Transformações químicas, caracterizações e estudo de modelagem molecular do clerodano bioativo trans-desidrocrotonina

In this work it were developed synthetic and theoretical studies for clerodane-type diterpenes obtained from Croton cajucara Benth which represents one of the most important medicinal plant of the Brazil amazon region. Specifically, the majoritary biocompound 19-nor-clerodane trans-dehydrocrotonin (t-DCTN) isolated from the bark of this Croton, was used as target molecule. Semi-synthetic derivatives were obtained from t-DCTN by using the followed synthetic procedures: 1) catalytic reduction with H2, 2) reduction using NaBH4 and 3) reduction using NaBH4/CeCl3. The semi-synthetic 19-nor-furan-clerodane alcohol-type derivatives were denominated such as t-CTN, tCTN-OL, t-CTN-OL, t-DCTN-OL, t-DCTN-OL, being all of them characterized by NMR. The furan-clerodane alcohol derivatives t-CTN-OL and tCTN-OL were obtained form the semi-synthetic t-CTN, which can be isolated from the bark of C. cajucara. A theoretical protocol (DFT/B3LYP) involving the prevision of geometric and magnetic properties such as bond length and angles, as well as chemical shifts and coupling constants, were developed for the target t-DCTN in which was correlated NMR theoretical data with structural data, with satisfactory correlation with NMR experimental data (coefficients ranging from 0.97 and 0.99) and X-ray diffraction data. This theoretical methodology was also validated for all semi-synthetic derivatives described in this work. In addition, topological data from the Quantum Theory of Atoms in Molecules (QTAIM) showed the presence of H-H and (C)O--H(C) intramolecular stabilized interactions types for t-DCTN e t-CTN, contributing to the understanding of the different reactivity of this clerodanes in the presence of NaBH4.

Características físico-químicas, sensoriais e perfil de ácidos graxos do leite de cabras saanen alimentadas com cactáceas

The objective of this research was to evaluate the influence of the supply of five types of native and exotic cacti Brazilian semiarid northeast on the sensory characteristics of milk of Saanen goats. Five multiparous goats were used with nine weeks of lactation, average live weight of 50 kg ± 4 kg., confined and distributed in a Latin square design 5 x 5 with five experimental diets and five periods. Each period lasted 17 days, with 10 days of adaptation to the diets of the animals and seven days for the data collection. The treatments were defined based on dry matter consisted of: 47.33 to 50.12% of a cactus (“Xiquexique”, “Mandacaru”, “Facheiro” or two species of forage cactus “Miúda” or “Orelha de Elefante Mexicana”) more 18.78 to 19.79% hay of plant “Sabiá” and 31.10 to 32.89% of concentrate. There was not effect of the experimental diets in the physical and chemical composition of milk for fat, total solids and salts, which showed mean values of 3.24%; 11.30% and 0.66%, respectively. However the protein, lactose, nonfat dry extract and freezing point were affected by diets. In the profile of fatty acids was higher concentration of fatty short and medium chain fatty acids, however, there were not changes between treatments, except for the butyric acid (C4:0), with mean values of 4.24% (“Orelha de Elefante Mexicana”) to 6.05% (“Facheiro”). The diets also did not provide sensory changes in milk for the parameters: odor, flavor, aftertaste and overall assessment. The use of the five cactus in the diet of dairy goats do not influence the sensory characteristics and lipid profile of milk. The physical and chemical composition of milk was showed within the minimum requirements of current legislation, except for nonfat dry extract and freezing point.

Síntese e caracterização de catalisadores baseados em vermiculita modificada com ferro: aplicação em processos do tipo foto-fenton

