Submitted by Marilene Donadel (marilene.donadel@unioeste.br) on 2019-02-06T18:22:36Z No. of bitstreams: 1 Leonardo_Megliorini_2018.pdf: 2265228 bytes, checksum: 5bec59af67778babe3b2590c1a6bf0f2 (MD5) / Made available in DSpace on 2019-02-06T18:22:36Z (GMT). No. of bitstreams: 1 Leonardo_Megliorini_2018.pdf: 2265228 bytes, checksum: 5bec59af67778babe3b2590c1a6bf0f2 (MD5) Previous issue date: 2018-07-27 / Nitrofurazone is a drug used to treat burns and skin transplants. The drug product is salled in cream and solution form. The ecovio® polymer is composed of poly(lactic acid) / poly(butylene adipate co-teraphtalate) and is biocompatible. In this work a film with the combination of ecovio® and nitrofurazone was produced by the electrospinning technique forming nanofibers. Two films were produced. The first was produced with dimethylformamide / tetrahydrofuran (15:85 v / v) and was capable of releasing 100% of the nitrofurazone reproducibly in the dissolution profile test evaluated for 300 minutes. The second film was produced with dimethylformamide/chloroform (15:85 v/v) and released about 90% of the nitrofurazone. But did not show reproducible results in the same range. Physicalchemical analyzes lead to the conclusion that the interaction of nitrofurazone with the polymer occurs mainly among the more polar groups. The dissolution test was performed following pharmacopoeial parameters. The quantitation of the released nitrofurazone was performed by UV-Vis spectrophotometry at 375 nm. The method used was validated and proved to be adequate, showing linearity in range 0.25 - 12.50 mg.L-1 with correlation coefficient 0.9999, high precision with relative standard deviation ≤ 1.6%, accuracy 98.9 - 100.4%, selectivity and limit of quantification 0.4 mg.L-1. / A nitrofurazona é um fármaco utilizado no tratamento de queimaduras e em transplantes de pele. O medicamento é comercializado na forma de pomada e solução. O polímero ecovio® é composto de poli(ácido lático)/poli(butileno adipato coteraftalato) e é biocompatível. Neste trabalho foi produzido um filme com a combinação de ecovio® e nitrofurazona pela técnica de eletrofiação formando nanofibras. Dois filmes foram produzidos. O primeiro foi produzido com dimetilformamida/tetrahidrofurano (15:85 v/v) e foi capaz de liberar 100% da nitrofurazona de forma reprodutível no teste de perfil de dissolução avaliado por 300 minutos. O segundo filme foi produzido com dimetilformamida/clorofórmio (15:85 v/v) e liberou cerca de 90% da nitrofurazona, mas não apresentou resultados reprodutíveis no mesmo intervalo. Análises físico-químicas levam à conclusão de que a interação da nitrofurazona com o polímero ocorre principalmente entre os grupamentos mais polares. O teste de dissolução foi realizado seguindo parâmetros farmacopeicos. A quantificação da nitrofurazona liberada foi realizada por espectrofotometria na região do UV-Vis em 375 nm. O método utilizado foi validado e comprovou-se estatisticamente que é adequado, apresentando linearidade no intervalo de 0,25 a 12,50 mg.L-1 com coeficiente de correlação de 0,9999, precisão elevada com desvio padrão relativo ≤ 1,6%, exatidão de 98,9 a 100,4%, seletividade e limite de quantificação de 0,4 mg.L-1.

