In order to find/design porous materials that could be used in practical applications involving adsorption, it is important to investigate the basic properties (i.e. isosteric heat, specific surface area, binding energy, pore size, pore volume, etc.) of each material. With this aim in mind we have looked at three different types of materials: single-walled carbon nanotubes (prepared by the HiPco and laser methods), single-walled nanohorns (dahlia-like and bud-like) and metal-organic frameworks (Cu-BTC and RPM-1). For these substrates we have measured volumetric adsorption isotherms using several gases such as neon, argon, tetrafluoromethane (CF4), xenon, and methane (not all gases for all substrates). Experimental adsorption isotherms were measured using methane, argon, xenon, and neon gases on unpurified single-walled carbon nanotubes prepared by the HiPco method. The main idea behind these experiments was to investigate, using different size gas molecules, the sites available for adsorption on this type of porous material. We found that surface area occupied by these adsorbates on the sample is the same, regardless of their size. This means that all the gases have access to the same group of adsorption sites. Since the biggest adsorbate in this experiment was Xe, and since it is unlikely that it could penetrate the interstitial channels in the nanotube bundles, we conclude that none of the gases, including the smallest one - Ne, are able to adsorb in the interstitial channels in bundles of single-walled carbon nanotubes. For the case of argon on laser produced single-walled carbon nanotubes we measured 21 adsorption isotherms using argon gas temperatures between 40 and 153 K that were used to determine the isosteric heat of adsorption for this system. Our experimental results were compared to the ones from computer simulations performed by J. K. Johnson (from the University of Pittsburgh) for the same gas on heterogeneous and homogenous bundles. It was observed that the isosteric heat data matches better with data computed for heterogeneous nanotube bundles. This indicates that at the lowest pressure and coverages argon might be adsorbing in the defect-induced interstitial channels. We studied Cu3(Benzene-1,3,5-tricarboxylate)2(H2O)3 (abbreviated as Cu-BTC) metal-organic framework with argon to determine the sites available for adsorption on this material. Volumetric adsorption isotherms were measured at temperatures between 66 and 143 K. We found two substeps in the isotherm data, indicating that there are two types of pores present in the material: tetrahedrally-shaped side pockets and the main channels. Our experimental results were compared with data from simulations conducted using the Grand Canonical Monte Carlo method. We determined that the theoretical results match reasonably well with ours if the coverage is scaled down by a factor of 1.6. We explored the potential of two different metal-organic framework materials (Cu-BTC and RPM-1) for gas separation application. We used argon and tetrafluoromethane (CF4) gases to check if this can be achieved through kinetic and steric mechanisms. We found that Cu-BTC has excellent potential in gas separation using a steric mechanism, since argon easily adsorbs into the small pores present in the sample, while CF4 is excluded from them. Adsorption properties of RPM-1 showed that it could be employed in gas separation using a kinetic mechanism - argon gas adsorbs and reaches equilibrium in the pores of the sample more than the order of magnitude faster than CF4. Closed-ended dahlia-like nanohorns were studied with neon and tetrafluoromethane gases. In the first layer of neon and tetrafluoromethane adsorbed on dahlia-like nanohorns we found two substeps. These results were compared with results of computer simulations performed by Prof. M. Calbi. We determined, after comparison with the simulation isotherms, that the lower pressure substeps correspond to adsorption of Ne and CF4 in the narrowest parts of interstitial channels of the aggregates. Surface area calculated from neon isotherms was found to be higher than the one obtained using CF4, meaning that the smaller Ne molecule has the access to the parts of the interstitial channels that are not accessible for the bigger CF4 molecule. Features that appeared in neon adsorption isotherms on bud-like nanohorn aggregates were quite different from the ones on dahlia-like aggregates. We measured neon adsorption isotherms on this type of sample at temperatures between 22 and 49 K. In the monolayer regime we observed one single substep whose origin we can not definitely identify, because the structure of the bud-like nanohorns is not well-known. The binding energy value that was calculated from the isotherm data was lower than the value for neon adsorbed in the grooves of nanotube bundles but higher than for neon on graphite.

