Utilização de co-produtos do biodiesel na reciclagem química de poli(tereftalato de etileno) para produção de novos materiais poliméricos

Orientador : Prof. Dr. Luiz Pereira RamosCoorientador : Profª. Drª. Maria Aparecida F. César-OliveiraDissertação (mestrado) - Universidade Federal do Paraná, Setor de Ciências Exatas, Programa de Pós-Graduação em Química. Defesa: Curitiba, 18/12/2008Inclui referências : f. 67-71Resumo: O recente interesse por fontes de energia alternativas, renováveis, de duração ilimitada e baixo impacto ambiental, tem levado ao aumento da utilização e produção de biodiesel, o que implica em crescente disponibilidade de glicerina no mercado exigindo o estudo de novas aplicações para aumentar o consumo desta matéria prima. Por outro lado, o grande aumento da produção e de utilização do PET nos mais variados segmentos do mercado, principalmente no de embalagens, trouxe um grande problema ambiental associado ao descarte das embalagens utilizadas. A reciclagem do PET tem sido uma opção para a solução deste problema, porém a reciclagem química envolvendo compostos polihidroxilados, como o glicerol, que pode dar origem a materiais com propriedades diferenciadas, tem sido pouco estudada. Unindo estas duas importantes demandas, este Trabalho propõe o desenvolvimento de alguns poliésteres aromáticos, de estrutura e propriedades variadas, obtidos a partir do glicerol envolvendo a reciclagem química do poli(tereftalato de etileno), que poderão servir a diversas aplicações com a possibilidade de ter sua arquitetura orientada à obtenção das propriedades adequadas a uma dada aplicação. Neste trabalho foram obtidos produtos de reação da solvólise de poli(tereftalato de etileno) com glicerol, catalisada por acetato de magnésio [Mg(OAc)2]. As condições de reação foram variadas quanto à temperatura, tempo, tipo de catalisador, proporção dos reagentes. Comprovou-se a maior eficiência do Mg(OAc)2 em relação ao acetato de zinco [Zn(OAc)2], o melhor catalisador dentre os metais de transição segundo a literatura. A recuperação dos produtos foi de 95% a 220ºC no período de 5 horas em comparação com 20 horas a 200ºC descritos na literatura. Não foi possível isolar o monômero devido à solubilidade do mesmo, porém logrou-se conseguir a polimerização no mesmo recipiente da reação de solvólise por destilação à vácuo do glicerol em excesso. O s produtos foram caracterizados por 1H-RMN, DSC, GPC, FTIR, índices de hidroxila e acidez. Foram obtidos polímeros com massa molar média ponderal (Mw) entre 3.000 e 7.000 g/mol e, com o uso de tereftalato de dimetila como extensor de cadeia, polímeros com Mw até 11.000 g/mol.Abstract: The recent interest in renewable energy alternative sources, with low environmental impact, has led the increase the production and use of biodiesel, that results in increasing of glycerin availability that require studies to propose new applications to increase the consumption of this raw material. On the other hand, a greater production and use of poly(ethylene terephthalate) - PET - in a several segments, mainly in packaging, has brought a major environmental problem associated with an inappropriate discard of used packaging. PET recycling has been an option to solve this problem, but the chemical recycling involving polyhydroxyl compounds such as glycerol, which may give rise to materials with different properties, has been little investigated. Combining these two important demands, this work presents the development of some aromatic polyesters with different structures and different properties obtained from chemistry recycling of PET using glycerol. These new polyesters might be used in a variety of applications with possibility of having its architecture oriented to obtaining the appropriate properties for a given application. In this work, was possible to obtain polyesters, from PET by solvolysis reactions catalyzed by magnesium acetate [Mg(OAc)2]. Several reaction conditions were investigated, such as, temperature, time, type of catalyst, reagents ratio. The efficiency of Mg(OAc)2 was better than zinc acetate [Zn(OAc)2], the latter being rated the best catalyst among transition metals according the literature. The products were obtained in 95% yield, at 220 °C in 5 hours. This is a better result than that cited by 20 hours at 200 °C using Zn(OAc)2, described in the literature. The new polyesters were made by one-pot synthesis techniques since it was not possible isolate the monomer due to the solubility of the same. Therefore, the polymerization reaction was carried out in the same bottle where it has been the reaction of solvolysis by distillation of glycerol excess in the reduced pressure. The products were characterized by 1H-NMR, DSC, GPC, FTIR, hydroxyl index and acidity index. The polymers were obtained with average molar mass () between 3,000 and 7,000 g/mol, and using dimethyl terephthalate as a chain extender, polymers of up to 11,000 g/mol were obtained