Background: Traumatic brain injuries (TBIs) can result in a number of consequences for those who has sustained the injuries, as well as having an impact on their wider system. Estimates of divorce and relationship dissolution among couples following TBI can be as high as 54% and partners are reported to experience high levels of stress. The majority of studies have explored couples' relationships following TBI from the perspective of either the person with TBI or the partner, as opposed to exploring this dyadically and, therefore, limiting the holistic understanding to this topic. Aim: The two aims of this thesis are as follows: firstly, the mixed-method synthesis review aimed to explore the current dyad evidence-base around couples' experiences and relationships following TBI; and secondly, the qualitative study aimed to explore the impact of TBI on couples' experiences and relationships. Method: The systematic review's search strategy consisted of a computerised search across five databases and manual searches for further references in other relevant literature reviews and reference lists. The quality of the qualitative and quantitative studies were analyses separately. Metaethnography was employed to synthesize the finding from the qualitative studies. In the qualitative empirical study, five dyad-couples participated in the semi-structured interviews. The individuals with TBI and their partners were interviewed independently. The data collected was analysed using a combined deductive-inductive framework analysis approach, which supported comparisons between and within couples. Results: The systematic review yielded eight eligible studies, three quantitative and five qualitative studies. Review of the quantitative studies suggested couples reported poor relationship quality and partners reported more dyadic dissatisfaction and overall poorer relationship adjustment than the people with TBI. Analysis of the qualitative studies suggested there were significant variations in the way couples' experience and respond to TBI. This included individual responses from the people with TBI, their partners or collectively as a couple, which influenced their relationship dynamics and also how they coped. The findings also drew attention to other contextual factors that influenced couples' attributions and perceptions toward the TBI-related changes. Deductive and inductive analysis of the interviews in the qualitative empirical study identified three overarching themes: 'You begin to realise that, actually, life may not be the same ever [again]...'; perceived influences on relationship endurance following TBI; and contextual and other factors. These explored the impact of TBI on couples' relationships and the processes that interacted with or influenced their perceived relationship endurance. Conclusion: Although limited by a small number of eligible studies in the systematic review and small sample size in the qualitative empirical study, this thesis emphasized the importance of dyadic research for gaining a holistic understanding of couples' experiences and relationships following TBI. This allows the complex interplay between the TBI, the person who has suffered the TBI, their partner and their relationship to be better understood. The interconnectedness between the individuals and how the difficulties are experienced raises possible issues for healthcare services around their views and approaches to the individual with TBI, their partner and the couple's relationship during the recovery and rehabilitation journey.

Fármacos pouco solúveis em água tendem a possuir baixa biodisponibilidade. Diversos métodos têm sido estudados para promover o aumento da solubilidade em água de fármacos pouco solúveis. As dispersões sólidas têm sido pesquisadas como uma estratégia de aumentar a solubilidade em água e melhorar o desempenho destes fármacos na biodisponibilidade, entretanto os mecanismos completamente elucidados parecem variar da combinação do fármaco e do polímero, bem como do método de obtenção empregado. No presente estudo, através da técnica de evaporação do solvente desenvolveu-se dispersões sólidas de loratadina em polivinilpirrolidona a fim de melhorar a solubilidade do fármaco. / Poorly water soluble drugs tend to have low bioavailability. Several methods have been studied to promote increased water solubility of poorly soluble drugs. Solid dispersions have been investigated as a strategy to increase the water solubility and improve performance on the bioavailability of these drugs, however elucidated the mechanisms seem to vary the combination of drug and polymer and production method employed. In this study, using the technique of solvent evaporation was developed from solid dispersions in polyvinylpyrrolidone loratadine to improve the solubility of the drug.