O tema desta pesquisa são as disputas travadas por veículos midiáticos na cobertura a ações de movimentos sociais. Busca-se, empiricamente, identificar os enquadramentos interpretativos construídos por três jornais (Zero Hora, Diário Gaúcho e Sul21) sobre o ciclo de protestos de 2013, em Porto Alegre/RS, em especial no que se refere às interações entre manifestantes e aparato policial. Metodologicamente, foi construído um banco de dados com todas as publicações de cada jornal, na cobertura ao ciclo de manifestações, bem como foram entrevistados(as) jornalistas responsáveis pela produção do conteúdo dessas publicações. Após a organização e a quantificação do corpus de dados, com a identificação de tendências de cobertura, foram selecionados eventos específicos de protesto (ocorridos em 27 de março, 04 de abril, 13 de junho e 20 de junho), bem como as “retrospectivas” de final de ano, para análise de conteúdo. A convergência entre o material empírico e os referenciais teóricos resultou em três dimensões centrais: a identidade dos(as) manifestantes; a caracterização da(s) reivindicação(ões) do protesto; as interações entre manifestantes e policiais. A partir de tais dimensões construiu-se um modelo analítico para operacionalização do estudo. Os resultados da pesquisa indicam que a construção de enquadramentos interpretativos por Zero Hora, Diário Gaúcho e Sul21 foi caracterizada pela multiplicidade de esquemas interpretativos. Essa multiplicidade diz respeito a diferenças (a) entre os conteúdos de cada jornal e a (b) transformações de enquadramento no curso das mobilizações. Zero Hora e Diário Gaúcho produziram enquadramentos similares. Inicialmente, as coberturas de ambos os jornais centraram-se na identificação de repertórios de dano a patrimônios por manifestantes, tomando-se a manifestação (denominada “baderna”) como ilegítima. Ao longo do ano, Zero Hora e Diário Gaúcho delimitaram uma distinção entre “manifestantes pacíficos” e um grupo específico - qualificado pelo termo “vândalos” -, o qual foi considerado responsabilizável pela realização de repertórios de dano a patrimônios. A referida transformação de enquadramento denotou uma autonomização deste repertório específico (tomado como ilegítimo) em relação à manifestação (considerada legítima). O Sul21 caracterizou-se, diversamente, pela ênfase, desde o início do ano, no questionamento à ação policial de repressão às mobilizações. Os protestos, por outro turno, foram invariavelmente considerados legítimos pelo Sul21. Por fim, as “retrospectivas” de final de ano indicaram similaridades no enquadramento de todos os jornais, com a construção de uma síntese interpretativa hegemônica a respeito do ciclo de protestos. A partir da análise de dados, formulou-se a seguinte tipologia dos enquadramentos interpretativos adotados em diferentes momentos do ano: “Manifestação como afronta à ordem”; “Polícia como instituição violenta”; “Maioria de manifestantes pacíficos em oposição à minoria de manifestantes violentos”; “Maioria de manifestantes pacíficos em oposição à minoria de manifestantes violentos e a uma polícia violenta”. A análise cronológica denotou disputas entre esses diferentes modelos de cobertura, com a constituição de um “campo de batalha” interpretativo. / The subject of this research is the disputes promoted by media vehicles at the coverage of social movements actions. We seek to, empirically, identify the interpretative frameworks built by three newspapers (Zero Hora, Diário Gaúcho and Sul21) about the 2013 protests cycle, in Porto Alegre/RS, in particular in what it refers to the interactions between protesters and police apparatus. Methodologically, we constructed a database with all the publications of each newspaper, at the coverage of the mobilization cycle and we interviewed journalists responsible for producing the content of these publications. After organizing and quantifying the database, identifying coverage trends, we selected specific protest events (occurred on March 27, April 04, June 13 and June 20) and the end-of-the-year "retrospectives" for content analysis. The convergence between empirical data and theoretical references resulted in three central dimensions: the identity of protesters; the characterization of protest claims; the interactions between protesters, and police. From these dimensions we constructed an analytical model for the implementation of the study. The survey results indicate that the construction of interpretative frameworks by Zero Hora, Diário Gaúcho, and Sul21 was characterized by the multiplicity of interpretative schemes. This multiplicity concerns about the differences (a) between the contents of each newspaper and about the (b) framework changes in the course of mobilizations. Zero Hora and Diário Gaúcho produced similar frameworks. Initially, the coverage of both newspapers focused on the identification of repertoires of patrimonial damage by protesters, taking the manifestation (called "hooliganism") as illegitimate. Throughout the year, Zero Hora and Diário Gaúcho delimited a distinction between "peaceful protesters" and a specific group - qualified as "vandals" -, which was considered responsible for conducting repertoires of patrimonial damage. This framework transformation denoted an increasing autonomy of this particular repertoire (taken as illegitimate) in relation with the mobilization itself (considered legitimate). Sul21 was characterized, diversely, by the emphasis, since the beginning of the year, on questioning the police action of repression to the manifestations. The protests, on the other hand, were invariably considered legitimate by Sul21. Finally, the end-of-the-year "retrospectives" indicated similarities between the frameworks of all the newspapers, with the construction of a hegemonic interpretative synthesis about the protest cycle. From the data analysis, we formulated the following typology of interpretative frameworks adopted in different moments of the year: "manifestation as an affront to order"; "Police as a violent institution"; "The majority of peaceful protesters opposed to the minority of violent protesters"; "The majority of peaceful protesters opposed to the minority of violent protesters and opposed to a violent police." The chronological analysis denoted disputes between these different types of coverage, with the establishment of a "battlefield" interpretation.

