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

Avaliação da biodegradabilidade de petróleo utilizando microrganismos isolados do estuário do Rio Potengi (RN)

The oil activity in the Rio Grande do Norte State (RN) is a permanent threat to coastal ecosystems, particularly mangroves, with the possibility of oil spills. In this context, the objective of this study was to evaluate the potential resistance of the mangrove environment of a possible spill. Were selected and isolated microorganisms degrading oil by the technique of enrichment cultures and formation of a bacterial consortium. The kinetic study of the consortium was held in rotary incubator shaken at 150 rpm and 30° C. Samples were taken at intervals of 4 hours for analysis of cell concentration and surface tension. The biodegradation was monitored using two methods of respirometry: manometric (OxiTop-C ®) and conductivimetry, where the biodegradation of oil was estimated indirectly by oxygen consumption and CO2 production, respectively. Furthermore, it was used a full 2² factorial design with triplicate at central point to the runs that used the conductivimetric methodology.. The technique of enrichment cultures allowed to obtain thirteen bacterial strains. Kinetic study of the consortium, we can showed the absence of the lag phase, reaching a maximum cell concentration of 2.55 g / L at 16 h of cultivation and a reduction on surface tension. When we adopted the methodology of OxiTop-C was detected a band indicating biodegradability (1% oil v/v), however when we used the conductivimetry methodology did not observe any band that would indicate effective biodegradation. By monitoring a process of biodegradation is necessary to observe the methodology will be adopted to evaluate the biodegradation process, since for the same conditions adopted different methodologies can produce different results. The oil-degrading isolates from soils of the mangrove estuary Potengi / RN are largely to be used in bioremediation strategies of these places, in the case of a possible oil spill, or it can be used in the treatment of waste oil generated in saline environments, since they are optimized the conditions of the tests so that the efficiency of biodegradation reach the minimum level suggested by the standarts

Metodologias estatísticas aplicadas a dados de análises químicas da água produzida em um campo maduro de petróleo

Produced water is characterized as one of the most common wastes generated during exploration and production of oil. This work aims to develop methodologies based on comparative statistical processes of hydrogeochemical analysis of production zones in order to minimize types of high-cost interventions to perform identification test fluids - TIF. For the study, 27 samples were collected from five different production zones were measured a total of 50 chemical species. After the chemical analysis was applied the statistical data, using the R Statistical Software, version 2.11.1. Statistical analysis was performed in three steps. In the first stage, the objective was to investigate the behavior of chemical species under study in each area of production through the descriptive graphical analysis. The second step was to identify a function that classify production zones from each sample, using discriminant analysis. In the training stage, the rate of correct classification function of discriminant analysis was 85.19%. The next stage of processing of the data used for Principal Component Analysis, by reducing the number of variables obtained from the linear combination of chemical species, try to improve the discriminant function obtained in the second stage and increase the discrimination power of the data, but the result was not satisfactory. In Profile Analysis curves were obtained for each production area, based on the characteristics of the chemical species present in each zone. With this study it was possible to develop a method using hydrochemistry and statistical analysis that can be used to distinguish the water produced in mature fields of oil, so that it is possible to identify the zone of production that is contributing to the excessive elevation of the water volume.

Desenvolvimento de metodologias analíticas alternativas por cromatografia gasosa para análise de biodiesel

Since the beginning of the National Program for Production and Use of Biodiesel in Brazil, in 2004, different raw materials were evaluated for biodiesel production, trying to combine the agricultural diversity of the country to the desire to reduce production coasts. To determine the chemical composition of biodiesel produced from common vegetables oils, international methods have been used widely in Brazil. However, for analyzing biodiesel samples produced from some alternative raw materials analytical problems have been detected. That was the case of biodiesel from castor oil. Due the need to overcome these problems, new methodologies were developed using different chromatographic columns, standards and quantitative methods. The priority was simplifying the equipment configuration, realizing faster analyses, reducing the costs and facilitating the routine of biodiesel research and production laboratories. For quantifying free glycerin, the ethylene glycol was used in instead of 1,2,4-butanetriol, without loss of quality results. The ethylene glycol is a cheaper and easier standard. For methanol analyses the headspace was not used and the cost of the equipment used was lower. A detailed determination of the esters helped the deeper knowledge of the biodiesel composition. The report of the experiments and conclusions of the research that resulted in the development of alternative methods for quality control of the composition of the biodiesel produced in Brazil, a country with considerable variability of species in agriculture, are the goals of this thesis and are reported in the following pages