Com a expansão do emprego de módulos fotovoltaicos para geração energética, surge o desafio do descarte adequado desse resíduo de equipamento eletroeletrônico. Através da elaboração de um processo multietapas, esse desafio torna-se possível de ser abordado. O presente estudo possui o objetivo de recuperar os materiais presentes nos módulos fotovoltaicos de silício cristalino e de silício amorfo. Diversas técnicas de caracterização física e química foram empregadas para determinar-se composição dos módulos fotovoltaicos e consequentemente o fluxo de processos necessários para recuperação dos materiais identificados. Foi identificado que o módulo de silício cristalino possuía no semicondutor alguns metais como prata (na concentração de 0,063% em massa do módulo) e silício, e na fase polimérica polidimetilsiloxano como encapsulante e PET como backsheet. A separação e recuperação dos polímeros foi realizada através do uso da teoria de dissolução de solventes de Hildebrand, abordando aspectos termodinâmicos e cinéticos. A separação ocorreu em 24h a 860rpm mergulhando-se os módulos em isopropanol, podendo ocorrer separação em até 6h a 860rpm utilizando-se tetrahidrofurano. A lixiviação da prata a partir do semicondutor foi possível com ácido sulfúrico 4mol.L-1, 95°C, sob adição de 6mL de peróxido de hidrogênio a cada 15min, alcançando-se 100% de lixiviação em 2h. Alterando-se a temperatura para 30°C a lixiviação foi completa apenas em 6h de experimento Precipitou-se a prata em solução na forma de cloreto de prata com adição de cloreto de sódio. O módulo de silício amorfo continha EVA na fração polimérica e silício, germânio, prata, estanho e índio (concentração 0,34g/m2 do módulo) na fração metálica, observados tanto por micrografias quanto por análise química quantitativa. A calcinação a 400°C permitiu a remoção do EVA e liberação dos contatos de prata. A lixiviação de índio foi de 100% para uma solução 1mol.L-1 de ácido fosfórico a 75°C, sob 800rpm de agitação e relação sólido-líquido 1g.10mL-1 em 1h. / As the photovoltaic module market grows, an increasingly challenging scenario arises for solar modules end of life management. Such a scenario can be tackled through a process comprising multiple steps. This study has the objective to recover materials present in photovoltaic modules of crystalline silicon and amorphous silicon. Several characterization techniques (physical and chemical) were employed to determine the composition of the modules and thus the process flow needed to recover the identified materials. Along the process, it was noticed that the crystalline silicon module had in its semiconductor metals such as silver (in concentration of at least 0,063% in weight of module) and silicon. Also polydimethylsiloxane was identified as encapsulant and polyethylene therephtalate as backsheet. A separation and recovery of these materials was possible using the theory of solvent dissolution of Hildebrand, comprising thermodynamics and kinetics. The separation occurred in 24h at 860rpm, rising the modules in isopropyl alcohol and potentially reaching 6h at 860rpm when rising them in tetrahydrofuran. The silver leaching from the semiconductor phase was possible in sulphuric acid 4 mol.L-1, 95°C, under addition of 6mL of hydrogen peroxide every 15min, reaching 100% silver leached in 2h. Shifting the temperature to 30°C, the leaching would occur completely only after 6h of experiment. The silver was precipitated as a chloride from the solution by addition of sodium chloride. The amorphous silicon module showed that EVA was present in the polymeric phase and silicon, germanium, silver, tin and indium (the last one at concentration of 0,34g/m2 in area of the module) in the metallic phase, observed on the micrographies and chemical analyses. Calcination was performed at 400°C, removing the EVA and freeing the silver contacts. Indium was 100% leached with a 1mol.L-1 phosphoric acid solution at 75°C, under 800rpm and solid-liquid ratio of 1g.10mL-1 in 1h.

No description available.

Adoption-focused psychoeducation is deemed essential in maintaining the permanency of traumatized children within a new family unit. However, adoptive parents of traumatized children struggle to find training to address their unique concerns. Guided by the lens of psychodynamic theory, the purpose of this study was to investigate the challenges faced by adoptive families of traumatized children. Special focus was placed on the social and emotional relationships of the adoptive parents of traumatized children, to identify the realistic expectations towards attachment from the families' perspectives. Fifteen families were randomly selected to participate in this study from a group of 30 parents who adopted traumatized children in Arizona. A phenomenological approach was utilized to gather information from face-to-face and telephone interviews. The data analysis utilized the horizontalization approach which highlighted significant statements that were classified into codes. Thematic categories were drawn and summarized. Textual descriptions evolved from the thematic groups acknowledging their experiences and how these lived experiences guided their decision to adopt a traumatized child. Verification techniques, data mining, journaling, clustering, brainstorming, and peer reviews were used to ensure the quality of data. Emergent themes emphasized the need for adoption-focused training specific to traumatized children. Further research on this phenomenon should determine the significance of specialized psychoeducational training versus general foster care training, before and after adoption. Positive social change may result in tailoring existing training programs to meet the needs of families who adopt traumatized children.

