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

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

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

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.

Violência, mídia e juventude: análise sobre o discurso adotado pelo jornalismo impresso sobre a realidade violenta de jovens da periferia da cidade do Natal

The work that follows has as its main objective the analysis of the discourse of media, with emphasis on newspapers printed on acts and events involving young offenders. The speech adopted by columnists of newspapers, based on formulas and journalistic practices exist, allows the reader a view of what happened in detail. But this wealth of information, contradictorily, it seems not permit, much less to encourage reflection on the what is being read. All information contained in narrative journalism seem to point to the establishment of maintenance of speech reinante of violence and repression against young offenders, from, and generally in the vast majority of cases, from poor neighborhoods and suburbs of large cities. The whole range of such important issues directly related to violence committed by these young people does not appear, does not appear in the text journalism. Words such as "marginal", "square" reinforce prejudices, stigmas against the youth, putting the company on constant alert against such "criminals", "malandros." The result of the survey was partial, but can conclude about the importance of the media against those social phenomena that amedrontam the society at present

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

Guiando almas femininas: a educação protestante da mulher em impressos confessionais no Brasil e em Portugal (1890-1930)

This paper treats confessional printings as a non formal space for the female education. It reflects on the importance of the woman s role to the diffusion of Protestantism in general, and its Presbyterian trend in particular, besides commenting on the proliferation of printings at the First Republic and its relation with education. In this study, Brazilian Northeastern is seen as a relevant space to the diffusion of Protestantism in Brazil; especially on what concerns the relations between Rio Grande do Norte and Pernambuco. Thereby some fountains were fundamental, as the confessional printings, that is, newspapers, magazines, prospects and other materials recollected in archives located in Natal/RN and Recife/PE, and São Paulo. It was also provided a brief incursion on Portuguese confessional printings kept in Oporto, PT. New Cultural History was chosen as theoretic-methodological guide, franchising ways inside the history of book and reading with the help of concepts like Interdependence, Social Configuration (ELIAS, 1993, 1994) and Representation (CHARTIER, 1990), considering that the survey worked out culture-manufactured products that is, intentional materials. It is well known that publishing, or better, the dissemination of printed material used to be associated to Protestants missionary practices since Reform began and, as what concerns the investigated period, in Portuguese and Brazilian lands indistinctly. Printing material in general books, booklets, fragments, as well as the press itself played a central role in divulging reformed ideas, their social options and the means of being and intervening in the world. In this regard, the confessional printings established themselves as an educative, although non schooled, informal space, but, all considered, relevant, seen that they dialogue with another important demand of that social group: formal, literate education. Because it dealt with the diffusion of a printed culture supported by the written word, it required of that group a different modus operandi: formal education. The first letters schools at first, then the high schools later represented spaces established for the circulation of printing material in order that they should be read, divulged and comprehended. This survey intends at last to take a look at Protestantism which, in this context of self-affirmation, reserved a specific place to woman by working out a non formal educational proposal disseminated by printing material. Three models were highlighted in the reformed proposal: Christian education in itself, household education, whose references of motherhood and care towards the neighbor were present and, at last, education to the public space, with emphasis on the practice of teaching. This study also offers a brief dialogue between Brazil and Portugal because, when some periodic printing, book or something like that got to be published in one margin of the Atlantic Ocean, the other margin surely was affected by that feat, received it, divulged it, corroborating the argument in support of the circulation of these printings. It was not only the same language that survived in both maritime coasts; some protestant specificities also crossed out along that sea

Materiais corretivos e nitrogênio na nutrição e na produção de matéria seca de cana-de-açúcar cultivada em vaso

Silicon is a beneficial element that can increase the yield of sugarcane, especially when associated with nitrogen. The aim of this study was to evaluate the effects of silicate slag as a source of Si and its interaction with soil N on nutrition and dry matter production of sugar cane. The treatments consisted of two sources of correctives (limestone and silicate slag) in three doses (one half, once and twice the dose shown to increase V to 60%), two N rates (300 e 600mg.dm(-3)) administered as urea, a control (without corrective and without N), arranged in a completely randomized factorial design 2x3x2+1, with four replicates. Each experimental unit was constituted by a 40dm(3) pot filled with an Oxisol (V= 10% and Si= 10.3mg.dm(-3)), and 4 seedlings (SP79-1011). The nutritional status (Si and N) was evaluated 10 months after planting the sugarcane, as well as the Si content of the soil and shoot dry matter The application of silicate slag increased the content of available Si in soil and the plant. The application of corrective materials improved the nutrition and dry matter production of sugarcane. Nitrogen fertilization was not significant for dry matter production of the sugarcane-plant, regardless of the source of corrective material.

