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

Implementação paralela escalável e eficiente do algoritmo simplex padrão em arquitetura multicore

This work presents a scalable and efficient parallel implementation of the Standard Simplex algorithm in the multicore architecture to solve large scale linear programming problems. We present a general scheme explaining how each step of the standard Simplex algorithm was parallelized, indicating some important points of the parallel implementation. Performance analysis were conducted by comparing the sequential time using the Simplex tableau and the Simplex of the CPLEXR IBM. The experiments were executed on a shared memory machine with 24 cores. The scalability analysis was performed with problems of different dimensions, finding evidence that our parallel standard Simplex algorithm has a better parallel efficiency for problems with more variables than constraints. In comparison with CPLEXR , the proposed parallel algorithm achieved a efficiency of up to 16 times better

Estudo da viabilidade da destilação solar para polimento de águas produzidas de petróleo

This work study of solar distillation feasibility in effluent of petroleum industry: produced water, making possible your reuse for irrigation of oleaginous cultures or fodder crops or in steam generation, as well the transport phenomena involved. The methodology for development of this project was to characterize the effluent to be treated and to accomplish physical and chemical analysis in the distilled, to build distillation equipment, concomitant operation of both equipments and implementation of data processing and economical evaluation. The methodology used for all parameters is outlined in APHA (1998) and sampling of the type compound. The feeding of distillation equipment was performed with treated effluent from UTPF of Guamaré. The temperature was monitored throughout the distillers and during the time of operation. The distillers feed occur, as a rule, for sifon. The distillers were operated by a period of 17 months between July 2007 and February 2009, in which 40 experiments were performed. The radiation and temperature datas were acquired in the INPE s site and the temperature inside of the distillers was registered by DATALOGGER Novus. The rates of condensation (mL / min) were determined by measuring of the flow in a graduate test tube of 10 mL and a chronometer. We used two simple solar effect distillers of passive type with different angles in coverage: 20 ° and 45 °. The results obtained in this study and the relevant discussions are divided into six topics: sample characterization and quality of distilled; construction of distillers; operation (data, temperature profile), climatic aspects, treatment of data and economical analysis. Results obtained can be inferred that: the energy loss by the adoption of vessel glass was not significant, however, complicates the logistics of maintenance the equipment on a large scale. In the other hand, the surface of the tub with a glass shield on the equipment deterioration, both devices showed similar performance, so there is not justified for use of equipment 450. With regard to the climatological study it was verified that the Natal city presents monthly medium radiation varying in a range between 350 and 600 W/m2, and medium of wind speed of 5 m / s. The medium humidity is around 70% and rainfall is very small. The regime of the system is transient and although it has been treated as a stationary system shows that the model accurately represents the distillers system's 20 degrees. The quality of the distilled with regard to the parameters evaluated in this study is consistent with the Class 3 waters of CONAMA (Resolution 357). Therefore we can conclude that solar distillation has viability for treat oilfield produced water when considered the technical and environmental aspects, although it is not economically viable

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