Investigate the interaction of nanomaterials with biological systems, known as nano-bio interaction is of great interest for the assessment of the concern arising from nanomaterials progressive use. Such interaction determines nanomaterials potential effect on human and environment becomes more and more important to understand how they interact with living organisms and the environment. The novel physicochemical characteristics of nanomaterials, such as their small size, large surface area to volume ratio and surface energy, may initiate new toxicological effects due to nanomaterials ability to enter into the biological systems through adsorption and dissolution and modify the structure of various macromolecules An example of these interactions is the adsorption of proteins on nanoparticles surface forming what is known as the 'protein corona'. Therefore, being able to understand how these molecules and other biologically important species are adsorbed and interact, should help us to reduce any adverse impacts of nanoparticles on human health and the environment. Due to the importance of surface composition and surface functionality in nanotoxicology, analytical tools that can probe the change in the structure and composition of the nanoparticles in aqueous media are crucial but remain limited. Therefore in this work, in situ characterization of the liquid–solid interface to probe surface adsorption of environmentally and biologically relevant media on nanoparticle surfaces has been conducted. Attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy provides the molecular information that allows for the determination of the adsorption mode such as conformational and structural changes of the coordinating ligand. Surface adsorption of titanium dioxide (TiO2) nanoparticles have been investigated in different biological media typically used for toxicity studies and show that the surface composition of TiO2 nanoparticles depends to a large extent on the composition of the medium due to surface adsorption. Moreover, hydrodynamic diameter and surface charge of TiO2 NPs were evaluated using dynamic light scattering DLS. The results indicated that TiO2 NPs undergo different trends in aggregation upon the adsorption of biological media on its surface and zeta potential measurements showed surface charge alterations which are consistent with the aggregation study. In order to understand the dynamic transformations of nanomaterials in biological environments, the effect of dissolution has been predicted. Copper oxide CuO and zinc oxide ZnO nanoparticles were used to study dissolution due to their instability in biological media. Once these particles exposed to solutions they release their ions and tend to aggregate. Therefore, the dissolution of these materials was conducted at size ca. 24 nm and nanoparticles coated with proteins and humic acid employing simulated lung fluids as models to develop a better understanding of how these properties effect the solubility and stability in biological systems. From this study, it was found that both copper oxide and zinc oxide NPs showed different trends in dissolution. Cu and Zn ions once coated with proteins and HA highly dissolved in ALF at low pH 4.5 compared with other fluids (Gamble’s solution and water) at extracellular pH which shows only slightly enhanced in the basal condition. The acidity of ALF may explain the higher solubility of metals that are phagocytized versus those that remain extracellular. Some general conclusions can be drawn from these investigations. It seems that analytical tools to characterize the interfacial region between nanopaerticles and these complex systems provide a reasonably good qualitative and quantitative description of the interactions.