Clays are materials with specific properties that make them promising for various studies. In this work we used the vermiculite clay as support for iron compounds, in order to obtain promising materials for application in the heterogeneous type photo-Fenton process. In all, the study included six solid, starting from the vermiculite (V0) was obtained calcined vermiculite (V0-C), the mixed material (V0/β-FeOOH) formed by vermiculite more akaganeite, exchanged vermiculite (v0t-C), vermiculite impregnated Wet (V0u-C) and V0u-CL that is the solid obtained by impregnating with a back washing. The solids of the study had their physical and chemical characteristics investigated by the following characterization techniques: X-Ray Diffraction (XRD), Infrared Spectroscopy (IR), Energy Dispersive Spectroscopy (EDS), X-Ray Fluorescence Spectroscopy (XRF), UV-Vis by Diffuse Reflectance (DR UV-Vis), Thermogravimetric Analysis (TGA) and Scanning Electron Microscopy (SEM). The V0 material showed three distinct phases, which are the very vermiculite, hidrobiotite and biotite, the last two phases are part of the geological of formation process vermiculite. The solids obtained after the modification showed an increase in the amount of iron present in the clay, these being quantities important for application in photocatalysis. The micrographs and EDS data, show that after treatment of addition of the metal , the iron was intercalary in structure of vermiculite for solid V0t-C and V0u-C, however, this did not occur with mixed material. In the photoFenton process, was observed a maximum removal of 88.8% of the dye methylene blue coloring for the catalyst V0/β-FeOOH, while for the other solids was obtained values between 76.8 and 62.6%, compared to 37.8% of discoloration without the presence of catalyst. Therefore, it is concluded that the vermiculite clay presents as a good catalyst and iron support for the, beyond of presenting a low cost because of its high abundance.

Polpa de jambolão (Eugenia jambolana Lam.) fresca e desidratada: características físico-químicas, bioativas e funcionais, efeitos biológicos em Caenorhabditis elegans e uso para produção de frozen yogurt caprino probiótico

This work evaluated the fresh, spray dried (with 10 % of Arabic Gum) and freeze dried jambolan pulp (Eugenia jambolana Lam.) in regard to physicochemical (pH, moisture, water activity, average particle diameter, solubility and color), bioactive [total phenolic content (TPC), monomeric anthocyanin, pronathocyanidin (PA), total elagic acid (TEA), myricetin and cyanidin] and in vitro functionality (antioxidant, antienzymatic and antimicrobial activities]. In addition, the in vivo functionality of jambolan pulp was investigated using the Caenorhabditis elegans model for insulin signaling, longevity and induced neurodegeneration (Alzheimer’s disease and Parkinson’s disease related symptoms). The dried jambolan pulp presented TPC retention (50% to 75%), PA (90% to 98%), TEA (31% to 83%), myricetin (40% to 84%), cyanidin (72% to 84%) and antioxidant activity (15%). The fresh jambolan pulp, the freeze dried pulp and the spray dried jambolan pulp presented high enzymatic inhibitory activity against pancreatic lipase (4,4 to 5,8 mg/mL), alpha-glycosidase (10,3 to 13,8 mg/mL) and alpha-amylase (8,9 to 11,2 mg/mL). They also were active inhibitors against the pathogen S. aureus. The dried jambolan experimental samples were able to increase the expression of several genes linked to the insulin signaling pathways (SIR-2.1, PPTR-1, DAF-16, SOD-3, e CTL) and increased the lifespan in C. elegans (18,07 % - 24,34 %), besides decreasing the amyloid AB1-42 aggregation induced paralysis and MPP+ (1-methyl-4-phenylpyridinium) induced neurodegeneration. Based on that, the jambolan pulp and the spray dried jambolan pulp were further selected for the production of caprine frozen yogurt with the addition of Bifidobacterium animalis subsp. lactis BI-07. The final product were evaluated in regard to their physicochemical (pH, acidity, total solids, protein, total reducing sugars, fat, ashes, overrun, melting test), bioactive (TPC and monomeric anthocyanin, antioxidant activity, probiotic viability and sensory analysis (sensory acceptance). The results showed that samples with probiotic had lowest pH and higher acidity, TPC, anthocyanin and antioxidant activity. It was also observed low overrun (14.2% to 22.6%). vi Samples with probiotic had lower flavor scores. Overall, this research presents the jambolan as a highly functional bioactive-rich fruit with the potential to modulate important biological pathways, extend lifespan and retard the development of neurodegenerative diseases. Jambolan is an underexploited exotic fruit with a high colorant potential and this thesis shows for the first time in the literature important technological, biological and scientific data about this fruit that could be used towards the development of health-oriented food products.