Intencionalidades e práticas na construção de metodologias o CEFET-SE

Successive curricular changes that occurred in professional education altered pedagogical practices, and these practices being developed by means of integrating projects, at Centro Federal de Educação Tecnológica de Sergipe (CEFET-SE), between 2001 and 2003, originated some questions which became the study object of this thesis. We search for theoretical support mainly in GEPEM research (GEPEM/UFRN) works and practices in order to analyze elements that emerged from this pedagogical practice. To do so, we take as main reference the research of qualitative approach. We developed documents analysis, interviews, considering three aspects: the scenery where these changes took place, the conception and implementation of the Integrating Projects for what, we ask support in pedagogy of projects studies and principles of interdisciplinary, and contextualization as curriculum structuring elements. This research brought out some difficulties, conflicts and possible consensus in developing the methodological strategies for the Projects. In this process of coexistence of the traditional and the new, of an unavoidable distance between what was thought and what was effectively done, elements for a new pedagogical practice emerged. This could be noticed in terms of participative work, formative moments, teacher s autonomy related to the pedagogical work. A new door could be open to the possibilities of taking conscience of accepting the differences and oneself autoexperimentation. These are the possibilities that make men, not being mere information deposit, can dialog and transform, producing his existence by this means. In the present case, the existence of being teacher, the build himself in the time of possibilities

Comparação entre metodologias de extração de HPAs em água utilizando um planejamento fatorial com quantificação no CG/EM

PAHs (Polycyclic Aromatic Hydrocarbons) are a group of organic substances which receive considerable attention because of the carcinogenic and mutagenic properties of some of them. It is therefore important to determine the PAHs in different environmental matrices. Several studies have shown the use of gas chromatography coupled to mass spectrometry as a technique for quantification of PAHs by presenting excellent detection limits. This study aimed to develop an analytical methodology for the determination of 16 PAHs listed by the USEPA, test two methods for extraction of PAHs in water from a 23 factorial design, quantify them through the analytical technique coupled to gas chromatography mass spectrometry (GC/MS) using the method developed, and finally apply the results in chemometrics. The sample was synthesized and subjected to tests of the 23 factorial design, which has the factors: the type of extraction technique (ultrasound and digester), the ratio solvent / sample (1:1 and 1:3) and the type of solvent (dichloromethane / hexane and acetone / dichloromethane). The responses of eight combinations of the factorial design were obtained from the quantification by external calibration in GC/MS. The quantification method was developed from an optimized adaptation of the USEPA Method 8270. We used the full scan mode as a way of acquiring the mass spectra of 16 PAHs. The time in which the samples were subjected to ultrasound was fixed at 10 min and held an investigation to establish the conditions of power and time in the digester. We had the best response in the investigation of the digester power of 100 watts and the time of six minutes. The factorial design of liquid-liquid extraction showed that the most representative factors were: the use of the digester as extraction technique, the ratio solvent / sample 1:1 and the use of a 1:1 mixture of dichloromethane / hexane as a solvent more suitable. These results showed that the 1:1 mixture of dichloromethane / hexane is an excellent mixture to recover the extraction of PAHs an aqueous sample using the microwave digester. The optimization of the method of separation, identification and quantification of PAHs in the GC/MS was valid for 16 PAHs present in each chromatogram of the samples

Influência de atividades antrópicas sobre a salinização da água em área de dunas no Município de Guamaré RN