Introdução: Quando os dilemas éticos surgem no âmbito de assistência à saúde, surge a necessidade de fazer uma reflexão no âmbito da Bioética Clínica, que pode ser entendida como sendo a identificação, análise e resolução de problemas ou dilemas morais que surgem no cuidado individual de pacientes. Embora as questões práticas sejam usualmente priorizadas na assistência ao paciente, é reconhecida a importância da teoria nos modelos de tomada de decisão. Quando a atenção se volta para a prática, descobrimos regras complexas de ação e percepção que raramente são discutidas. O Modelo da Bioética Complexa busca agregar estas visões, e sugere que a Bioética é uma reflexão complexa, compartilhada e interdisciplinar sobre a adequação das ações que envolvem a vida e o viver. Objetivos: O objetivo desta tese é analisar as consultorias de Bioética Clínica realizadas em um hospital geral universitário de grande porte, verificando os aspectos teóricos e práticos identificados e as suas interações. Métodos: Foi realizado um estudo transversal das 317 consultorias de Bioética Clínica realizadas no Hospital de Clinicas de Porto Alegre de fevereiro de 2009 até abril de 2013, que tiveram registros nos prontuários de 300 pacientes internados. O levantamento dos prontuários foi fornecido pelo Serviço de Arquivo Médico e Informações em Saúde, que é o responsável pela guarda e manutenção destes registros. Os referenciais teóricos utilizados foram analisados a partir da abordagem complexa da Bioética, utilizando quatro grandes referenciais: Virtudes, Princípios, Direitos Humanos e Alteridade. Os temas das consultorias foram analisados de acordo com a classificação proposta pela National Reference Center for Bioethics Literature, da Georgetown Law Library, adaptada nesta tese. Resultados: Foi possível identificar que 94,7% dos solicitantes eram médicos e 5,3% eram enfermeiros. Os Serviços que mais solicitaram consultorias foram o de Medicina Interna (22,3%), Pediatria (15,7%) e Psiquiatria (9,3%). O referencial das Virtudes estava presente em 99,3% dos casos, o dos Princípios em 99,0%; o dos Direitos Humanos em 97,3% e o da Alteridade em 94,4%. Dos pacientes, 50,0% eram do sexo feminino, com idade média de 37,42 + 25,61 anos, e tempo médio de internação de 52,1+120,82 dias. Destes, 63,0% tiveram alta para o domicílio e 33,3% foram a óbito. Os três temas mais frequentes nas consultorias foram: Morte e Morrer, (81,7%), Relacionamento Profissional (66,0%), e Consentimento Informado (64,7%). A média anual de consultorias foi de 78,0 e a mensal de 6,52, e o tempo para responder às consultorias foi, em média, de 40,0+102,1 horas. Avaliando os aspectos translacionais em prontuário, foi possível identificar que em 73,3% houve transposição evidente das condutas sugeridas para a prática assistencial. Conclusão: As características dos profissionais que solicitaram consultorias, para quais pacientes ocorreram estas solicitações, e os respectivos seviços médicos associados, possibilitaram identificar os temas mais relevantes nas consultorias de Bioética Clínica, e quais os referenciais teóricos que estão envolvidos nestes problemas éticos. Esta análise permitiu verificar a interação existente entre teoria e prática e a transposição das reflexões da Bioética à assistência aos pacientes. / Background: When ethical dilemmas arise in the context of health care, arises the need to think in the Clinical Ethics field, which can be understood as the identification, analysis and resolution of problems and moral dilemmas that arise in the individual patients care. Although practical issues are usually prioritized in patient care, the importance of theory in models of decision making process is recognized. When attention turns to practice, we find complex rules of action and perception that are rarely discussed. The Complex Bioethics Model intended to add these visions, and suggests that bioethics is a complex, interdisciplinary and shared reflection on the actions adequacy involving life and living. Objective: The aim of this thesis is analyze the Clinical Ethics consultations performed in a large general university hospital, verifying theoretical and practical aspects identified and their interactions. Methods: A cross-sectional study was conducted with 317 Clinical Bioethics consultations performed at Hospital de Clinicas de Porto Alegre in February 2009 until April 2013, registered in 300 inpatients medical records. The Medical Records and Health Information Service, responsible for the custody and maintenance of these records, provided medical records survey. The theoretical frameworks were analyzed using the bioethics complex approach to, using four major benchmarks: Virtues, Principles, Human Rights and Alterity. The consultations themes were analyzed according to the classification proposed by the National Reference Center for Bioethics Literature, the Georgetown Law Library, adapted for this purpose. Results: We found that 94.8 % of applicants were physicians and 5.3 % were nurses. Services that most requested consultations were Internal Medicine (22.3%), Pediatrics (15.7%) and Psychiatry (9.3%). The Virtues benchmark was present in 99.3% cases, Principles in 99.0%, Human Rights in 97.3 % and Alterity in 94.4 %. About patients, 50.0 % were female, mean age was 37.42 + 25.61 years, and mean hospital stay 52.1 days +120.82. Of these, 63.0 % were discharged home and 33.3 % died. The three most frequent themes in consultations were: Death and Dying, (81.7%), Professional Relationship (66.0%), and Informed Consent (64.7%). Annual consultations average was 78.0 and monthly average 6.52, time to respond to consultations was on average 40.0 +102.1 hours. Evaluating patient records translational aspects, we found that 73.3% had evident transposition of conduct suggested for clinical practice. Conclusion: Professionals characteristics of those who have requested consultations, which patients had these requests and their associated medical services, allowed to identify the most relevant Clinical Bioethics consultations topics, and which theoretical frameworks are involved in these ethical problems. This analysis enables to verify the theory and practice interaction and the transposition of the Bioethics reflections to patients’ assistance.

