was made of its environmental risk. The results indicate that the concretes of category 20 MPa present a better performance than the concrete made with natural sand, thus making it a viable substitute. For the category 40 MPa, the better performance is from the concrete containing natural sand. The adaptation of the galvanostatic electrochemical technique to the study of the corrosion of reinforced steel within concrete proved to be valid for obtaining electrochemical parameters with a high degree of reliability, considering the number of degrees of freedom

Avaliação da corrosão em dutos por técnica gravimétrica e de resistência elétrica

With the increasing of demand for natural gas and the consequent growth of the pipeline networks, besides the importance of transport and transfer of oil products by pipeline, and when it comes to product quality and integrity of the pipeline there is an important role regarding to the monitoring internal corrosion of the pipe. This study aims to assess corrosion in three pipeline that operate with different products, using gravimetric techniques and electrical resistance. Chemical analysis of residues originated in the pipeline helps to identify the mechanism corrosive process. The internal monitoring of the corrosion in the pipelines was carried out between 2009 and 2010 using coupon weight loss and electrical resistance probe. Physico-chemical techniques of diffraction and fluorescence X-rays were used to characterize the products of corrosion of the pipelines. The corrosion rate by weight loss was analyzed for every pipeline, only those ones that has revealed corrosive attack were analyzed located corrosion rate. The corrosion potential was classified as low to pipeline gas and ranged from low to severe for oil pipelines and the pipeline derivatives. Corrosion products were identified as iron carbonate, iron oxide and iron sulfide

Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc

Degradacao termica e catalitica da borra oleosa de Petroleo com materiais nanoestruturados al-mcm-41 e AL-SBA-15

Aiming to reduce and reuse waste oil from oily sludge generated in large volumes by the oil industry, types of nanostructured materials Al-MCM-41 and Al-SBA-15, with ratios of Si / Al = 50, were synthesized , and calcined solids used as catalysts in the degradation of oily sludge thermocatalytic oil from oilfield Canto do Amaro, in the state of Rio Grande do Norte. Samples of nanostructured materials were characterized by thermogravimetric analysis (TG / DTG), X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared Fourier transform (FT-IR) and adsorption nitrogen (BET). The characterization showed that the synthesized materials resulted in a catalyst nanostructure, and ordered pore diameter and surface area according to existing literature. The oily sludge sample was characterized by determining the API gravity and sulfur content and SARA analysis (saturates, aromatics, resins and asphaltenes). The results showed a material equivalent to the average oil with API gravity of 26.1, a low sulfur content and considerable amount of resins and asphaltenes, presented above in the literature. The thermal and catalytic degradation of the oily sludge oil was performed from room temperature to 870 ° C in the ratios of heating of 5, 10 and 20 ° C min-1. The curves generated by TG / DTG showed a more accelerated degradation of oily sludge when it introduced the nanostructured materials. These results were confirmed by activation energy calculated by the method of Flynn-Wall, in the presence of catalysts reduced energy, in particular in the range of cracking, showing the process efficiency, mainly for extraction of lightweight materials of composition of oily sludge, such as diesel and gasoline

Aplicação de técnicas eletroquímicas na determinação do potencial de corrosividade de ligas de alumínio em água produzida

The resistance of aluminum and their alloys, to the corrosion phenomenon, in aqueous solutions, is a result of the oxide layer formed. However, the corrosion process in the aluminum alloy is associated with the presence a second phase of particles or the presence of chloride ions which promote the disruption of the oxide layer located producing the corrosion process. On the other hand, the term water produced is used to describe the water after the separation of the oil and gas in API separators. The volumes of produced water arrive around 5 more times to the volume of oil produced. The greatest feature of the water is the presence of numerous pollutants. Due to the increased volume of waste around the world in the current decade, the outcome and the effect of the discharge of produced water on the environment has recently become an important issue of environmental concern where numerous treatments are aimed at reducing these contaminants before disposal. Then, this study aims to investigate the electrochemical corrosion behavior of aluminum alloy 6060 in presence of water produced and the influence of organic components as well as chloride ions, by using the electrochemical techniques of linear polarization. The modification of the passive layer and the likely breakpoints were observed by atomic force microscopy (AFM). In the pit formation potential around -0.4 to -0.8 V/EAg/AgCl was observed that the diffusion of chloride ions occurs via the layer formed with the probable formation of pits. Whereas, at temperatures above 65 °C, it was observed that the range of potential for thepit formation was -0.4 to -0.5 V/EAg/AgCl. In all reactions, the concentration of Al(OH)3 in the form of a gel was observed

Efetividade do flúor e da escovação e eficácia dos materiais de colagem ionômero de vidro e resina composta na reversão das microporosidades criadas pelo condicionamento ácido no esmalte dentário