Avaliação tribológica de novas modificações superficiais para cilindros de laminação a frio

The present work analyzed the tribological behavior of coatings/surface modifications traditionally used in cold rolling mill rolls and new coatings/surface modificationswith potential to replace the carcinogenic hard chrome. The study started with identification of wear mechanisms occurring in real coldrollingmill rolls. Due the high cost and dimensions of the rolls, thereplication technique was used. Replicas were obtained from 4 different rolling millBrazilian companies before and after a normal rolling campaign. Initial sliding tests were conducted using spherical and cylindrical counter bodies in order to verifywhichtribological conditions allowed to reproduce the wear mechanisms found in the replicas. These tests indicated the use of reciprocating sliding tests with cylindrical counter bodies (line contact), normal load of 100 N, and test times of and 1 h and 5 h. Different surface modifications were carried out on samples produced from a fragment of a rolling mill roll. The specimens were heat treated and ground on both sides. After, some specimens were surface textured by electrical discharge texturing (EDT). For both groups (ground and EDT), subsequent treatments of chromium plating, electroless NiP coating and plasma nitriding were carried out. The results of the reciprocating tests showed that specimens with electroless NiP coating presented the lowest friction coefficients, while plasma nitrided specimens showed the highest. In general, previous surface texturing before the coating/surface modification increased the wear of the counter bodies. Oneexceptionwas for EDT with subsequent electroless NiP coating, which presented the lowest counter bodies wear rate. The samples withelectroless NiP coating promoted a tribolayer consisting of Nickel, Phosphorus and Oxygen on both the specimens andthecounter bodies, which was apparently responsible for the reduction of friction coefficient and wear rate. The increase of the test time reduced the wear rate of the samples, apparently due the stability of the tribolayers formed, except for the nitrided samples. For the textured specimens, NiP coating showed the best performance in maintaining the surface topography of the specimens after the sliding tests.

O Ensino de ligações químicas por meio do conceito de energia: uma proposta didática para o ensino médio

This work presents discussions on the teaching of Chemical Bonds in high school and some implications of this approach in learning chemistry by students. In general, understanding how the chemicals combine to form substances and compounds, it is a key point for understanding the properties of substances and their structure. In this sense, the chemical bonds represent an extremely important issue, and their knowledge is essential for a better understanding of the changes occurring in our world. Despite these findings, it is observed that the way in which this concept is discussed in chemistry class has contributed, paradoxically, to the emergence of several alternative designs, making the understanding of the subject by students. It is believed that one of the explanations for these observations is the exclusive use of the "octet rule" as an explanatory model for the Chemical Bonds. The use of such a model over time eventually replace chemical principles that gave rise to it, transforming knowledge into a series of uninteresting rituals and even confusing for students. Based on these findings, it is deemed necessary a reformulation in the way to approach this content in the classroom, taking into account especially the fact that the explanations of the formation of substances should be based on the energy concept, which is fundamental to understanding how atoms combine. Thus, the main question of the survey and described here of the following question: Can the development of an explanatory model for the Chemical Bonds in high school based on the concept of energy and without the need to use the "octet rule"? Based on the concepts and methodologies of modeling activity, we sought the development of a teaching model was made through Teaching Units designed to give subsidies to high school teachers to address the chemical bonds through the concept of energy. Through this work it is intended to make the process of teaching and learning of Chemical Bonds content becomes more meaningful to students, developing models that contribute to the learning of this and hence other basic fundamentals of chemistry.

O Ensino de ligações químicas por meio do conceito de energia: uma proposta didática para o ensino médio

This work presents discussions on the teaching of Chemical Bonds in high school and some implications of this approach in learning chemistry by students. In general, understanding how the chemicals combine to form substances and compounds, it is a key point for understanding the properties of substances and their structure. In this sense, the chemical bonds represent an extremely important issue, and their knowledge is essential for a better understanding of the changes occurring in our world. Despite these findings, it is observed that the way in which this concept is discussed in chemistry class has contributed, paradoxically, to the emergence of several alternative designs, making the understanding of the subject by students. It is believed that one of the explanations for these observations is the exclusive use of the "octet rule" as an explanatory model for the Chemical Bonds. The use of such a model over time eventually replace chemical principles that gave rise to it, transforming knowledge into a series of uninteresting rituals and even confusing for students. Based on these findings, it is deemed necessary a reformulation in the way to approach this content in the classroom, taking into account especially the fact that the explanations of the formation of substances should be based on the energy concept, which is fundamental to understanding how atoms combine. Thus, the main question of the survey and described here of the following question: Can the development of an explanatory model for the Chemical Bonds in high school based on the concept of energy and without the need to use the "octet rule"? Based on the concepts and methodologies of modeling activity, we sought the development of a teaching model was made through Teaching Units designed to give subsidies to high school teachers to address the chemical bonds through the concept of energy. Through this work it is intended to make the process of teaching and learning of Chemical Bonds content becomes more meaningful to students, developing models that contribute to the learning of this and hence other basic fundamentals of chemistry.