Desenvolvimento de antenas de microfita com Patch em anel utilizando materiais ferrimagnéticos e metamateriais

In general, the materials used as substrates in the project of microstrip antennas are: isotropic, anisotropic dielectrics and ferrimagnetic materials (magnetic anisotropy). The use of ferrimagnetic materials as substrates in microstrip patch antennas has been concentrated on the analysis of antennas with circular and rectangular patches. However, a new class of materials, called metamaterials, has been currently the focus of a great deal of interest. These materials exhibit bianisotropic characteristics, with permittivity and permeability tensors. The main objective of this work is to develop a theoretical and numerical analysis for the radiation characteristics of annular ring microstrip antennas, using ferrites and metamaterials as substrates. The full wave analysis is performed in the Hankel transform domain through the application of the Hertz vector potentials. Considering the definition of the Hertz potentials and imposing the boundary conditions, the dyadic Green s function components are obtained relating the surface current density components at the plane of the patch to the electric field tangential components. Then, Galerkin s method is used to obtain a system of matrix equations, whose solution gives the antenna resonant frequency. From this modeling, it is possible to obtain numerical results for the resonant frequency, radiation pattern, return loss, and antenna bandwidth as a function of the annular ring physical parameters, for different configurations and substrates. The theoretical analysis was developed for annular ring microstrip antennas on a double ferrimagnetic/isotropic dielectric substrate or metamaterial/isotropic dielectric substrate. Also, the analysis for annular ring microstrip antennas on a single ferrimagnetic or metamaterial layer and for suspended antennas can be performed as particular cases

Desenvolvimento de antenas de microfita e antenas DRA Broadband

The search for ever smaller device and without loss of performance has been increasingly investigated by researchers involving applied electromagnetics. Antennas using ceramics materials with a high dielectric constant, whether acting as a substract element of patch radiating or as the radiant element are in evidence in current research, that due to the numerous advantages offered, such as: low profile, ability to reduce the its dimensions when compared to other devices, high efficiency of ratiation, suitability the microwave range and/or millimeter wave, low temperature coefficient and low cost. The reason for this high efficiency is that the dielectric losses of ceramics are very low when compared to commercially materials sold used in printed circuit boards, such as fiberglass and phenolite. These characteristics make ceramic devices suitable for operation in the microwave band. Combining the design of patch antennas and/or dielectric resonator antenna (DRA) to certain materials and the method of synthesis of these powders in the manufacture of devices, it s possible choose a material with a dielectric constant appropriate for the design of an antenna with the desired size. The main aim of this work is the design of patch antennas and DRA antennas on synthesis of ceramic powders (synthesis by combustion and polymeric precursors - Pe- chini method) nanostructured with applications in the microwave band. The conventional method of mix oxides was also used to obtain nanometric powders for the preparation of tablets and dielectric resonators. The devices manufactured and studied on high dielectric constant materials make them good candidates to have their small size compared to other devices operating at the same frequency band. The structures analyzed are excited by three different techniques: i) microstrip line, ii) aperture coupling and iii) inductive coupling. The efficiency of these techniques have been investigated experimentally and compared with simulations by Ansoft HFSS, used in the accurate analysis of the electromagnetic behavior of antennas over the finite element method (FEM). In this thesis a literature study on the theory of microstrip antennas and DRA antenna is performed. The same study is performed about the materials and methods of synthesis of ceramic powders, which are used in the manufacture of tablets and dielectric cylinders that make up the devices investigated. The dielectric media which were used to support the analysis of the DRA and/or patch antennas are analyzed using accurate simulations using the finite difference time domain (FDTD) based on the relative electrical permittivity (er) and loss tangent of these means (tand). This work also presents a study on artificial neural networks, showing the network architecture used and their characteristics, as well as the training algorithms that were used in training and modeling some parameters associated with the devices investigated

Materiais supercondutores HTS para arranjos de antenas e aplicação de PBG para micro-ondas

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior

Antenas planares multicamadas com materiais supercondutores e fotônico para comunicações móveis

