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

Simulação de desempenho luminoso para salas de aula em Natal-RN

The city of Natal has a significant daylight availability, although it use isn’t systematically explored in schools architecture. In this context, this research aims to determine procedures for the analysis of the daylight performance in school design in Natal-RN. The method of analysis is divided in Visible Sky Factor (VSF), simulating and analyzing the results. The annual variation of the daylight behavior requires the adoption of dynamic simulation as data procedure. The classrooms were modelled in SketchUp, simulated in Daysim program and the results were assessed by means of spreadsheets in Microsoft Excel. The classrooms dimensions are 7.20mx 7.20m, with windows-to-wall-ratio (WWR) of 20%, 40% and 50%, and with different shading devices, such as standard horizontal overhang, sloped overhang, standard horizontal overhang with side view protection, standard horizontal overhang with a dropped edge, standard horizontal overhang with three horizontal louvers, double standard horizontal overhang, double standard horizontal overhang with three horizontal louvers, plus the use of shelf light in half the models with WWR of 40% and 50%. The data was organized in spreadsheets, with two intervals of UDI: between 300lux and 2000 lux and between 300lux and 3000lux. The simulation was performed with the weather file of 2009 to the city of NatalRN. The graphical outputs are illuminance curves, isolines of UDI among 300lux and 2000 lux and tables with index of occurrences of glare and to an UDI among 300lux 3000lux. The best UDI300-2000lux performance was evidenced to: Phase 1 (models with WWR of 20%), Phase 2 (models with WWR of 40% and 50% with light shelf). The best UDI300-3000lux performance was evidenced to: Phase 1 (models with WWR of 20% and 40% with light shelf) and Phase 2 (models with WWR of 40% and 50% with light shelf). The outputs prove that the daylight quality mainly depends on the shading system efficacy to avoid the glare occurrence, which determines the daylight discomfort. The bioclimatic recommendations of big openings with partial shading (with an opening with direct sunlight) resulted in illuminances level higher than the acceptable upper threshold. The improvement of the shading system percentage (from 73% to 91%) in medium-size of openings (WWR 40% and 50%) reduced or eliminate the glare occurrence without compromising the daylight zone depth (7.20m). The passive zone was determined for classrooms with satisfactory daylight performance, it was calculated the daylight zone depth rule-of-thumb with the ratio between daylight zone depth and the height of the window for different size of openings. The ratio ranged from 1.54 to 2.57 for WWR of 20%, 40% and 50% respectively. There was a reduction or elimination of glare in the passive area with light shelf, or with awning window shading.

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

Cálculos AB initio de propriedades estruturais, eletrônicas e ópticas de colmpostos CaXo3 (X=Si, Ge, Sn)

In this work we present a study of structural, electronic and optical properties, at ambient conditions, of CaSiO3, CaGeO3 and CaSnO3 crystals, all of them a member of Ca-perovskite class. To each one, we have performed density functional theory ab initio calculations within LDA and GGA approximations of the structural parameters, geometry optimization, unit cell volume, density, angles and interatomic length, band structure, carriers effective masses, total and partial density of states, dielectric function, refractive index, optical absorption, reflectivity, optical conductivity and loss function. A result comparative procedure was done between LDA and GGA calculations, a exception to CaSiO3 where only LDA calculation was performed, due high computational cost that its low symmetry crystalline structure imposed. The Ca-perovskite bibliography have shown the absence of electronic structure calculations about this materials, justifying the present work