Made available in DSpace on 2016-04-18T21:43:56Z (GMT). No. of bitstreams: 5 Wilma Maria Sampaio Lima1.pdf: 1215062 bytes, checksum: 205e94d96866af229f6586b6d866f885 (MD5) Wilma Maria Sampaio Lima2.pdf: 2183228 bytes, checksum: d19455673abca3032810811ec288a317 (MD5) Wilma Maria Sampaio Lima3.pdf: 3619173 bytes, checksum: 9b48aed6a3ded01bacb4e5fdca4f25d1 (MD5) Wilma Maria Sampaio Lima4.pdf: 3282636 bytes, checksum: 05e58ae394f36e8e108cfcaa9e6b6ee5 (MD5) Wilma Maria Sampaio Lima5.pdf: 1213062 bytes, checksum: d2325267f071d69bdec9f8bb96dc3650 (MD5) Previous issue date: 2009-09-01 / Man is an animal that writes letters this phrase is present in a Lewis Carroll s letter, it not only points out the importance of correspondence in the author s life but it also suggests that the genre plays a fundamental role in the construction and expression of human identity. Nevertheless, the study of the genres ( discursive and textual) at school is focused on the presentation of standardized model for reading and, by producing, exercise the writing of texts which do not circulate outside the classroom. That is what is inferred from the analysis of the work with the letter genres especially personal letters present in thirteen compilations for the initial grades of Elementary Education (2nd to 5th grades) part of the Programa Nacional para o Livro Didático 2007 (PNLD). In these grades, there are general concepts about letters which are expected to be known by the students and used at the following grades, and it has become relevant, in this paper, to compare this knowledge: a) with concepts by different theorists about discursive genres and textual genres, what allowed to observe a reductive conception of them in school manuals; b) with a brief history of the letter genre, which showed a proximity between the models brought to the students and the proposals of the medieval rhetoric, distancing itself from positions turned to a diversity of individual constructions before each discursive situation, used, between other ages, in the nineteenth century, when Lewis Carroll produced his literary works and letters; c) with the data from a survey made in a private school, with 226 students from the 5th, 7th and 8th grades, which inquired their concepts about letters and which suggests that there is a remarkable distance between the standardized information in the manuals up to the 5th grade and the knowledge built by the student in the same period and in the following grades while, through writing letters in traditional supports, such as paper, and new ones, such as email, they exercise an effective social participation outside school; d) with the use that writers make of the creative aspects of letters, taking as an example, Lewis Carroll s letters written to children in the nineteenth century and bearing in mind, in this point of view, the weight of the Alice s Adventures in Wonderland s author in the world or literary production for children and his extensive epistolary production; from this proximity it was possible not only the contrast it with the artificiality of the models presented in school manuals, but also the resumption of the role of writers epistolary production in harboring the literary system and in the reception of the texts by the readers. These are some conclusions of this paper: a) the teaching of letter as a genre, present in school manuals, has underestimated the knowledge contemporary students have about letters; b) the work with letters in manuals do not consider the importance of some material aspects of the text (size, format, texture etc.) in the construction of meanings by the reader, as the students point out as necessary to the effects they expect to cause with their production outside school; the student s contact with letters written by Brazilian and foreign authors, contemporary or not, is a way to a more meaningful work of writing as a solution of a problematic situation , not a sheer model reproduction exercise; d) the reading of an author s correspondence can be an open door to his literary production; e) the contact with writer s letters and other authentic texts allows to bring, to school space, discussions about the ethics of publication of what initially belonged to the private space, which is permeating the epistolary study. This present work does not aim to be a manual of teaching letters at school, but to discuss ideas that help teachers to reflect about their work and find means to get them closer to the premises of Parâmetros Curriculares Nacionais which say that the linguistic knowledge learned at school must