Assessment of metals contamination (Cd, Pb, Ni) at the Óbidos Lagoon using Cerastoderma edule as a biomonitoring tool

A poluição marinha é um problema ambiental Mundial que afeta as constituintes bióticas e abióticas do Ecossistema. Os resultados de diversas atividades antropogénicas chegam ao meio marinho através de escorrências terrestres, industriais e agrícolas assim como através de descargas domésticas, causando distúrbios neste Ecossistema. Sendo assim, a avaliação da contaminação por metais é uma das prioridades tendo em conta que estes químicos têm comportamentos acumulativos e podem ser transportados ao longo de grandes distâncias. Nos estuários, os bivalves são componentes chaves das comunidades macrobentónicas devido o seu papel vital na comunidade e também por serem uma ótima fonte de alimentação para os seres Humanos. Na Lagoa de Óbidos, uma das espécies com estas características e intensamente apanhada é o berbigão Cerastoderma edule. Este berbigão foi descrito por vários autores como sendo tolerante a diversos poluentes. Sendo assim, no presente estudo, o principal objetivo foi utilizar C. edule como ferramenta de biomonitorização de contaminações por metais na Lagoa de Óbidos, avaliando a contaminação por Cádmio, Chumbo e Níquel durante as estações do ano de 2009 e 2010 em duas estações de amostragens (estação ML e BSB). Os resultados foram complementados com a análise de contaminações por metais em amostras de águas e sedimentos. Diversas respostas fisiológicas do berbigão foram também averiguadas de modo a perceber os efeitos da presença de metais e sua acumulação. Finalmente, avaliou-se a Dose Semanal Admissível Provisória (DSAP) para o consumo de berbigão para os mínimos e máximos de concentrações de metais detetados em cada estação de amostragem. Todos os metais foram detetados em amostras de água enquanto apenas o Pb foi detetado no sedimento. O Pb e o Ni foram detetados mais vezes na amostras biológicas do que o Cd. No entanto, as contaminações por metais Pb e Cd no berbigão foram frequentemente acima do limiar fixado pelas autoridades responsáveis enquanto o Ni se encontrou perto dos valores legislados. A avaliação da DSAP revelou a necessidade de aumentar a monitorização biológica neste berbigão visto que a dose semanal admissível foi muito baixa para os três metais. De um modo geral, C. edule refletiu as modificações ambientais, respondendo a modificações físico-químicas e contaminações por metais durante o período de estudo em ambas as estações de amostragem. Assim, este estudo permitiu concluir que Cerastoderma edule foi um bom e sensível indicador de contaminações por metais, especialmente para o Pb e preferencialmente para o Ni.

Estudo das características físico-químicas e biológicas pela adesão de osteoblastos em superfícies de titânio modificadas pela nitretação em plasma

SILVA, J. S. P. Estudo das características físico-químicas e biológicas pela adesão de osteoblastos em superfícies de titânio modificadas pela nitretação em plasma. 2008. 119 f. Tese (Doutorado) - Faculdade de Medicina, Universidade de São Paulo. São Paulo, 2008.

Estudo das características físico-químicas e biológicas pela adesão de osteoblastos em superfícies de titânio modificadas pela nitretação em plasma

SILVA, J. S. P. Estudo das características físico-químicas e biológicas pela adesão de osteoblastos em superfícies de titânio modificadas pela nitretação em plasma. 2008. 119 f. Tese (Doutorado) - Faculdade de Medicina, Universidade de São Paulo. São Paulo, 2008.

Avaliação da interação entre aflatoxina M1 e B1 com a fração proteica do leite

Dissertação composta por 02 artigos.

Obtenção de concentrado proteico do farelo de arroz e avaliação das propriedades químicas e funcionais

Esta dissertação é composta por 5 artigos.