O conto “Negrinha” nas linhas e entrelinhas: um diálogo entre literatura e história

O conto “Negrinha”, de Monteiro Lobato, publicado em livro do mesmo nome, em 1920, coloca em cena um recorte da sociedade pós-abolição do início do século passado. O texto, de valor literário, histórico e sociológico, contempla situações que possibilitam uma série de contribuições acerca do contexto ao qual se insere obra e autor. Com base nessas assertivas, o artigo tem o objetivo de verificar, de forma parcial, a situação histórico/social do Brasil à época apontada por meio do conto. Vale ressaltar que o estudo interdisciplinar deste artigo vai ao encontro de propostas pedagógicas inseridas no âmbito da História que, invariavelmente, sofre pela constituição de textos frios, diretos e cada vez mais sintéticos, o que na literatura se condensa de forma diversa, embora sem o compromisso com a verdade. O texto se apoia em Chartier (2009), Fausto (2010) e Bosi (2010), entre outros, para discutir as particularidades propostas.  

Classification of glomerular hypercellularity using convolutional features and support vector machine

Glomeruli are histological structures of the kidney cortex formed by interwoven blood capillaries, and are responsible for blood filtration. Glomerular lesions impair kidney filtration capability, leading to protein loss and metabolic waste retention. An example of lesion is the glomerular hypercellularity, which is characterized by an increase in the number of cell nuclei in different areas of the glomeruli. Glomerular hypercellularity is a frequent lesion present in different kidney diseases. Automatic detection of glomerular hypercellularity would accelerate the screening of scanned histological slides for the lesion, enhancing clinical diagnosis. Having this in mind, we propose a new approach for classification of hypercellularity in human kidney images. Our proposed method introduces a novel architecture of a convolutional neural network (CNN) along with a support vector machine, achieving near perfect average results with the FIOCRUZ data set in a binary classification (lesion or normal). Our deep-based classifier outperformed the state-of-the-art results on the same data set. Additionally, classification of hypercellularity sub-lesions was also performed, considering mesangial, endocapilar and both lesions; in this multi-classification task, our proposed method just failed in 4\% of the cases. To the best of our knowledge, this is the first study on deep learning over a data set of glomerular hypercellularity images of human kidney.Comment: 26 page

Oligocat: Oligoesters as Pseudo-Homogenous Catalysts for Biodiesel Synthesis

Biodiesel production from first-generation feedstock has shown a strong correlation with the increase in deforestation and the necessity of larger areas for land farming. Recent estimation from the European Federation for Transport and Environment evidenced that since the 2000s decade, an area equal to the Netherlands was deforested to supply global biodiesel demand, mainly originating from first-generation feedstock. Nevertheless, biodiesel is renewable, and it can be a greener source of energy than petroleum. A promising approach to make biodiesel independent from large areas of farming is to shift as much as possible the biodiesel production chain to second and third generations of feedstock. The second generation presents three main advantages, where it does not compete with the food industry, its commercial value is negligible, or none, and its usage as feedstock for biodiesel production reduces the overall waste disposal. In this manuscript, we present an oligomeric catalyst designed to be multi-functional for second-generation feedstock transesterification reactions, mainly focusing our efforts to optimize the conversion of tallow fat and sauteing oil to FAME and FAEE, applying our innovative catalyst. Named as Oligocat, our catalyst acts as a Brønsted-Lowry acid catalyst, providing protons to the reaction medium, and at the same time, with the course of the reaction, it sequesters glycerol molecules from the medium and changes its physical phase during the transesterification reaction. With this set of properties, Oligocat presents a pseudo-homogenous behavior, reducing the purification and separation steps of the biodiesel process production. Reaction conditions were optimized applying a 4$^{2}$ factorial planning. The output parameter evaluated was the conversion rate of triacylglycerol to mono alkyl esters, measured through gel permeation chromatography (GPC). After the optimization studies, a conversion yield of 96.7 (±1.9) wt% was achieved, which allows classifying the obtained mono alkyl esters as biodiesel by ASTM D6751 or EN 14214:2003. After applying the catalyst in three reaction cycles, Oligocat still presented a conversion rate above 96.5 wt% and as well an excellent recovery rate