allow the students to have an effective social participation, the exercise of citizenship, which is defined as a possibility of the construction and expression of ideas, feelings and their own identity in the interaction with the diversity of ideas, feelings and identities mediated by reading and writing texts. / O homem é um animal que escreve cartas essa frase presente em carta de Lewis Carroll, não só aponta a importância da correspondência na vida do autor, como também sugere um papel primordial do gênero na construção e expressão da identidade humana. Entretanto o estudo de gêneros (discursivos e textuais) na escola se mostra voltado para apresentar modelos padronizados para leitura e, pela produção, exercitar a escrita de textos que não circulam para além da sala de aula. É o que se infere da análise do trabalho com os gêneros da correspondência especialmente das cartas pessoais presente em treze coleções para as séries iniciais do Ensino Fundamental (2º ao 5º ano), parte do Programa Nacional para o Livro Didático 2007 (PNLD). Nessas séries, veiculam-se conceitos gerais sobre cartas que, espera-se, sejam conhecimentos de que os alunos se valham nas séries posteriores, o que tornou relevante, nesta tese, confrontar esses conhecimentos: a) com conceitos de teóricos diversos sobre gêneros discursivos e gêneros textuais, o que permitiu observar uma conceituação redutora dos mesmos pelos manuais escolares; b) com um breve histórico do gênero carta, o que apresentou uma proximidade entre os modelos trazidos aos alunos e as propostas da retórica medieval, distanciando-se de posições voltadas para a diversidade de construções individuais frente a cada situação discursiva, veiculadas, entre outros períodos, no século XIX, época em que Lewis Carroll produziu sua obra literária e epistolar; c) com dados de pesquisa realizada em escola particular, com 226 alunos de 5º, 7º e 8º ano, que investigou seus conceitos sobre cartas e que sugere haver uma distância bem marcada entre as informações padronizadas dos manuais até o 5º ano e os conhecimentos construídos pelo aluno no mesmo período e em séries posteriores enquanto, por meio da escrita de cartas em suportes tradicionais, como o papel, e novos, como o e-mail, exercitam uma participação social efetiva fora da escola; d) com o uso que escritores fazem da face criativa da carta, tomando, como exemplos, cartas de Lewis Carroll escritas para crianças no século XIX e tendo-se em mente, nessa escolha, o peso do autor de As aventuras de Alice no País das Maravilhas na produção literária infantil mundial e sua extensa produção epistolar; dessa aproximação, foi possível não só o contraste com a artificialidade dos modelos apresentados nos manuais escolares, como também a retomada do papel da produção epistolar dos escritores na alimentação do sistema literário e na recepção dos textos pelos leitores. São algumas conclusões deste trabalho que: a) o ensino de gêneros da correspondência, presente nos manuais escolares, tem subestimado os conhecimentos que os alunos contemporâneos possuem sobre cartas; b) o trabalho com cartas nos manuais apaga a importância dos aspectos materiais do texto (tamanho, forma, textura etc.) na construção de sentidos pelo leitor, enquanto os alunos os salientam como necessários aos efeitos que esperam provocar com sua produção de cartas fora da escola; c) o contato de alunos com cartas escritas por autores estrangeiros e brasileiros, contemporâneos ou não é um caminho para trabalho mais significativo de escrita como resolução de situações-problema, não mero exercício de reprodução de modelos; d) a leitura da correspondência de um autor pode ser uma das portas de entrada para a leitura de sua produção literária; e) o contato com cartas de escritores e outros textos autênticos permite trazer, para o espaço escolar, discussões sobre a ética da publicação do que, inicialmente, pertenceu ao espaço privado, que vem permeando os estudos da epistolografia. O presente trabalho não se pretende como manual de ensino de cartas na escola, mas como espaço de discussão de ideias que ajudem professores a refletir sobre o trabalho que realizam e buscar meios de aproximá-lo melhor da premissa dos Parâmetros Curriculares Nacionais de que os conhecimentos linguísticos conseguidos na escola devem permitir ao aluno a participação social efetiva, o exercício da cidadania, que circunscrevemos como a possibilidade de construção e expressão de ideias, sentimentos e da própria identidade na interação com a diversidade de ideias, sentimentos e identidades mediadas pela leitura e escrita de textos.