The objectives of this clinical study was to evaluate the use of the toothpaste with fluoride and without fluoride and the daily tooth brushing are effective in the reversion of the dental enamel conditioned by acid. Another objective of this clinical study was to evaluate if the positioning of orthodontic accessories with glass ionomer cement helps in the reversion of the dental enamel conditioned by acid, when compared to composed resin. One hundred and twenty teeth were selected with indication of extraction by orthodontic reasons. The 30 volunteers were divided, randomly, in two groups. A group used toothpaste without fluoride and the other with it. The teeth of the sample were shuffled, in each volunteer. The teeth were conditioned by the 37% orthophosphoric acid. One of the conditioned teeth stayed in the mouth and suffered action of the abrasion for the tooth brushing, in another teeth a stainless steel mesh protection was positioned with glass ionomer cement, in another tooth the screen was glued with composed resin, in a fourth tooth (the control) was only conditioned after the extractions, 60 days later. All the teeth were appraised through DIAGNOdent, MEVA and EDS. In the obtained data it was possible to observe that there were not statistic significant differences in any comparison, even in the group that did not have access to the fluoride in the toothpaste as in the other that had. According with the used methodology, it was possible to observe too that there was not statistic significant differences in any comparison, even in the group that had the stainless steel mesh positioned with glass ionomer cement as in the group that the stainless steel mesh was positioned with composed resin. However, it was observed that there was an improvement in the topography of the enamel in all the teeth. The accomplishment of this study was facilitated due to the participation of the researchers' of the health area (dentistry), materials engineer, physics and chemistry. The researchers were originating from the Federal University of Rio Grande do Norte and of the University of Queensland, in Australia. This interdisciplinary group was decisive in the accomplishment of the study. It can be concluded that the enamel tends to return to its initial aspect, even if the patient does not have access to fluoride. That is probably due the action of the abrasion for the tooth brushing and mastication. In spite of it not being significant, it is suggested that the conditioned enamel was more resistant to the abrasion in the group that had access to fluoride. It was also possible to conclude that the fluoride liberated by the glass ionomer was not enough to provide a significant difference in the enamel conditioned by the acid, when compared with the composed resin, even in the group that did not use fluoride in the toothpaste as in the group that used

Desenvolvimento de Sistemas Microparticulados Superparamagnéticos Gastro-resistentes para Diagnóstico e Terapêutica

This work aimed to develop a suitable magnetic system for administration by the oral route. In addition to that, it was intended to review the current uses of magnetic systems and the safety related to magnetic field exposure. Methods: Coprecipitation and emulsification/crosslinking were carried out in order to synthesize magnetite particles and to coat them, respectively. Results: According to literature review, it was found that magnetic particles present several properties such as magnetophoresis in magnetic field gradient, production of a surrounding magnetic field, and heat generation in alternated magnetic field. When the human organism is exposed to magnetic fields, several interaction mechanisms come into play. However, biological tissues present low magnetic susceptibility. As a result, the effects are not so remarkable. Concerning the development of a magnetic system for oral route, uncoated magnetite particles did undergo significant dissolution at gastric pH. On the other hand, such process was inhibited in the xylan-coated particles. Conclusions: Due to their different properties, magnetic systems have been widely used in biosciences. However, the consequent increased human exposure to magnetic fields has been considered relatively safe. Concerning the experimental work, it was developed a polymer-coated magnetic system. It may be very promising for administration by the oral route for therapy and diagnostic applications as dissolution at gastric pH hardly took place

Caracterização fenotípica e genotípica de Staphylococcus aureus resistentes à meticilina isolados na cidade do Natal/RN

