Structural, Spectroscopic (NMR, IR, and Raman), and DFT Investigation of the Self-Assembled Nanostructure of Pravastatin-LDH (Layered Double Hydroxides) Systems

Layered double hydroxide (LDH) nanocontainers, suitable as carriers for anionic drugs, were intercalated with Pravastatin drug using magnesium-aluminum and zinc-aluminum in a M-II/Al molar ratio equal 2 and different Al3+/Pravastatin molar ratios. Postsynthesis treatments were used in order to increase the materials crystallinity. Hybrid materials were characterized by a set of physical chemical techniques: chemical elemental analysis, X-ray diffraction (XRD), mass coupled thermal analyses, vibrational infrared and Raman spectroscopies, and solid-state C-13 nuclear magnetic resonance (NMR). Results were interpreted in light of computational density functional theory (DFT) calculations performed for Sodium Pravastatin in order to assign the data obtained for the LDH intercalated materials. XRD peaks of LDH-Pravastatin material and the one-dimensional (1D) electron density map pointed out to a bilayer arrangement of Pravastatin in the interlayer region, where its associated carboxylate and vicinal hydroxyl groups are close to the positive LDH. The structural organization observed for the stacked assembly containing the unsymmetrical and bulky monoanion Pravastatin and LDH seems to be promoted by a self-assembling process, in which local interactions are maximized and chloride ion cointercalation is required. It is observed a high similarity among vibrational and C-13 NMR spectra of Na-Pravastatin and LDH-Pravastatin materials. Those features indicate that the intercalation preserves the drug structural integrity. Spectroscopic techniques corroborate the nature of the guest species and their arrangement between the inorganic layers. Changes related to carboxylate, alcohol, and olefinic moieties are observed in both vibrational Raman and C-13 NMR spectra after the drug intercalation. Thus, Pravastatin ions are forced to be arranged as head to tail through intermolecular hydrogen bonding between adjacent organic species. The thermal decomposition profile of the hybrid samples is distinct of that one observed for Na-Pravastatin salt, however, with no visible increase in the thermal behavior when the organic anion is sequestrated within LDH gap.

Transformação urbana e vivência termal: caso das Caldas da Rainha

Tese de Doutoramento em Sociologia Urbana, Território e Ambiente

Análise estrutural da deformação cenozóica na Bacia de Cumuruxatiba (BA)

The Cumuruxatiba basin is located at the southern coast State of Bahia in northeastern of Brazil. This basin was formed in distensional context, with rifting and subsequent thermal phase during Neocomian to late Cretaceous. At Cenozoic ages, the Abrolhos magmatism occurs in the basin with peaks during the Paleocene and Eocene. In this period, there was a kinematic inversion in the basin represented by folds related to reverse faults. Structural restoration of regional 2D seismic sections revealed that most of the deformation was concentrated at the beginning of the Cenozoic time with the peak at the Lower Eocene. The post-Eocene is marked by a decrease of strain rate to the present. The 3D structural modeling revealed a fold belt (trending EW to NE-SW) accommodating the deformation between the Royal Charlotte and Sulphur Minerva volcanic highs. The volcanic eruptions have caused a differential overburden on the borders of the basin. This acted as the trigger for halokinesis, as demonstrated by physical modeling in literature. Consequently, the deformation tends to be higher in the edges of the basin. The volcanic rocks occur mainly as concordant structures (sills) in the syn-tectonic sediment deposition showing a concomitant deformation. The isopach maps and diagrams of axis orientation of deformation revealed that most of the folds were activated and reactivated at different times during the Cenozoic. The folds exhibit diverse kinematic patterns over time as response to behavior of adjacent volcanic highs. These interpretations allied with information on the petroleum system of the basin are important in mapping the prospects for hydrocarbons

Ecologia termal da jararaca-ilhoa, Bothrops insularis (Serpentes, Viperidae): um estudo em condições naturais

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Vestuário de proteção, materiais têxteis e conforto térmico: uma análise com aplicadores de agrotóxico, EPI e ambiente agrícola

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Análise da percepção da variação do campo térmico na cidade de São Paulo-SP: o exemplo da subprefeitura Sé