M.A. / Although a serious Christian apologist and academic writer, Clive Staples Lewis was also well known (and loved) for his fictional works. Lewis was of the opinion that one's faith and chosen profession cannot be separated and he thus aligned the two in his own writing (Schultz and West 1998: 120). Therefore, his writings reflect his Christian faith (after his conversion in 1931) and, although his Ransom (Cosmic) Trilogy (1938, 1943 and 1945), mythological work Till We Have Faces (1956) and The Chronicles of Narnia (1950-1956) are not openly theological, they all deal with figurative representations of both Christ and the Biblical devil. Many studies have explored Lewis's portrayal of Biblical truths in his fictional writing. As Christopher Mitchell pointed out in his essay entitled "Bearing the Weight of Glory," a few months before his death, Lewis stated that he was writing in order to bring about an encounter between the reader and Christ (Mills 1998: 5). While on the surface these novels are not emphatically about the battle between heaven and hell, underlying the stories is a broader message of rivalry between good and evil. A student of Lewis's, Harry Blamires, remembers Lewis saying that he went about the task of writing The Chronicles of Narnia much as he did the writing of his serious theological work, Mere Christianity (Mills 1998: 15). Much research has thus been conducted to explore Lewis's portrayal of God in his fiction, yet there has been very little research on his metaphysical perspective on Satan. His fictional novels — most notably The Chronicles of Namia — are largely allegorical and often subtly allude to the devil through the characters. It is this subtle allusion to evil, and specifically characteristics of the Biblical Satan in The Chronicles, that I would like to explore in this dissertation.

Cette thèse porte sur la production d'acide lactique par conversion de la biomasse lignocellulosique catalysée par des acides de Lewis solides dans l'eau puis l'estérification d'acide lactique aqueux avec de l'éthanol. La conversion de la cellulose est étudiée en autoclave, en utilisant comme catalyseurs, de la zircone et de l'alumine contenant du W ou Sn (ZrW, AlSn) et différents hydroxydes métalliques. L'étude de la conversion de la cellulose en acide lactique en présence de ZrW non calcinée, ZrW calcinée, Zr(OH)4 et ZrO2, montre que la phase active du catalyseur est constituée de Zr4+, les centres acides de Lewis et de groupes hydroxyles. Les performances catalytiques des catalyseurs AlSn, préparés à partir de chlorure d'étain comme précurseur, dépendent fortement de la présence résiduelle de chlorure, ce qui favorise la formation d'acide lévulinique. Les hydroxydes de certains métaux de transition se sont révélés être des catalyseurs solides efficaces pour la conversion de la cellulose en acide lactique. Il a été observé que le rendement en acide lactique dépend de la concentration et de la basicité des groupes OH superficiels des hydroxydes de métaux de transition et de la présence de sites acides de Lewis. L'estérification de l'acide lactique, à différentes concentrations en l'eau, a été étudiée en présence d'Amberlyst 15, de charbon sulfoné et d'oxyde de graphène pour étudier l'activité et la tolérance à l'eau de catalyseurs solides acides à base de carbone. Il est montré, par calorimétrie d'adsorption d'ammoniac, que l'oxyde de graphène présente des sites superacides et qu'il conduit à la plus grande activité et tolérance à l'eau. L'augmentation de la teneur en eau montre un fort effet inhibiteur sur l'activité du charbon sulfoné alors que d'Amberlyst 15 et l'oxyde de graphène sont plus tolérants. Les catalyseurs ne sont pas stables dans des conditions d'estérification, en présence d'eau / This thesis reports the synthesis of lactic acid from lignocellulosic biomass catalyzed by solid Lewis acid catalysts in water and then esterification of aqueous lactic acid solutions with ethanol. The cellulose conversion was tested in autoclave, in hot water, using zirconia and alumina containing W or Sn (ZrW, AlSn) and different solid metal hydroxides. The conversion of cellulose to lactic acid using uncalcined ZrW, calcined ZrW, Zr(OH)4 and ZrO2 shows that the active surface of the catalyst consists of Zr4+ Lewis centers and OH groups. The catalytic performances of AlSn catalysts, prepared from Sn chloride as precursors, strongly depend on the residual amount of chloride which favors the formation of levulinic acid. Some hydroxides of transition metals were disclosed as efficient solid catalysts for the conversion of cellulose to lactic