Células a combustível regenerativas unitizadas (URFCs) são dispositivos eletroquímicos capazes de atuar como um eletrolisador de água ou como uma célula a combustível. Contudo, para que o potencial de uma URFC seja plenamente alcançado é essencial o desenvolvimento de componentes ativos e estáveis nos dois modos de operação, em especial em relação ao catalisador a ser utilizado no eletrodo de oxigênio. Em meio ácido, catalisadores obtidos pela combinação de platina e óxido de irídio têm apresentado desempenho satisfatório para as reações de redução (RRO) e evolução de oxigênio (REO), mas a estabilidade desses materiais ainda é relativamente pouco explorada. Neste trabalho, catalisadores bifuncionais foram sintetizados pela deposição de nanopartículas de platina sobre óxido irídio amorfo (Pt/IrOx) e cristalino (Pt/IrO2), e caracterizados físico-quimicamente através de diferentes técnicas, como EDX, XRD, XPS, XAS e XPS. A caracterização eletroquímica e a avaliação da atividade catalítica foi realizada em célula eletroquímica de três eletrodos, no qual é mostrado que, enquanto catalisadores Pt/IrO2 possuem maior atividade para a RRO, materiais Pt/IrOx são mais ativos para a REO. A estabilidade dos catalisadores bifuncionais foi avaliada empregando-se diferentes protocolos de envelhecimento. Uma investigação detalhada dos processos de degradação foi feita através da técnica de microscopia eletrônica de transmissão de localização idêntica (IL-TEM), enquanto que a dissolução eletroquímica dos catalisadores foi monitorada online utilizando-se uma célula eletroquímica de fluxo hifenada a um espectrômetro de massas com plasma indutivamente acoplado (SFCICP-MS). / Unitized regenerative fuel cells (URFCs) are electrochemical devices that can operate as a water electrolyzer or as a fuel cell. However, for the potential of an URFC to be fully achieved, it is essential to develop components that are active and stable in both operation modes, especially in relation to the catalyst to be used in the oxygen electrode. In acidic media, catalysts obtained by the combination of platinum and iridium oxide have shown satisfactory performance for the oxygen reduction (ORR) and evolution (OER) reactions, but the stability of these materials is still relatively little explored. In this work, bifunctional catalysts were synthesized by the deposition of platinum nanoparticles on hydrous (Pt/IrOx) and crystalline (Pt/IrO2) iridium oxide, and physicochemically characterized by different techniques such as EDX, XRD, TEM, XPS and XAS. The electrochemical characterization and the evaluation of the catalytic activity were performed in a three-electrodes electrochemical cell, in which it is shown that, while Pt/IrO2 catalysts have higher activity for the ORR, Pt/IrOx materials are more active for the OER. The stability of the bifunctional catalysts was evaluated using different aging protocols. A detailed investigation of the degradation processes was done using the identical location transmission electron microscopy (IL-TEM) technique, while the electrochemical dissolution of the catalysts was monitored online using a scanning flow cell inductively coupled to a plasma mass spectrometer (SFC-ICP-MS) setup.

As carbon dissolution rates have been determined for a few chars only, a systematic and comprehensive study was undertaken in this project on the dissolution behaviour of carbon from non-graphitic materials into liquid iron. In addition to measuring the kinetics of carbon dissolution from a number of coal chars into liquid iron as a function of parent coal and coal ash composition, the influence of chemical reactions between solute/solid carbon and ash oxides was also investigated. These studies were supplemented with investigations on one metallurgical coke for the sake of comparison. The wettability of coal chars and coke with liquid iron at 1550 degrees C was measured as a function of time. Being essentially non-wetting, only a marginal improvement in contact angles was observed with time. The accumulation of alumina at the interface was detected for all materials and was seen to increase with time in all cases. Calcium and sulphur also appeared to preferentially accumulate at the interface, concentrating at levels in excess of those expected from the ash composition alone. Despite the high levels of silica in the ash initially, very little silica was detected in the interfacial region, implying ongoing silica reduction reactions. A small amount of silicon was however detected in the iron droplets, indicating silica reduction with solute carbon. It was identified that the reduction reactions can also consume solute carbon in the liquid iron. As this is occurring simultaneously with carbon dissolution into liquid iron, the interdependency of silica reduction and carbon dissolution could potentially limit the observed carbon dissolution rate. A theoretical model was developed for estimating the interfacial contact area between chars and liquid iron. Wettability was found to have a very significant effect on the area of contact. A two-step behaviour was observed in the carbon dissolution of two chars and coke. Slow rates of carbon dissolution in stage II were attributed to very high levels of interfacial blockage by reaction products leading to much reduced areas of contact between carbonaceous material and liquid iron. The first order dissolution rate constants for four chars/coke and the observed trend in first order dissolution rate constants were calculated. These dissolution results compare well with the previously measured dissolution rate constants. The trends in dissolution can be adequately explained on the basis of carbon structure, silica reduction, sulphur concentration in the metal and ash impurities.