This research aimed to analyze the spatial area for the design of the Heat Island of Subprefecture Sé, in São Paulo-SP, with the support of geotecnology and based on the study of environmental perception. We used remote sensing products such as maps ofland use and soil temperature and apparent surface to evaluate the thermal conditions considered critical points in the central area of the municipality. The methodology used was qualitative analysis, based on interviews with the people, allowing rescue geoecology the conditioning aspects of the city, with an emphasis on environmental perception. This study aimed toanalyze the perception of the variation of the thermal field in São Paulo. The results indicated that (95%) of respondents feel that the temperature of the central area has increased each year, and the district that stood out was the Sé, due to intense use and occupation of land and contribute one of the largest shopping centers. Districts with points given for having better thermal comfort were Santa Cecília, the República and Bela Vista, due to their larger amount of green areas by fiscal court, which act as local refrigerators. It was found that the respondents have the perception and awareness of their spa directly related to the quality of life. Through analysis of several variables involved, proposals and strategies may support public policies and urban planning

O USO DE GEOTECNOLOGIAS NA ANÁLISE DAS MUDANÇAS CLIMÁTICAS NAS METROPOLE DE SÃO PAULO

O rápido crescimento demográfico nas grandes cidades gera conseqüências em zonas que geralmente não estão preparadas para a brusca ampliação. Em um espaço intensamente ocupado e sem planejamento proliferam problemas que comprometem profundamente a qualidade de vida da população.  A análise e diagnóstico da Região Metropolitana de São Paulo (RMSP) é delineada com base na utilização de sistemas de geoprocessamento (SIG) e produtos de sensoriamento remoto. A análise envolve a descrição quantitativa e qualitativa dos diversos eixos temáticos (vegetação, recursos hídricos, uso e ocupação do solo e clima urbano) visando o estudo do clima urbano e sua relação com a qualidade ambiental. Um banco de dados de atributos espaciais integrou as técnicas de geoprocessamento através do uso de imagens de alta resolução. O eixo temático clima urbano contemplará o uso de séries temporais de imagens do TM e ETM+/LANDSAT no infravermelho termal para a identificação da configuração das ilhas de calor. A análise de dióxido de carbono será realizada com a distribuição espacial da intensidade de tráfego urbano de São Paulo, bem como através de dados das Instituições Ambientais e o produto final pode contribuir no subsídio às políticas públicas locais.

Aplicação do escore MELD em pacientes submetidos a transplante de fígado: análise retrospectiva da sobrevida e dos fatores preditivos a curto e longo prazo

BACKGROUND: The model for end-stage liver disease (MELD) was developed to predict short-term mortality in patients with cirrhosis. There are few reports studying the correlation between MELD and long-term posttransplantation survival. AIM: To assess the value of pretransplant MELD in the prediction of posttransplant survival. METHODS: The adult patients (age >18 years) who underwent liver transplantation were examined in a retrospective longitudinal cohort of patients, through the prospective data base. We excluded acute liver failure, retransplantation and reduced or split-livers. The liver donors were evaluated according to: age, sex, weight, creatinine, bilirubin, sodium, aspartate aminotransferase, personal antecedents, brain death cause, steatosis, expanded criteria donor number and index donor risk. The recipients' data were: sex, age, weight, chronic hepatic disease, Child-Turcotte-Pugh points, pretransplant and initial MELD score, pretransplant creatinine clearance, sodium, cold and warm ischemia times, hospital length of stay, blood requirements, and alanine aminotransferase (ALT >1,000 UI/L = liver dysfunction). The Kaplan-Meier method with the log-rank test was used for the univariable analyses of posttransplant patient survival. For the multivariable analyses the Cox proportional hazard regression method with the stepwise procedure was used with stratifying sodium and MELD as variables. ROC curve was used to define area under the curve for MELD and Child-Turcotte-Pugh. RESULTS: A total of 232 patients with 10 years follow up were available. The MELD cutoff was 20 and Child-Turcotte-Pugh cutoff was 11.5. For MELD score > 20, the risk factors for death were: red cell requirements, liver dysfunction and donor's sodium. For the patients with hyponatremia the risk factors were: negative delta-MELD score, red cell requirements, liver dysfunction and donor's sodium. The regression univariated analyses came up with the following risk factors for death: score MELD > 25, blood requirements, recipient creatinine clearance pretransplant and age donor >50. After stepwise analyses, only red cell requirement was predictive. Patients with MELD score < 25 had a 68.86%, 50,44% and 41,50% chance for 1, 5 and 10-year survival and > 25 were 39.13%, 29.81% and 22.36% respectively. Patients without hyponatremia were 65.16%, 50.28% and 41,98% and with hyponatremia 44.44%, 34.28% and 28.57% respectively. Patients with IDR > 1.7 showed 53.7%, 27.71% and 13.85% and index donor risk <1.7 was 63.62%, 51.4% and 44.08%, respectively. Age donor > 50 years showed 38.4%, 26.21% and 13.1% and age donor <50 years showed 65.58%, 26.21% and 13.1%. Association with delta-MELD score did not show any significant difference. Expanded criteria donors were associated with primary non-function and severe liver dysfunction. Predictive factors for death were blood requirements, hyponatremia, liver dysfunction and donor's sodium. CONCLUSION: In conclusion MELD over 25, recipient's hyponatremia, blood requirements, donor's sodium were associated with poor survival.