acid. The yield of lactic acid was observed to depend on the concentration and the basicity of the superficial OH groups and on the presence of Lewis acid sites. The esterification of lactic acid, at different concentrations in water, was studied using Amberlyst 15, sulfonated carbon and graphene oxide to evaluate the activities and water tolerance of carbon based solid catalysts. Graphene oxide, shown by calorimetry of NH3 adsorption to exhibit super-acid sites, leads the highest activity and water tolerance. Increasing amounts of water has a strong inhibiting effect on the activity of sulfonated carbon and less influence on activity of Amberlyst 15 and graphene oxide. However, all catalysts were not stable in esterification conditions, in presence of water

Les glucides, les biomolécules les plus abondants dans la nature, sont essentiels pour le maintien et la survie des organismes. Certaines molécules à base de glucides à la fois d'origine synthétique et naturelle sont connues pour leurs activités pharmacologiques et utilisés pour traiter différentes maladies. Deux projets ont été réalisés sur la base d'oligosaccharides biologiquement actifs dans cette thèse. Sialyl Lewis X (sLex), un tétrasaccharide exprimé sur la surface cellulaire d'un tissu embryonnaire et un tissu tumoral, a été découvert pour jouer un rôle important dans l'adhésion entre les cellules tumorales et les cellules endothéliales dans les métastases tumorales à travers la liaison de E-sélectine avec une forte affinité et sélectivité. E-sélectine est un membre de famille des sélectines des molécules d'adhésion cellulaire, exprimée sur l'endothélium tumoral qui est activé par la cytokine. En conséquence, un type de sonde moléculaire basé sur sLex a été conçu et synthétisé dans le but de diagnostiquer le cancer. Aminoéthyle glycoside de sLex 36 a été efficacement préparé à partir de quatre synthons monosaccharidiques par sept étapes d’une manière hautement stéréosélective et régiosélective avec un rendement total de 18%. La sonde moléculaire conjuguant 36 avec une protéine marqué a été montré capable de visualiser une tumeur implantée chez la souris par imagerie in vivo, alors que le contrôle négatif a donné seulement un profil de circulation vasculaire. Ce travail est actuellement dans le processus d'un dépot de brevet. D'autre part, le mécanisme de traitement des N-glycanes par l'endo-α-mannosidase et les inhibiteurs de cette enzyme ont été étudiés. Décorations de N-glycane existent sur la plupart des protéines eucaryotes et leurs compositions aberrantes sont associés à diverses maladies, y compris les infections virales et le cancer. Endo-α-mannosidase hydrolyse la liaison α-1,2-mannosidique entre le mannose en glucose-substitué et le reste de la N-glycane dans l'appareil de Golgi, en fournissant une voie indépendante de glucosidase I et II pour la maturation de N-glycane. Le but de présente étude est de confirmer le mécanisme catalytique nouvellement proposé pour endo-α-mannosidase: la participation du groupe voisin via un 1,2-anhydro intermédiaire de sucre. Etant donné que cet intermédiaire est instable, le glycosyl-1,2-β-anhydro carbasucre 53 a été conçu et synthétisé pour soutenir l'existence de cet intermédiaire pour l'hydrolyse catalysée par glycosidase. De plus, le glycosyl-1,2-β-aziridine carbasucre 64 et le glycosyl-1,2-oléfinique carbasucre 63 ont été conçus et synthétisés comme nouveaux inhibiteurs d’endo-α-mannosidase pour le développement d'agents thérapeutiques. En outre, le glycosyl-1,2-α-anhydro carbasucre 52 et le glycosyl-1,2-α-aziridine carbasucre 65 ont également été synthétisés comme références. Tous les composés cibles ont été préparés de manière efficace à partir du même glycosyl-carbasucre qui a été obtenu de D-(+)-maltose par plusieurs étapes de protections, de modifications, du réarrangement de Claisen. L'évaluation biologique est en cours. / As the most abundant biomolecules found in nature, carbohydrates are essential for sustaining and survival of organisms. Some carbohydrate-based molecules both of synthetic and natural origin are known for their pharmacological activities and used to treat different diseases. Two projects were carried out based on biologically active oligosaccharides in this thesis. Sialyl Lewis X (SLex), which is a tetrasaccharide expressed on cell surface of embryonic tissue and tumor tissue, was discovered to play an important role in the adhesion between tumor cells and blood endothelial cells in tumor metastases through binding E-selectin with high affinity and selectivity. E-selectin is a member of the selectin family of cell