Staphylococcus aureus resistente à meticilina (MRSA) é um dos principais agentes de infecções associadas a serviços de saúde em todo o mundo. No Brasil, há a predominância de um clone de MRSA multirresistente denominando clone epidêmico brasileiro (CEB). Entretanto, novos clones nãomultirresistentes com alta virulência têm sido descritos em infecções comunitárias e hospitalares. O objetivo desse estudo foi realizar a caracterização fenotípica e genotípica de cepas de MRSA isoladas na cidade do Natal/RN. Inicialmente avaliamos 60 amostras de S. aureus quanto a resistência à meticilina através de diferentes técnicas fenotípicas, utilizando a detecção do gene mecA por PCR como padrão. O antibiograma de todas as cepas foi realizado utilizando 12 antimicrobianos conforme descrito pelo CLSI. As cepas de MRSA foram caracterizadas geneticamente através da tipagem do cassete cromossômico estafilocócico mec (SCCmec) e da eletroforese em campo elétrico alternado (PFGE). Dos 60 S. aureus estudados, 45 foram resistentes à meticilina. Observamos que para algumas cepas de MRSA os testes de triagem em ágar com 6μg/mL de oxacilina e difusão em meio sólido com oxacilina-1μg apresentaram dificuldades na sua interpretação. No entanto, todas as 45 amostras de MRSA, foram facilmente detectadas pelos testes com o disco de cefoxitina-30μg e pesquisa da PBP2a. A análise molecular das cepas de MRSA mostrou 8 padrões distintos de PFGE (A-H), com predominância do padrão A (73%), relacionado ao CEB. Estas carreavam o SCCmec tipo IIIA, e apresentaram uma considerável variedade de subtipos (A1-A16). Cinco cepas de MRSA portando SCCmec IV também foram xiv identificadas, três delas relacionadas geneticamente ao clone USA800 (Padrão B). Destas cinco, três (2 padrão F e 1 padrão B) foram altamente susceptíveis as drogas testadas, entretanto, dois outros isolados, padrão B, apresentaram multirresistência. As amostras restantes pertenciam a padrões de PFGE distintos dos clones internacionais predominantes em nosso continente. Para realização deste projeto de pesquisa, a metodologia exigiu a interação com pesquisadores de áreas como: infectologia, microbiologia e biologia molecular. Portanto, esta dissertação apresentou um caráter de multidisciplinaridade e transdiciplinaridade no seu desenvolvimento

Coeficientes de difusão de metais em materiais não convencionais (agarose e acetato de celulose) usados na técnica de difusão em filmes finos por gradientes de concentração

The DGT technique allows one to measure quantitatively free and labile metal species in aquatic systems. Nevertheless, for this approach, knowledge is required of the diffusion coefficients of the analytes in a diffusive layer. In this study, the diffusion coefficients of Hg(II), As(III), Mn(II), Mg(II), Cu(II), Cd(II) were determined in agarose gel and those of Ba(II), Cd(II), Cu(II), Mg(II), Mn(II) e Zn(II) in cellulose acetate membranes. These materials presented good performance and the reported results can be used as a data base for further DGT studies.

Controle químico de biótipos de buva (Conyza canadensis e Conyza bonariensis) resistentes ao glyphosate

Studies were conducted at Estacao Experimental de Citricultura de Bebedouro, SP to evaluate the response of glyphosate-resistant horseweed and hairy fleabane biotypes to herbicides glyphosate, bromacil + diuron, diuron e paraquat isolated and in mixture and effect of a sequential application of glyphosate. The experimental design was of complete randomized blocks with four replication and seven treatments. The herbicides were applied with costal sprayer, constant pressure with three nozzles TT110015, the equivalent spray volume was 150 L ha(-1). The control was visually evaluated, trough percentile note scale. The best results were obtained to general control of weed with diuron isolated and glyphosate in mixture with bromacil + diuron while to glyphosate-resistant horseweed and hairy fleabane there was no difference between the treatments. After sequential application to Conyza sp control, the best treatment was obtained associated with diuron and bromacil+diuron.

Preferência alimentar de Dione juno juno (Cramer) por genótipos de maracujazeiro e avaliação do uso de extratos aquosos

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Limites formais e materiais ao controle de constitucionalidade pelo Supremo Tribunal Federal

This document approaches the formal and material limits of the constitucionalidade control for the Supreme Federal Court, iniating with the study of the Constitution, detaching its evolution, nature and meanings, passing for its historical evolution, offering still a unconstitutionality concept. Is work the principles as material Constitution, making the distinction entere principles and rules, detaching the characteristics of the principles constitutional, and the basic principle of the Constituition. It analyzes metodologics the historical parameters and of the brazilian system of constitutionality control and detaches the paper of the Supreme Federal Court as positive legislator. It observes the beddings of the constitutionality control and the legitimacy of the Supreme Federal Court. Is examines the performance of the Supreme Federal Court in face of the principle of the legal security. Is offers a vision on the experience of the control of constitutionality in other constries. It still approaches the control of constitutionality in Brazil, detaching the critical points of its formal and material limits. Is verifies the application of the principles constitutional for the Supreme Federal Court in the diffuse control and the intent control of constitutionality, as well as the performance of the Supreme Federal Court ahead of the unconstitutional omissions. It brings to the debate the new perspectives how much to the formal and material limits of the control of constitutionality for the Supreme Federal Court. Objective to elaborate considerations concerning the limits of the constitutional jurisdiction from the model of Constituition, the character politican of the difficulties with respect to the definition of its formal and material limits from the performance of the Supreme Federal Court

Seleção de porta-enxertos resistentes ao cancro da haste e seus efeitos na produtividade de melão 'Bônus nº 2'

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

Estudo de métodos de inoculação para a avaliação de cultivares de soja a Fusarium tucumaniae

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