ÍNDIOS URBANOS: A MIGRAÇÃO DO POVO PANKARARU PARA A CIDADE DE SÃO PAULO: ASPECTOS TERRITORIAIS E IDENTIT´ÁRIOS

O povo Pankararu é uma etnia indígena que tem sua origem no sertão de Pernambuco e há décadas estabeleceu uma rota migratória para a cidade de São Paulo, em especial para a favela do Real Parque, localizada no distrito do Morumbi. Devido à escassez de recursos, problemas fundiários e adversidades climáticas, uma parcela da população migra para São Paulo em busca de melhores condições de subsistência e tenta se estabelecer no local onde já existe um grupo dessa etnia. A presente pesquisa possui abordagem qualitativa e tem como objetivo compreender as relações estabelecidas no processo migratório do povo indígena Pankararu e questões territoriais, culturais, sociais e históricas decorrentes deste processo, do interior de Pernambuco para a cidade de São Paulo. Através de entrevistas semiestruturadas, realizadas com os indígenas moradores do Real Parque, pôde-se perceber o contraste social entre a favela do Real Parque e o bairro de mesmo nome e o Morumbi

ANALYSIS OF SLEEP QUALITY, RISK OF FALLS AND FUNCTIONAL CAPACITY IN PHYSICALLY ACTIVE ELDERLY: A CROSS-SECTIONAL STUDY

Introdução: O envelhecimento provoca alterações na qualidade do sono, sendo considerado um fator de risco para as quedas, além disso pode influenciar a capacidade funcional dos idosos. A atividade física é considerada um fator de prevenção aos danos advindos do envelhecimento. Objetivo: Avaliar a qualidade do sono, risco de quedas e a capacidade funcional em idosos fisicamente ativos. Metodologia: estudo transversal, composto por 29 idosos participantes do programa de fisioterapia preventiva para a terceira idade do estágio em atenção básica à saúde do curso de Fisioterapia na cidade de Uberlândia. A coleta iniciou-se pelos questionários: IPAQ (International Physical Activity Questionnaire) que avaliou o nível de atividade física e o MEEM (Mini Exame do Estado Mental) mensura comprometimento cognitivo, ambos utilizados como critérios de inclusão dos participantes. A partir da inclusão foram aplicados os instrumentos: MSQ (Mini-Sleep Questionare) para avaliação da qualidade do sono e o Índice de Barthel que avaliou a capacidade funcional, e o teste TUG (Time Up and Go) avaliou risco de quedas. Resultados: A amostra apresentou que 18 (62.06%) idosos tinham sono bom, 21 (72.40%) idosos com baixo risco de quedas e 22 (75.86%) idosos com independência total para executar as atividades de vida diária. Conclusão: A maioria dos idosos avaliados no estudo apresentaram um sono bom, baixo risco de quedas e independência total para realizar as atividades de vida diária.Introduction: Aging causes changes in the quality of sleep, which is considered a risk factor for falls, in addition to influencing the functional capacity of the elderly. Physical activity is considered a factor in preventing damage from aging. Objective: To assess sleep quality, risk of falls, and functional capacity in physically active elderly people. Methodology: a cross-sectional study, consisting of 29 elderly participants in the preventive physiotherapy program for the elderly in the basic health care internship of the physiotherapy course in the city of Uberlândia. The collection started with the questionnaires: the IPAQ (International Physical Activity Questionnaire), which evaluated the level of physical activity, and the MMSE (Mini-Mental State Examination), which measures cognitive impairment, both were used as inclusion criteria for the participants. From the inclusion, the instruments were applied: MSQ (Mini-Sleep Questionnaire) to assess sleep quality, and the Barthel Index which assessed functional capacity, and the TUG (Time Up and Go test) assessed the risk of falls. Results: The sample showed that 18 (62.06%) seniors had a good sleep, 21 (72.40%) seniors indicated a low risk of falls, and 22 (75.86%) seniors showed complete independence to perform activities of daily living. Conclusion: Most of the elderly evaluated in the study had good sleep, a low risk of falls, and total independence to carry out activities of daily living