A presente pesquisa tem como objetivo analisar as relações estabelecidas entre as formulações teóricas e práticas no campo do feminismo. Para tanto, consistem em objeto empírico deste trabalho o Movimento de Mulheres Camponesas (MMC) e a organização não-governamental (ONG) Coletivo Feminino Plural, ambas com atuação no estado do Rio Grande do Sul e identificadas com o feminismo. A partir do conceito movimento social para tratar do feminismo – que passa a ser entendido enquanto rede que admite uma diversidade de atores e proposições-, as formulações teóricas das organizações foram abordadas segundo o conceito quadros interpretativos e as práticas, repertórios de ação, afim de que fossem reestruturados para posterior análise os elementos teóricos e práticos das mesmas. Tal argumentação foi acompanhada pelo resgate do desenvolvimento do feminismo no Brasil, em especial no Rio Grande do Sul, fazendo emergir o contexto no qual MMC e Coletivo Feminino Plural surgem. Análises intra-organizacionais e inter-organizacionais foram realizadas, optando-se, para isso, por uma pesquisa qualitativa relacional, na qual foram utilizadas entrevistas semi-estruturadas com as dirigentes e coordenadoras das organizações para apreender, principalmente, os repertórios de ação e análise de documentos para apreender os quadros interpretativos. / This research aims to analyze the relations established between theoretical formulations and practices in the field of feminism. For this purpose, consist of empirical object of this work the Movimento de Mulheres Camponesas (MMC) and the non-governmental organization (NGO) Coletivo Feminino Plural, both with operations in the state of Rio Grande do Sul and identified with feminism. From concept to treat social movement of feminism - which happens to be understood as a network that supports a diversity of actors and propositions-the theoretical formulations of organizations were approached according to the interpretative frames concept and practices, repertoires of action in order to that were restructured to further analysis the theoretical and practical elements of the same. That argument was accompanied by rescue of the development of feminism in Brazil, especially in Rio Grande do Sul, giving rise to the context in which MMC and Coletivo Feminino Plural arise. Analyzes intra-organizational and inter-organizational were performed, choosing to do so, by a relational qualitative research, in which semi-structured interviews with the managers and coordinators of organizations interviews were used to capture mainly the repertoires of action and analysis documents to seize interpretive frameworks.