Recently, planar antennas have been studied due to their characteristics as well as the advantages that they offers when compared with another types of antennas. In the mobile communications area, the need for this kind of antennas have became each time bigger due to the intense increase of the mobile communications this sector. That needs of antennas which operate in multifrequency and wide bandwidth. The microstrip antennas presents narrow bandwidth due the loss in the dielectric generated by radiation. Another limitation is the radiation pattern degradation due the generation of surface waves in the substrate. In this work some used techniques to minimize the disadvantages (previously mentioned) of the use of microstrip antennas are presented, those are: substrates with PBG material - Photonic Bandgap, multilayer antennas and with stacked patches. The developed analysis in this work used the TTL - Transverse Transmission Line method in the domain of Fourier transform, that uses a component of propagation in the y direction (transverse to the direction real of propagation z), treating the general equations of electric and magnetic field as functions of Ey and Hy. One of the advantages of this method is the simplification of the field equations. therefore the amount of equations lesser must the fields in directions x and z be in function of components Ey and Hy. It will be presented an brief study of the main theories that explain the superconductivity phenomenon. The BCS theory. London Equations and Two Fluids model will be the theories that will give support the application of the superconductors in the microfita antennas. The inclusion of the superconductor patch is made using the resistive complex contour condition. This work has as objective the application of the TTL method to microstrip structures with single and multilayers of rectangular patches, to obtaining the resonance frequency and radiation pattern of each structure

Avaliação de diferentes materiais no ensacamento de pêssegos

O trabalho foi realizado em um pomar comercial de pêssego da cultivar Aurora 2, de três anos de idade, conduzida em sistema de vaso moderno e espaçamento de 6 x 4 m. O delineamento experimental foi em blocos casualizados, utilizando-se de 15 tratamentos, 8 repetições e 16 frutos por tratamento. Os tratamentos foram os seguintes: T1 - Sacolas de TNT branco de 45 gramaturas por m² (45G/m², fechado; T2 - Sacolas de TNT branco de 45 gramaturas por m² (45G/m²) aberto; T3 - Sacolas de TNT branco de 20 gramaturas por m² (20G/m²) fechado; T4 - Sacolas de TNT branco de 20 gramaturas por m² (20G/m²) aberto; T5 - Sacolas de polipropileno microperfurado transparente (furos de 1mm) fechado; T6 - Sacolas de polipropileno microperfurado transparente (furos de 1mm) aberto; T7 - Sacolas de polipropileno microperfurado transparente (furos de 2mm) fechado; T8 - Sacolas de polipropileno microperfurado transparente (furos de 2mm) aberto; T9 - Sacolas de polietileno microperfurado leitoso (furos de 1mm) fechado; T10 Sacolas de polietileno microperfurado leitoso (furos de 1mm) aberto; T11 Sacolas de polietileno microperfurado leitoso (furos de 2mm) fechado; T12 - Sacolas de polietileno microperfurado leitoso (furos de 2mm) aberto; T13 - Sacolas de papel impermeável fechado; T14 - Sacolas de papel impermeável aberto; T15 - Testemunha (sem ensacamento). As sacolas de TNT (Tecido-não-Tecido) e as de papel impermeável tinham as dimensões de 11,5 x 15,0 cm, e as de polipropileno microperfurado, de 13,0 x 20,0 cm. Os resultados obtidos permitiram concluir que as embalagens de polipropileno transparentes podem ser empregadas para o ensacamento de frutos de pessegueiro, uma vez que as mesmas possibilitam a visualização da coloração dos frutos no momento da colheita, não comprometem o desenvolvimento da coloração dos mesmos e apresentam facilidade no manuseio.

Viabilidades térmica, econômica e de materiais de um sistema solar de aquecimento de água a baixo custo para fins residenciais

An solar alternative system for water heating is presented. Is composed for one low cost alternative collector and alternative thermal reservoir for hot water storing. The collector of the system has box confectioned in composite material and use absorption coils formed for PVC tubes. The box of hot water storage was confectioned from a plastic polyethylene drum used for storage of water and garbage, coated for a cylinder confectioned in fiber glass. The principle of functioning of the system is the same of the conventionally. Its regimen of work is the thermosiphon for a volume of 250 liters water. The main characteristic of the system in considered study is its low cost, allowing a bigger socialization of the use of solar energy. It will be demonstrated the viabilities thermal, economic and of materials of the system of considered heating, and its competitiveness in relation to the available collectors commercially. Relative aspects will be boarded also the susceptibility the thermal degradation and for UV for the PVC tubes. It will be shown that such system of alternative heating, that has as main characteristic its low cost, presents viabilities thermal, economic and of materials