Les dangers potentiels liés à l'augmentation de la teneur en CO2 de l'atmosphère, tels que les changements climatiques ou l'élévation du niveau des mers, ont provoqué un grand intérêt pour la séquestration du gaz carbonique dans les formations géologiques. Le moyen thermodynamiquement le plus sûr pour stocker le carbone est sous la forme de minéraux carbonatés, mais il exige une source de cations divalents qui ne soit pas carbonatée. Les roches basaltiques qui présentent de fortes teneurs en calcium, magnésium et fer peuvent être une de ces sources et la possibilité de former des minéraux carbonatés par injection de CO2 dans les roches basaltiques est en cours d'investigation en Islande et dans d'autres endroits du monde. Dans ce cadre, l'objectif de cette thèse est de contribuer à l'optimisation de la précipitation des carbonates dans les basaltes lors de l'injection de CO2 grâce à une série d'études de terrain et de laboratoire complémentaires.<br>Une étude détaillée de la composition chimique des eaux souterraines au pied du volcan Mont Hekla, dans le sud de l'Islande, a d'abord été menée afin d'évaluer l'évolution chimique des fluides et la mobilité des métaux toxiques lors des interactions entre basalte et fluides riches en CO2. Ces fluides fournissent un analogue naturel pour estimer les conséquences de la séquestration du CO2 dans les basaltes. La teneur de ces fluides en carbone inorganique dissous diminue de 3,88 à 0,746 mmole/kg avec l'augmentation de la mise en solution du basalte tandis que le pH passe de 6,9 à 9,2. Ces observations fournissent une preuve directe du potentiel qu'offre la dissolution du basalte pour séquestrer le CO2. Les concentrations des métaux toxiques dans ces eaux sont faibles et la modélisation des chemins réactionnels suggère que la calcite et les (oxy)hydroxydes de fer piègent ces métaux, suite à l'alcalinisation des fluides induite par la dissolution continue du basalte.<br>On sait que ce sont les cations divalents libérés par la dissolution du verre basaltique qui contrôlent la minéralisation du gaz carbonique dans les basaltes. La vitesse de dissolution du verre basaltique peut être accrue par l'addition de ligands qui se complexent avec Al3+. L'ion SO42- fait partie de ces ligands et l'étude de son impact sur la vitesse de dissolution du verre basaltique a été conduite dans des réacteurs de type ‘mixed flow' à 50°C et 3 < pH < 10. Le soufre est souvent présent dans les gaz émis par les centrales électriques et son stockage constitue un challenge environnemental. La co-injection avec CO2, si elle est réalisable, peut donc constituer une nouvelle méthode peu couteuse de stockage du soufre généré par l'industrie. En accord avec les modèles actuels décrivant la cinétique de dissolution du verre basaltique en fonction de la composition de la solution aqueuse, les résultats de ce travail montrent que SO42-augmente la vitesse de dissolution du verre aux conditions acide mais qu'il n'a aucun effet aux pH alcalins. Ces résultats suggèrent à la fois que 1) la co-injection de sulfate peut accélérer la minéralisation du CO2 dans les basaltes et 2) les modèles cinétiques existant permettent une description précise de la dissolution du verre basaltique.<br>Afin d'évaluer plus précisément l'impact des ions sulfates sur la vitesse de précipitation des carbonates, la vitesse de précipitation de la calcite en régime stationnaire a été mesurée dans des réacteurs à circulation ‘mixed flow' à 25°C et pH ~9.1. Les résultats montrent qu'en présence de 0.005 M de Na2SO4 la vitesse de précipitation de la calcite est diminuée d'environ 40% et qu'ainsi la co-injection de sulfate peut ralentir la précipitation de la calcite aux pH typiques de la précipitation de ce minéral en subsurface. Des expériences supplémentaires sont prévues pour caractériser définitivement l'effet du sulfate aux conditions attendues aux sites d'injection du CO2 en subsurface.