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

Prevalência e fatores associados a lesões labiais e periorais decorrentes da exposição solar em trabalhadores de praia

This study aimed to verify the prevalence of lip and perioral lesions in worker who were under sunshine on the beaches of Natal/RN and to investigate possible associations of these with sociodemographic, occupational and general health variables. For this, 362 individuals who had one of the urban beaches (Ponta Negra / Environment / Redinha) in the city of Natal/RN as a working environment in the study. We excluded people under 18 years old. Data collection was done through epidemiological analysis and extra-oral validated questionnaire with questions that characterize socioeconomic and demographic factors, occupational exposure and general health. The male subjects (72.6%) were the majority in the sample. The people who worked directly exposed to high peaks of ultraviolet radiation, as well as informal workers predominated. Considering the total sample of individuals, ephelides in the perioral region (33.7%) and labial region (24.0%), solar lentigo perioral (15.2%) and actinic cheilitis (13.8%) stood out as the most prevalent lesions. Indoor workers and those who had a habit occurrence of injuries by 19% and 21% respectively higher when compared to outdoor workers and people without habits. The variable use of cap / hat was associated with the presence of cold sores (Qui2 = 1,328, p = 0,058). On the threshold of significance, the type of work was also associated with lesions in lip occurrence (p = 0,042). Men showed a lower incidence of perioral lesions when compared to female workers (PR=0,716, p valor = 0,002). The present study showed high prevalence of lip and perioral lesions. The premalignant lesions were the most identified, both as in lip skin. It is important therefore to be encouraged to adopt protective measures against excessive sun exposure, fairly and consistently