abstract: ABSTRACT Large-pore metal-organic framework (MOF) membranes offer potential in a number of gas and liquid separations due to their wide and selective adsorption capacities. A key characteristic of a number of MOF and zeolitic imidazolate framework (ZIF) membranes is their highly selective adsorption capacities for CO2. These membranes offer very tangible potential to separate CO2 in a wide array of industrially relevant separation processes, such as the separation from CO2 in flue gas emissions, as well as the sweetening of methane. By virtue of this, the purpose of this dissertation is to synthesize and characterize two linear large-pore MOF membranes, MOF-5 and ZIF-68, and to study their gas separation properties in binary mixtures of CO¬2/N2 and CO2/CH4. The three main objectives researched are as follows. The first is to study the pervaporation behavior and stability of MOF-5; this is imperative because although MOF-5 exhibits desirable adsorption and separation characteristics, it is very unstable in atmospheric conditions. In determining its stability and behavior in pervaporation, this material can be utilized in conditions wherein atmospheric levels of moisture can be avoided. The second objective is to synthesize, optimize and characterize a linear, more stable MOF membrane, ZIF-68. The final objective is to study in tandem the high-pressure gas separation behavior of MOF-5 and ZIF-68 in binary gas systems of both CO2/N2 and CO2/CH4. Continuous ZIF-68 membranes were synthesized via the reactive seeding method and the modified reactive seeding method. These membranes, as with the MOF-5 membranes synthesized herein, both showed adherence to Knudsen diffusion, indicating limited defects. Organic solvent experiments indicated that MOF-5 and ZIF-68 were stable in a variety of organic solvents, but both showed reductions in permeation flux of the tested molecules. These reductions were attributed to fouling and found to be cumulative up until a saturation of available bonding sites for molecules was reached and stable pervaporation permeances were reached for both. Gas separation behavior for MOF-5 showed direct dependence on the CO2 partial pressure and the overall feed pressure, while ZIF-68 did not show similar behavior. Differences in separation behavior are attributable to orientation of the ZIF-68 membranes. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2015

abstract: Affect signals what humans care about and is involved in rational decision-making and action selection. Many technologies may be improved by the capability to recognize human affect and to respond adaptively by appropriately modifying their operation. This capability, named affect-driven self-adaptation, benefits systems as diverse as learning environments, healthcare applications, and video games, and indeed has the potential to improve systems that interact intimately with users across all sectors of society. The main challenge is that existing approaches to advancing affect-driven self-adaptive systems typically limit their applicability by supporting the creation of one-of-a-kind systems with hard-wired affect recognition and self-adaptation capabilities, which are brittle, costly to change, and difficult to reuse. A solution to this limitation is to leverage the development of affect-driven self-adaptive systems with a manufacturing vision. This dissertation demonstrates how using a software product line paradigm can jumpstart the development of affect-driven self-adaptive systems with that manufacturing vision. Applying a software product line approach to the affect-driven self-adaptive domain provides a comprehensive, flexible and reusable infrastructure of components with mechanisms to monitor a user’s affect and his/her contextual interaction with a system, to detect opportunities for improvements, to select a course of action, and to effect changes. It also provides a domain-specific architecture and well-documented process guidelines, which facilitate an understanding of the organization of affect-driven self-adaptive systems and their implementation by systematically customizing the infrastructure to effectively address the particular requirements of specific systems. The software product line approach is evaluated by applying it in the development of learning environments and video games that demonstrate the significant potential of the solution, across diverse development scenarios and applications. The key contributions of this work include extending self-adaptive system modeling, implementing a reusable infrastructure, and leveraging the use of patterns to exploit the commonalities between systems in the affect-driven self-adaptation domain. / Dissertation/Thesis / Doctoral Dissertation Computer Science 2016

Made available in DSpace on 2016-06-02T19:05:36Z (GMT). No. of bitstreams: 1 1977.pdf: 7827443 bytes, checksum: b7d5ce8bc5bb133ce610c499fdd47f85 (MD5) Previous issue date: 2008-05-21 / Financiadora de Estudos e Projetos / Software systems must satisfy the users requeriments and use current technologies. Thus, these systems are in constant evolution and several software maintenance tasks are carried out in order to adapt them to the user s requirements as well as to the current technologies. When there is a change in the technology used by these systems, an approach to their revitalization is reengineering, which is classified as a preventive maintenance. This research project presents the iterative process applied during the reengineering of the GREN framework, which is built based on the GRN pattern language. The GREN framework was originally implemented in Smalltalk, a very spread programming language, mainly within the academic community. In the proposed reengineering process the JavaTMlanguage and AspectJ, which is an aspect-oriented JavaTMextension, were used during the framework implementation resulting from the reengineering process. This new framework is called GRENJ. The proposed process can be used to reengineer systems developed with OO paradigm, in order to change its implementation language to another OO language. That process is iterative, incremental, and applies reverse engineering patterns, test-driven development and refactoring. The GRENJ framework has approximately twenty-eight thousand source code lines, of which approximately ten thousand are related to tests created during the development. The GRENJ framework documentation was generated using the javadoc tool. A hypothetical system that satisfies the basics requirements of a rental video store was instantiated using the GRENJ framework. / Os sistemas de software devem atender aos requisitos dos usuários utilizar as tecnologias atuais. Dessa forma, esses sistemas permanecem em constante evolução e passam por várias atividades de manutenção a fim de se adequar tanto às necessidades dos usuários quanto às tecnologias. Quando há mudança de tecnologia, uma das formas de revitalizar esses sistemas é com a aplicação de reengenharia, classificada como manutenção preventiva. Este projeto de pesquisa apresenta o processo iterativo usado durante a realização da reengenharia do framework caixa-branca GREN (Gerenciamento de REcursos de Negócios), construído com base na linguagem de padrões GRN (Gerenciamento de Recursos de Negócios). O framework GREN foi implementado originalmente em Smalltalk, linguagem de programação muito difundida, principalmente, na comunidade acadêmica. No processo de reengenharia proposto, as linguagem JavaTMe AspectJ, extensão da linguagem JavaTMpara programação orientada a aspectos, foram utilizadas para implementação da nova versão do framework, denominada GRENJ (Gerenciamento de REcursos de Negócios em JavaTM). O processo de reengenharia proposto pode ser utilizado na reengenharia de outros sistemas desenvolvidos com o paradigma OO, em que a mudança de linguagem de programação é desejada, pois é iterativo, incremental, utiliza padrões de engenharia reversa, desenvolvimento guiado por testes (Test-Driven Development, TDD) e refatoração. O framework GRENJ tem aproximadamente vinte e oito mil linhas de código fonte, das quais pouco mais de dez mil estão relacionadas aos testes criados durante o desenvolvimento. A documentação desse framework foi produzida utilizando a ferramenta javadoc. Um sistema hipotético que atende aos requisitos básicos de uma locadora de DVDs foi instanciado usando o GRENJ.