The municipality of Guamaré is located on the north coast of RN, Salineira zone, with a land area of 259 km2 and a population of approximately 12,500 inhabitants (IBGE, 2010). Presents strong morphological instability caused mainly by the influence of human activities in the region. The present study aims to assess the existing levels of salts in the springs of the region, by evaluating the electrical conductivity, pH, salinity, chlorides, hardness, calcium, magnesium and heavy metals in the water. The collection and analysis methods adopted in the survey are based on APHA (2005). The electrical conductivity, salinity and chloride behaved similarly throughout the study. Some points suffered the direct effect of the salt ponds and others. Given the existence of a drainage ditch between the saline and monitored region, there was little change in the environment, including the native vegetation. The opposite situation occurred in farms where the region is fully committed local vegetation and water holes and wells used in the past for domestic use are practically disabled (high salt content). In Rio Miassaba formation of an estuary is reversed, with the farther out from the sea showing higher salt concentracions, which may be associated with the discharge of organic matter and natural evaporation rate. In periods of no rainfall had a few points higher than the levels of salts found in seawater and may be associated with high evaporation in the region. Detected a positive factor is the high resilience and reducing salt, after periods of rainfall incidence

Otimização de metodologias para determinação de hidrocarbonetos policíclicos aromáticos:aplicação em água do Rio Potengi

This work aims to detect polycyclic aromatic hydrocarbons (PAHs) through optimized analytical techniques, such as gas chromatography with flame-ionisation detector (CGFID), gas chromatography coupled to mass spectrometry (CGMS), Fluorescence Spectroscopy of Molecular and Purpot of oils and greases (POG). Apply to chemometrics, Factorial Planning 23, in the preparation of samples by liquid-liquid extraction. The sample preparation was used for liquid-liquid extraction and factors in this sample was used for the application of factorial planning 23, such as the use of ultrasound, solvents (dichloromethane, hexane and chloroform) and ratio of solvent / synthetic sample. These factors were assigned two types of levels: positive and negative. It was used to form the cube to better analyze the answers. The responses of the eight combinations were obtained in reading the spectrofluorimetric. The optimization of equipment were used, and they served in the HPA's identification of the samples collected in Rio Potengi. The optimization of the equipment was observed every 16's and PAH in the samples was found that the HPA's came from contamination of the Rio Potengi. The contamination comes through organic household waste, hospital waste, and among other contamination that comes from industries that are installed around the River The factorial design of high validity, it was observed a more effective sample preparation. The factorial design of liquid-liquid extraction showed a way to spend less solvent in less time using an ideal solvent, but also a way to extract more analyte from the matrix itself is water. In planning a smaller form factor extraction was the use of ultrasound, the ratio 1:3 corresponding to a solvent and sample 3 and the best solvent was dichloromethane who presented a viable extraction, not discarding the possibility of using also the hexane. The chloroform and may be toxic not had a good extraction

AVALIAÇÃO DE DUAS METODOLOGIAS DE EXPANSÃO AO FORNO do POLVILHO AZEDO

Duas metodologias de expansão ao forno foram comparadas em 52 amostras de polvilho azedo de três Estados: Santa Catarina, Paraná e Minas Gerais. Os resultados obtidos permitiram visualizar uma proposta de classificação em nível nacional da expansão ao forno do polvilho azedo. No método instrumental foi usado o Farinógrafo Brabender para estabelecer uma massa de consistência padrão de 60UF e no método prático, a consistência semelhante da massa foi determinada de forma empírica. Com a metodologia instrumental obteve-se biscoitos com expansão superior à metodologia prática, mas maior coeficiente de variação, o que pode ser devido a maior sensibilidade do método. Ambas as metodologias poderão ter aplicação, dependendo da finalidade. A metodologia instrumental, pelo custo do equipamento, é mais adequada para laboratórios, desde que se utilize maior número de repetições, para reduzir o coeficiente de variação. Ambas as metodologias ensaiadas permitiram classificar as amostras com o mesmo perfil de desempenho. As amostras provenientes do Estado do Paraná apresentaram as maiores expansões ao forno quando comparados com os outros Estados. Pela metodologia prática a expansão média das amostras do Estado do Paraná foi de 14,1mL/g. As amostras do Estado de Minas Gerais apresentaram as menores expansões ao forno, em média de 13,3mL/g. Foi proposta neste artigo uma classificação para avaliar a qualidade do polvilho azedo, complementando a legislação brasileira que não estabelece este índice para o produto. Quanto à propriedade de expansão ao forno, as amostras avaliadas podem ser divididas em 3 tipos A, B e C. No tipo A (10%) amostras de polvilhos azedo são classificadas como qualidade extra, no tipo B (80%) os polvilhos são de média qualidade e o tipo C (10%) de qualidade inferior. Os resultados obtidos pela metodologia prática permitiram estabelecer como tipo A o polvilho azedo que apresenta um índice de expansão ao forno superior a 16,0mL/g, o tipo B o polvilho com índice de expansão entre 12,0mL/g a 16,0mL/g e o tipo C o polvilho com índice de expansão menor que 12,0mL/g.

