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

Análise de desempenho de um fogão solar construído a partir de sucatas de antena de tv

Given the growing environmental crisis caused by degradation, mainly due to the use of polluting energy sources, increasing the growing use of renewable energies worldwide, with emphasis on solar energy, an abundant supply and available to everyone, which can be harnessed in several ways: electricity generation; dehydration of food; heating, disinfection and distillation and cooking. The latter has as its primary feature the viability of clean, renewable energy for society, combating ecological damage caused by large-scale use of firewood for cooking foods, use in tropical countries with high solar radiation, and has funding NGOs throughout the world with the goal of achieving low-income population. The proposed project consists of a solar cooker for concentration, working from the reflection of sunlight by a hub that they converge to a focal point at the bottom of the pot, getting lots of heat. The solar cooker under study consists of two elliptical reflecting parabolas made from the recycling of scrap TV antenna, having 0.29 m² of surface area for each antenna, which were covered by multiple mirrors of 2 mm thick and mounted on a metal structure, with correction for the mobility of the apparent movement of the sun. This structure was built with the recycling of scrap metal, possessing a relatively low cost compared with other solar cookers, around US$ 50.00. This cost becomes negligible, since that will involve a great benefit to not have fuel costs for each meal, unlike the use of gas or firewood for cooking food. The tests show that the cooker has reached the maximum temperature of 740 ° C, for boiling water in an average time of 28 minutes, cooking various types of foods such as potatoes, rice and pasta in an average time of 45 minutes and still going as a solar oven, making pizza baking and meat. These cooking times do not differ much from the cooking times on a gas stove, it becomes the solar cooker as a good consumer acceptance, and furthermore not to deliver the same gases that can poison the food as with the wood stove. Proves the viability of using the stove to cook or bake in two daily meals for a family, still presenting a position to improve his performance with the addition of new materials, equipment and techniques

Algoritmos de agrupamento aplicados a dados de expressão gênica de câncer: um estudo comparativo

The use of clustering methods for the discovery of cancer subtypes has drawn a great deal of attention in the scientific community. While bioinformaticians have proposed new clustering methods that take advantage of characteristics of the gene expression data, the medical community has a preference for using classic clustering methods. There have been no studies thus far performing a large-scale evaluation of different clustering methods in this context. This work presents the first large-scale analysis of seven different clustering methods and four proximity measures for the analysis of 35 cancer gene expression data sets. Results reveal that the finite mixture of Gaussians, followed closely by k-means, exhibited the best performance in terms of recovering the true structure of the data sets. These methods also exhibited, on average, the smallest difference between the actual number of classes in the data sets and the best number of clusters as indicated by our validation criteria. Furthermore, hierarchical methods, which have been widely used by the medical community, exhibited a poorer recovery performance than that of the other methods evaluated. Moreover, as a stable basis for the assessment and comparison of different clustering methods for cancer gene expression data, this study provides a common group of data sets (benchmark data sets) to be shared among researchers and used for comparisons with new methods

Evolução termocronológica do sistema de falhas Senador Pompeu-CE

The region of the Senador Pompeu Shear Zone (SPSZ), in the North Tectonic Domain of the Borborema Province (BP), has its recent history associated with to South Atlantic Ocean formation event at the Jurassic. A lot of geologics models have discussed about crustal axis elevation in local scale and large scale (Borborema Province), relative to importants regionals tectonics directions of it. The identification and the relationship among this surfaces, stepped in many topographyc levels by tectonics mecanisms, is dificult because of the erosion process on it. Over there, sedimentary deposits is complex and it has not biostratigraphyc record in continental deposits. The analysis metodology on apatita fission-track, in the region of the SPSZ, purpose the more knowledge about morphotectonics mecanisms of the area and the impruvement of its morphotectonics models. For this, it was moleled the age and thermal history of the 11 apatites samples collected on both sides of this shear zone, taking relationships among other results of the thermochronology studies in the BP. Based on the thermal studies in this search, the region of the BP developed on two distint cooling events, separated for one period of relative stabilited. The first episode occur between 130 and 90 M.y., has been began when the samples cross the 120°C isoterm for last time and fineshed at 70°C. The second moment of the cooling process was began about 30 M.y., when the temperature was 90°C, from this to the equlibrium with present surface temperature at 30°C. Some evidences indicated a relacionship between thermal episodes and uplift events of the regional relief. The fundaments of the interpretation was based mainly on comparatives studies among results of the thermochronology analysis and geologics studies about BP. Nóbrega et al.(2005), e.g., on studies about the Portalegre Shear Zone, got similar results on SPSZ, with some details relative to local tectonic activity. Morais Neto et al. (2000) interpreted two importants cooling events in the BP based on their regional studies, that can be associated to regional uplift events. When Assine (1992) studied the stratigraphyc sequences of the Araripe Basin, in the south of Ceará state, conclude that the abrupt return to continentals condictions from the last sedimentar sequency (albiano-cenomaniane) indicate a regional uplift of the NE region of the Brazil at the 100 M.y., in the Albiano Intermediate/Superior. This ages are compatible to termal model of the SPSZ. This two periods of the thermal history of the BP are completely registered in the apatites samples just one age groups of the fission-track, that it is the most ancient age groups. This one suggest it has happened in response to heating before 75 M.y and it has erased the last report of the first moment relief evolution of the BP. The NNE-SSW and E-W structure reativation can have created ideal condictions for heating and local elevations of the geothermal gradients. The equilibrium between the apatites temperatures of this groups and the regionais temperatures took place about 50 M.y., when the samples of the two ages groups had a simillar evolution to present surfaces temperatures