A nova lei seca: mudanças ocasionadas pela antiga e nova lei no código de trânsito brasileiro

A lei seca foi instituída com o objetivo de diminuir drasticamente a quantidade de acidentes de trânsito, ocorridos no Brasil, fazendo assim, alterações no código de trânsito brasileiro. Esta mudança acarretou resultados positivos, como a diminuição do número de motoristas que combinam a ingestão de bebidas alcoólicas com a direção de veículos automotores, causando assim, acidentes de trânsito. Além da utilização da lei seca, utilizam-se também métodos como, o registro do nível alcoólico, através do bafômetro ou exames de sangue, e também pelas chamadas blitz, que inibem esse tipo de ação. Com isso, o objetivo da pesquisa é analisar as mudanças ocorridas no CTB, ocasionados pela nova lei Seca e seus efeitos sobre a população. Palavras - chave: Lei Seca. CTB. Álcool. Direção. Veículos Automotores. Acidente de trânsito

Salicylic acid as a mitigator of water stress in black oats seeds

Oats are a very popular grass used in crop rotation to provide organic matter, green mass and assist in the natural aeration of the soil. Agronomic factors such as acidity correction and soil fertility adjustments can be controlled, but when it comes to climatic factors, cultivation depends on favorable climate conditions for good plant development. For instance, low rainfall occurrences result in decreased percentage of germination and plant development. Water stress affects plant development. Therefore, this study aimed to evaluate the effect of salicylic acid as a water stress mitigator on black oats. The experiment was carried out in the Laboratory of Molecular Biology and Biotechnology of Products and Microorganisms of the University of Parana. Black oats (Avena strigosa Schreb) seeds were submitted to different imbibition treatments: without imbibition, soaked in distilled water, and soaked in salicylic acid. Then, they were placed in gerbox boxes previously moistened with 6000 polyethylene glycol solution with different osmotic potentials (0.0; -0.2; -0.4; -0.6 and -0.8 MPa). The experiment was conducted in a completely randomized design with four replicates. Ten days after the experiment, the following parameters were evaluated: germination percentage, germination velocity index, shoot length and radicle length. Salicylic acid at the concentration used in this study promotes a mitigating effect of water stress caused by PEG6000, increasing the germination percentage of black oat seeds

Natural Products as Promising Pharmacological Tools for the Management of Fibromyalgia Symptoms – A Review

Fibromyalgia (FM) is the second most common rheumatologic disorder, affecting 5% of the world population, and has a serious effect on the quality of life of patients, as well as an economic impact through lost workdays. This pain syndrome is a common cause of chronic widespread pain and is characterized by reduced pressure pain thresholds with hyperalgesia and allodynia, nonrestorative sleep, fatigue, cognitive dysfunction, and mood disturbances. The pharmacological treatment strategies for FM include the use of antidepressants, calcium channel modulators, muscle relaxants, and analgesics but have shown limited efficacy and therapeutic adherence. Thus, researchers have been seeking potential substances (new chemical entities or through drug repositioning) that could be used for FM treatment. In this context, natural products (NPs) have been shown to be promising pharmacological tools due to the variety of their pharmacological activity and the number of molecular sites available as possible active targets. Recent clinical and preclinical studies have been conducted to verify the possible applicability of NPs such as essential oils (EOs), plants extracts, terpenes, sapogenins, and alkaloids in the treatment of FM. The results have shown that natural products have an analgesic effect in different animal models of FM, probably by activation of inhibitory descending pathways, such as the periaqueductal gray and rostroventromedial medulla. Natural products and their secondary metabolites could therefore be a promising source for FM management. However, translational studies that seek to validate the preclinical studies are scarce, incipient, and lacking an approach focused on the traditional pharmaceutical market