Conseqüências da análise incorreta de experimentos blocados

Errors are always present in experimental measurements so, it is important to identify them and understand how they affect the results of experiments. Statistics suggest that the execution of experiments should follow random order, but unfortunately the complete randomization of experiments is not always viable for practical reasons. One possible simplification is blocked experiments within which the levels of certain factors are maintained fixed while the levels of others are randomized. However this has a cost. Although the experimental part is simplified, the statistical analysis becomes more complex.

O estado da arte da cromatografia associada à espectrometria de massas acoplada à espectrometria de massas na análise de compostos tóxicos em alimentos

Chromatography combined with several different detection systems is one of the more used and better performing analytical tools. Chromatography with tandem mass spectrometric detection gives highly selective and sensitive analyses and permits obtaining structural information about the analites and about their molar masses. Due to these characteristics, this analytical technique is very efficient when used to detect substances at trace levels in complex matrices. In this paper we review instrumental and technical aspects of chromatography-tandem mass spectrometry and the state of the art of the technique as it is applied to analysis of toxic substances in food.

Validação e estimativa da incerteza de método para análise de licopeno e β-caroteno em polpa de tomate por cromatografia líquida de alta eficiência

A method to quantify lycopene and β-carotene in freeze dried tomato pulp by high performance liquid chromatography (HLPC) was validated according to the criteria of selectivity, sensitivity, precision and accuracy, and uncertainty estimation of measurement was determined with data obtained in the validation. The validated method presented is selective in terms of analysis, and it had a good precision and accuracy. Detection limit for lycopene and β-carotene was 4.2 and 0.23 mg 100 g-1, respectively. The estimation of expanded uncertainty (K = 2) for lycopene was 104 ± 21 mg 100 g-1 and for β-carotene was 6.4 ± 1.5 mg 100 g-1.

Experimento didático de quimiometria para análise exploratória de óleos vegetais comestíveis por espectroscopia no infravermelho médio e análise de componentes principais: um tutorial, parte I

This manuscript aims to show the basic concepts and practical application of Principal Component Analysis (PCA) as a tutorial, using Matlab or Octave computing environment for beginners, undergraduate and graduate students. As a practical example it is shown the exploratory analysis of edible vegetable oils by mid infrared spectroscopy.

Análise do investimento em climatização para bovinos de leite em sistema de alojamento free-stall

The difficulty in adapting European dairy cows breeds in Brazil affect considerably the milk production sector. Brazilian climatic conditions are not totally favorable and the development of new tecnologies is needed for the animals express their genetic potential, as well as their best feed conversion. An economical analysis of the applied investment in the free-stall climatization equipment in dairy housing, for estimating studies related to profit, possibility of return investment as well as time for this return is necessary. The objective of this research was to evaluate the influence of climatization investment in the milk production process and analyze the economical aspect of this investment. There were used 470 high productive dairy cows with genetic and morphologic homogeneous characteristics, and analyzed in two similar periods. Investment calculations were done using Excell®. The results were satisfactory and the invested capital was proved to return to the producer in a short term, 57 days.

Modelo de programação quadrática para análise da movimentação logística e comercialização da soja brasileira

The purpose of this work was to analyze the logistical distribution of Brazilian soybean by applying a quadratic programming to a spatial equilibrium model. The soybean transportation system is an important part of the soybean complex in Brazil, since the major part of the costs of this commodity derives from the transportation costs. Therefore, the optimization of this part of the process is essential to a better competitiveness of the Brazilian soybean in the international market. The Brazilian soybean complex have been increasing its agricultural share in the total of the exportation value in the last ten years, but due to other countries' investments the Brazilian exportations cannot be only focused on increasing its production but it still have to be more efficient. This way, a model was reached which can project new frames by switching the transportation costs and conduce the policy makers to new investments in the sector.