Submitted by JADER BARBOSA DA SILVA FLOR null (jader@iq.unesp.br) on 2017-05-22T17:08:38Z No. of bitstreams: 1 TESE VERSÃO FINAL para a impressão.pdf: 8986552 bytes, checksum: 9b079a86ffb72f7d5def9d9e6c6ba45e (MD5) / Approved for entry into archive by Luiz Galeffi (luizgaleffi@gmail.com) on 2017-05-23T17:35:16Z (GMT) No. of bitstreams: 1 flor_jbs_dr_araiq.pdf: 8986552 bytes, checksum: 9b079a86ffb72f7d5def9d9e6c6ba45e (MD5) / Made available in DSpace on 2017-05-23T17:35:16Z (GMT). No. of bitstreams: 1 flor_jbs_dr_araiq.pdf: 8986552 bytes, checksum: 9b079a86ffb72f7d5def9d9e6c6ba45e (MD5) Previous issue date: 2017-05-03 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Neste projeto foram sintetizados e caracterizados materiais porosos conhecidos como Metal-Organic Frameworks (MOFs) que abrangem uma área da química que tem experimentado um crescimento muito grande nas duas últimas décadas. MOFs são compostos cristalinos contendo espaços potencialmente vazios (poros) construídos a partir de íons ou clusters metálicos interconectados por espaçadores orgânicos. Além da diversidade estrutural e topológica, estes materiais têm enorme potencial para muitas aplicações. Dentro desse contexto, o objetivo central do trabalho foi a preparação de MOFs de cobre(II) e zinco(II) e investigação da potencialidade de aplicação em catálise heterogênea. Dentre outros materiais, a MOF MOF-INZ foi preparada pela primeira vez a partir da funcionalização da HKUST-1 via processo PSM (Pos-Synthetic Modification) pela coordenação da isoniazida nos centros coordenativamente insaturados (CUSs) do íon cobre(II) do material precursor ativado. A utilização desse material como catalisador em reações de cicloadição de CO2 frente ao epóxido de propileno resultou em 95% de conversão do reagente em carbonato de propileno (após 72 horas, em presença de TBAI). A última etapa do trabalho consistiu na preparação das MOFs ZIF-8 e HKUST-1 em escala nanométrica, usando moduladores de concentração, e no desenvolvimento de uma técnica muito elegante para a formação de filmes finos sobre nanotubos de dióxido de titânio (com diâmetros da ordem de 50-100 nm). Os materiais híbridos preparados foram então submetidos a reações foto- e fotoeletrocatalíticas de redução de CO2. As MOFs adsorvidas nos eletrodos nanoestruturados mostraram atividades significativamente mais altas em comparação com o eletrodo não modificado. Sob irradiação de luz e na presença de ácido ascórbico, o compósito Ti/TiO2-ZIF-8 gerou cerca de 30 mmol/L de etanol e 2 mmol/L de metanol em fase gasosa, enquanto que reações fotoeletrocatalíticas de redução de CO2 produziram 104 mmol/L e 17 mmol/L desses mesmos produtos, respectivamente. Do que seja do nosso conhecimento, essa é a primeira vez que a redução fotoeletrocatalítica desse importante gás causador do efeito estufa é realizada sobre materiais baseado em MOFs e abre uma frente de pesquisa bastante promissora no que tange a introdução dessa importante classe de materiais porosos no design de fotoeletrocatalisadores para reações gasosas. / In this project, porous materials known as Metal-Organic Frameworks (MOFs) were synthesized and characterized, which cover a chemistry area that has experienced a very large growth in the last two decades. MOFs are crystalline compounds containing potentially empty spaces (pores) constructed from ions or metal clusters interconnected by organic spacers. In addition to structural and topological diversity, these materials have enormous potential for many applications. In this context, the main objective of the work was the preparation of copper (II) and zinc (II) MOFs and the investigation of the potentiality of application in heterogeneous catalysis. Among other materials, MOF MOF-INZ was prepared for the first time from the functionalization of HKUST-1 via PSM (Post-Synthetic Modification) process by the coordination of isoniazid to the coordinated unsaturated (CUSs) centers of the copper (II) activated precursor. The use of this material as a catalyst in CO2-cycloaddition reactions to propylene epoxide resulted in 95% conversion of the reactant into propylene carbonate (after 72 hours in the presence of TBAI). The last stage of the work consisted in the preparation of the ZIF-8 and HKUST-1 MOFs at nanoscale using concentration modulators and the development of a very elegant technique for the formation of thin films on titanium dioxide nanotubes (with diameters in the order of 50-100 nm). The prepared hybrid materials were then submitted to photo- and photoelectrocatalytic CO2 reduction reactions. The MOFs adsorbed on the nanostructured electrodes showed significantly higher activities compared to the unmodified electrode. Under light irradiation and in the presence of ascorbic acid, the Ti / TiO2-ZIF-8 composite generated about 30 mmol / L of ethanol and 2 mmol / L of methanol in the gas phase, while photoelectrocatalytic CO2 reduction reactions produced 104 Mmol / L and 17 mmol / L of these same products, respectively. To our knowledge, this is the first time that the photoelectrocatalytic reduction of this important greenhouse gas is carried out on materials based on MOFs and opens a very promising research front regarding the introduction of this important class of porous materials in the design of photoelectrocatalysts for gaseous reactions.