Avaliação das Sub-Frações dos Carboidratos e das Proteinas, Usando as Metodologias do Cncps e In situ com Bovinos da Raça Nelore. 1. Silagem de Milho

To validate the use of the Cornell Net Carbohydrate and Protein System (CNCPS) under Brazilian conditions, the chemical composition, the potential and the effective degradabilities of the carbohydrate and protein subfractions, and the solid phase passage rate were determined for corn silage in diets with forage:concentrate ratios of 80:20 (DI) and 60:40 (D2) using Nellore cattle. The chromium mordant technique was used to determine the particulate passage rate of solids. For diet 2, there was a reduction in the potentially degradable dry matter (DM), and however not significant, a reduction in the degradation rates of neutral detergent Fiber (NDF, 49%) and neutral detergent insoluble nitrogen (NDIN, 32%), and an increase in the degradation rare of starch (ST, 25%). The use of lag time increased the effective DM degradation (EDDM) of corn silage in both diets (23% and 53% for D1 and D2, respectively). The concentrate ratios did not influence the particulate passage rate of the diets. The higher values related ro the availability of the protein subfractions may indicate a underestimation by CNCPS, Rnd(or) could be attributed to the Zebu animals used in this study.

Avaliação das Sub-Frações dos Carboidratos e das Proteínas, Usando as Metodologias do Cncps e In situ com Bovinos da Raça Nelore. 2. Milho e Farelo de Algodão

The chemical composition of corn and cottonseed meal was determined in accordance with the Cornell Net Carbohydrate and Protein System (CNCPS) in diets with forage:concentrate ratios of 80:20 (D1) and 60:40(D2) using Nellore cattle. The potential and effective degradabilities of the carbohydrate and protein subfractions were also determined. For corn. diet 2 resulted in an increase for potentially degradable dry matter (DM). An increase was observed in the effective degradation of DM (EDDM) when lag time was not considered, however, the use of Eng time increased the EDDM for both diets, 23 and 18% for DI and D2. respectively. For cottonseed meal, diet 2 determined a reduction in the potentially degradable DM: therefore, the use of lag time increased the EDDM for bath diets, 14% for D1 and 15% for D2. The availability of corn starch (fraction B1) was lower than that determined by CNCPS. The higher values for the degradability of corn and cottonseed meal protein subfractions may indicate an underestimation by the model, and, or, could be attributed to the Zebu animals used in this study.

Desempenho das metodologias convencionais de quantificacao de reservas<>9d\estudo de um deposito de niquel

Ten working-groups were formed for estimation of nickel ore reserves, associated to an ultrabasic body, at Ipanema, MG. Each group employed six methods: parallel sections, isolines, triangles, polygons, blocks and statistical method. The triangles method showed more variability, and the smallest dispersion was obtained by the polygons method; the other methods induced fluctuations in relation to the mean. Top and bottom ore irregularities produced difficulties in the performance of the parallel sections method. Different ways of application of isolines method also produced some variations. Excepting for few calculated data, the overall results are very close to 2 200 000 t or ore. -English summary

Extração de feições rodoviárias em imagens digitais: Metodologias desenvolvidas pelo GP-F&VC

Several kinds of research in road extraction have been carried out in the last 6 years by the Photogrammetry and Computer Vision Research Group (GPF&VC - Grupo de Pesquisa em Fotogrametria e Visão Computacional). Several semi-automatic road extraction methodologies have been developed, including sequential and optimizatin techniques. The GP-F&VC has also been developing fully automatic methodologies for road extraction. This paper presents an overview of the GP-F&VC research in road extraction from digital images, along with examples of results obtained by the developed methodologies.