adhesion molecules, expressed on cytokine activated tumoral endothelium. Accordingly, a kind of molecular probe based on sLex was designed and synthesized for the purpose of diagnosing cancer. Aminoethyl glycoside of sLex 36 was efficiently prepared from four monosaccharide building blocks through seven steps with high stereoselectivity and regioselectivity in 18% total yield. The molecular probe conjugating 36 with a labelled scaffold protein was shown to visualize an implanted tumor in the mouse by in vivo imaging, whereas the negative control gave only a vascular circulation profile. This work is currently in the process of a patent application. On the other hand, N-linked glycans processing mechanism by endo-α-mannosidase and this enzyme’s inhibitors were studied. N-glycan decorations exist on the majority of eukaryotic proteins and their aberrant compositions are associated with various diseases, including viral infection and cancer. Endo-α-mannosidase hydrolyzes the α-1,2-mannosidic bond between the glucose-substituted mannose and the rest of the N-glycan in Golgi apparatus, providing a glucosidase I and II independent pathway for the maturation of N-glycan. The aim of the present study is to confim the newly proposed catalytic mechanism for endo-α-mannosidase: neighboring group participation via a 1,2-anhydro sugar intermediate. Since this intermediate is unstable, glycosyl-1,2-β-anhydro carbasugar 53 was designed and synthesized to support the existence of this intermediate for glycosidase-catalyzed hydrolysis. Moreover, glycosyl-1,2-β-aziridine carbasugar 64 and glycosyl-1,2-olefinic carbasugar 63 were designed and synthesized as novel endo-α-mannosidase inhibitors for the development of therapeutic agents. In addition, glycosyl-1,2-α-anhydro carbasugar 52 and glycosyl-1,2-α-aziridine carbasugar 65 were also synthesized as compare. All the target compounds were prepared efficiently from the same glycosyl-carbasugar that was obtained from D-(+)-maltose through several steps of protections, modifications, and Claisen rearrangement. The biological evaluation is underway.

The goal of the present thesis is a corpus stylistic analysis of Alice in Wonderland (1865), and it presents the possibilities of using corpus methods in the study of literary texts. In the theoretical part, the thesis is concerned with an explanation of the words norm, foregrounding, deviance and prominence (Leech, 2008), which are key terms in stylistics. The text then focuses in detail on various concerns connected to keywords and clusters, which are investigated later on in the theoretical part. The relation of keywords to the reference corpus and aspects of the length and frequency of occurrence of clusters are analyzed. An important element in a corpus-based analysis is that it is supposed to decrease bias, as the researcher studies statistically based significant markers of the text. The next part of the thesis focuses on the position of Alice in Wonderland between other members of the children's literature of the Golden Age (Knowles & Malmkjaer, 1995), and the role of nonsense and non-observance of pragmatic principles of interaction in the text. The reference corpora are described and primary hypotheses stated. In the practical part, keywords are studied first. They are divided into part of speech categories and interpreted from the point of view of their role and mutual relations in the text....

Over 1150 m of middle to late Eocene nonmarine arkose, lithic arkose, mudstone, and siltstone, referred to here as the Chambers Creek beds, are int~r.stratified with, and overlain by over 1600 m of late Eocene-Oligocsne(?) andesitic volcaniclastic and subordinate volcanic rocks assigned to the Ohanapecosh Formation, in a dissected structural high in the southern Washington Cascade Range, about 18 km south-southeast of the town of Packwood.

The purpose of this project was to prepare a group interpretation script based upon the life of Sinclair Lewis and to direct a production of the script. Major sources for the script are Mark Schorer, Sinclair Lewis: An American Life; Grace Hegger Lewis, With Love From Gracie; and Vincent Sheean, Dorothy and Red. The script employs five readers and has a performance time of approximately fifty-five minutes. The thesis includes a biography of Lewis, a justification for the project, the purpose and procedures followed, as well as discussions of the production concept, adapting material for group interpretation, direction, rehearsal procedures, and evaluations of the script and the performance. The complete script is also included in the thesis.