Introdução: Quando os dilemas éticos surgem no âmbito de assistência à saúde, surge a necessidade de fazer uma reflexão no âmbito da Bioética Clínica, que pode ser entendida como sendo a identificação, análise e resolução de problemas ou dilemas morais que surgem no cuidado individual de pacientes. Embora as questões práticas sejam usualmente priorizadas na assistência ao paciente, é reconhecida a importância da teoria nos modelos de tomada de decisão. Quando a atenção se volta para a prática, descobrimos regras complexas de ação e percepção que raramente são discutidas. O Modelo da Bioética Complexa busca agregar estas visões, e sugere que a Bioética é uma reflexão complexa, compartilhada e interdisciplinar sobre a adequação das ações que envolvem a vida e o viver. Objetivos: O objetivo desta tese é analisar as consultorias de Bioética Clínica realizadas em um hospital geral universitário de grande porte, verificando os aspectos teóricos e práticos identificados e as suas interações. Métodos: Foi realizado um estudo transversal das 317 consultorias de Bioética Clínica realizadas no Hospital de Clinicas de Porto Alegre de fevereiro de 2009 até abril de 2013, que tiveram registros nos prontuários de 300 pacientes internados. O levantamento dos prontuários foi fornecido pelo Serviço de Arquivo Médico e Informações em Saúde, que é o responsável pela guarda e manutenção destes registros. Os referenciais teóricos utilizados foram analisados a partir da abordagem complexa da Bioética, utilizando quatro grandes referenciais: Virtudes, Princípios, Direitos Humanos e Alteridade. Os temas das consultorias foram analisados de acordo com a classificação proposta pela National Reference Center for Bioethics Literature, da Georgetown Law Library, adaptada nesta tese. Resultados: Foi possível identificar que 94,7% dos solicitantes eram médicos e 5,3% eram enfermeiros. Os Serviços que mais solicitaram consultorias foram o de Medicina Interna (22,3%), Pediatria (15,7%) e Psiquiatria (9,3%). O referencial das Virtudes estava presente em 99,3% dos casos, o dos Princípios em 99,0%; o dos Direitos Humanos em 97,3% e o da Alteridade em 94,4%. Dos pacientes, 50,0% eram do sexo feminino, com idade média de 37,42 + 25,61 anos, e tempo médio de internação de 52,1+120,82 dias. Destes, 63,0% tiveram alta para o domicílio e 33,3% foram a óbito. Os três temas mais frequentes nas consultorias foram: Morte e Morrer, (81,7%), Relacionamento Profissional (66,0%), e Consentimento Informado (64,7%). A média anual de consultorias foi de 78,0 e a mensal de 6,52, e o tempo para responder às consultorias foi, em média, de 40,0+102,1 horas. Avaliando os aspectos translacionais em prontuário, foi possível identificar que em 73,3% houve transposição evidente das condutas sugeridas para a prática assistencial. Conclusão: As características dos profissionais que solicitaram consultorias, para quais pacientes ocorreram estas solicitações, e os respectivos seviços médicos associados, possibilitaram identificar os temas mais relevantes nas consultorias de Bioética Clínica, e quais os referenciais teóricos que estão envolvidos nestes problemas éticos. Esta análise permitiu verificar a interação existente entre teoria e prática e a transposição das reflexões da Bioética à assistência aos pacientes. / Background: When ethical dilemmas arise in the context of health care, arises the need to think in the Clinical Ethics field, which can be understood as the identification, analysis and resolution of problems and moral dilemmas that arise in the individual patients care. Although practical issues are usually prioritized in patient care, the importance of theory in models of decision making process is recognized. When attention turns to practice, we find complex rules of action and perception that are rarely discussed. The Complex Bioethics Model intended to add these visions, and suggests that bioethics is a complex, interdisciplinary and shared reflection on the actions adequacy involving life and living. Objective: The aim of this thesis is analyze the Clinical Ethics consultations performed in a large general university hospital, verifying theoretical and practical aspects identified and their interactions. Methods: A cross-sectional study was conducted with 317 Clinical Bioethics consultations performed at Hospital de Clinicas de Porto Alegre in February 2009 until April 2013, registered in 300 inpatients medical records. The Medical Records and Health Information Service, responsible for the custody and maintenance of these records, provided medical records survey. The theoretical frameworks were analyzed using the bioethics complex approach to, using four major benchmarks: Virtues, Principles, Human Rights and Alterity. The consultations themes were analyzed according to the classification proposed by the National Reference Center for Bioethics Literature, the Georgetown Law Library, adapted for this purpose. Results: We found that 94.8 % of applicants were physicians and 5.3 % were nurses. Services that most requested consultations were Internal Medicine (22.3%), Pediatrics (15.7%) and Psychiatry (9.3%). The Virtues benchmark was present in 99.3% cases, Principles in 99.0%, Human Rights in 97.3 % and Alterity in 94.4 %. About patients, 50.0 % were female, mean age was 37.42 + 25.61 years, and mean hospital stay 52.1 days +120.82. Of these, 63.0 % were discharged home and 33.3 % died. The three most frequent themes in consultations were: Death and Dying, (81.7%), Professional Relationship (66.0%), and Informed Consent (64.7%). Annual consultations average was 78.0 and monthly average 6.52, time to respond to consultations was on average 40.0 +102.1 hours. Evaluating patient records translational aspects, we found that 73.3% had evident transposition of conduct suggested for clinical practice. Conclusion: Professionals characteristics of those who have requested consultations, which patients had these requests and their associated medical services, allowed to identify the most relevant Clinical Bioethics consultations topics, and which theoretical frameworks are involved in these ethical problems. This analysis enables to verify the theory and practice interaction and the transposition of the Bioethics reflections to patients’ assistance.

A presente pesquisa tem como objetivo analisar as relações estabelecidas entre as formulações teóricas e práticas no campo do feminismo. Para tanto, consistem em objeto empírico deste trabalho o Movimento de Mulheres Camponesas (MMC) e a organização não-governamental (ONG) Coletivo Feminino Plural, ambas com atuação no estado do Rio Grande do Sul e identificadas com o feminismo. A partir do conceito movimento social para tratar do feminismo – que passa a ser entendido enquanto rede que admite uma diversidade de atores e proposições-, as formulações teóricas das organizações foram abordadas segundo o conceito quadros interpretativos e as práticas, repertórios de ação, afim de que fossem reestruturados para posterior análise os elementos teóricos e práticos das mesmas. Tal argumentação foi acompanhada pelo resgate do desenvolvimento do feminismo no Brasil, em especial no Rio Grande do Sul, fazendo emergir o contexto no qual MMC e Coletivo Feminino Plural surgem. Análises intra-organizacionais e inter-organizacionais foram realizadas, optando-se, para isso, por uma pesquisa qualitativa relacional, na qual foram utilizadas entrevistas semi-estruturadas com as dirigentes e coordenadoras das organizações para apreender, principalmente, os repertórios de ação e análise de documentos para apreender os quadros interpretativos. / This research aims to analyze the relations established between theoretical formulations and practices in the field of feminism. For this purpose, consist of empirical object of this work the Movimento de Mulheres Camponesas (MMC) and the non-governmental organization (NGO) Coletivo Feminino Plural, both with operations in the state of Rio Grande do Sul and identified with feminism. From concept to treat social movement of feminism - which happens to be understood as a network that supports a diversity of actors and propositions-the theoretical formulations of organizations were approached according to the interpretative frames concept and practices, repertoires of action in order to that were restructured to further analysis the theoretical and practical elements of the same. That argument was accompanied by rescue of the development of feminism in Brazil, especially in Rio Grande do Sul, giving rise to the context in which MMC and Coletivo Feminino Plural arise. Analyzes intra-organizational and inter-organizational were performed, choosing to do so, by a relational qualitative research, in which semi-structured interviews with the managers and coordinators of organizations interviews were used to capture mainly the repertoires of action and analysis documents to seize interpretive frameworks.