[ES] Las zeolitas son catalizadores ampliamente utilizados en una gran variedad de procesos químicos, por lo que la optimización de sus propiedades físico-químicas es fundamental para mejorar su aplicación en procesos de interés industrial y medioambiental. En la presente tesis doctoral se proponen diversas metodologías de síntesis directa y post-sintéticas con el fin de controlar aspectos importantes de estos materiales desde la escala microscópica hasta la molecular y atómica, así como su implicación directa en su aplicación como catalizadores y/o materiales conductores. En un primer objetivo, se estudia la influencia del tamaño de cristal y la estructura zeolítica en la transformación selectiva de CO2 hacia productos de interés como olefinas y aromáticos cuando se combina con un catalizador de hierro dopado con potasio. Por un lado, la estructura zeolítica tipo MFI (poro medio) permite maximizar la formación de productos aromáticos, mientras que las zeolitas tipo CHA (poro pequeño) y beta (poro grande) favorecen la formación de olefinas ligeras en distinta proporción. La utilización de las zeolitas ácidas nanocristalinas permite incrementar la formación de olefinas ligeras y aumentar el tiempo de vida de los catalizadores bifuncionales. Asimismo, se estudia el efecto del confinamiento a nivel molecular de diferentes estructuras zeolíticas de poro pequeño con distinto tipo de cavidad para la reacción de metanol a olefinas (MTO), pudiéndose correlacionar la selectividad hacia distintas olefinas ligeras con un parámetro teórico que depende de las dimensiones y la forma de las cavidades de los materiales microporosos. En segundo lugar, se estudia la estabilización de distintas especies metálicas en posiciones extra-red de los materiales zeolíticos, controlando su formación desde átomos individuales a clústeres y/o nanopartículas. La estructura de la zeolita CHA permite encapsular nanopartículas de Pt en el interior de sus cavidades, que son activas y estables para la reacción de oxidación de CO incluso tras tratamientos de envejecimiento a elevadas temperaturas. Por otro lado, se racionaliza la formación de nanopartículas de germanio dispersas en distintas matrices zeolíticas híbridas aprovechando la labilidad del germanio en la red cristalina de las mismas para su aplicación como materiales conductores. Se realiza una optimización de dichos materiales híbridos orgánicos-inorgánicos basados en nanopartículas de Ge mediante diversos tratamientos post-sintéticos, maximizando la dispersión de las nanopartículas y la formación de especies carbonosas para, finalmente, evaluar sus propiedades como materiales conductores. En último lugar, se utiliza esa labilidad del Ge en posiciones cristalinas de las zeolitas como estrategia para controlar a escala atómica la incorporación selectiva de distintos heteroátomos (Si y Sn). La síntesis de la estructura ITT con poros extra-grandes está limitada a bajas relaciones de Si/Ge, presentando por tanto una limitada estabilidad hidrotermal. Por ello, se lleva a cabo una sustitución isomórfica de átomos de Ge por átomos de Si, mejorando la estabilidad hidrotermal de dicho material para su aplicación en la reacción de craqueo catalítico de un gasoil de vacío, posibilitando su regeneración, y obteniendo similar selectividad a diésel y más propileno que con la muestra de origen. Por otro lado, se incorpora selectivamente Sn en la estructura BEC (polimorfo C de la zeolita beta) mediante tratamientos post-sintéticos en los defectos estructurales generados tras la eliminación de átomos de Ge, favoreciéndose la formación de sitios "abiertos" de Sn, que han demostrado ser más activos para reacciones de moléculas oxigenadas en comparación a los sitios "cerrados" de Sn. Las ventajas catalíticas del material Sn-BEC sintetizado se demuestran en la reacción Meerwein-Ponndorf-Verley-Oppenauer (MPVO), obteniéndose mayores velocidades de reacción por sitio de Sn "abierto" que con la zeolita Sn-beta(F) convencional. / [CA] Les zeolites són catalitzadors àmpliament utilitzats en una gran varietat de processos químics, per la qual cosa l'optimització de les seues propietats fisicoquímiques és fonamental per a millorar la seua aplicació en processos d'interès industrial i mediambiental. En la present tesi doctoral es proposen diverses metodologies de síntesi directa i post-sintètiques amb la finalitat de controlar aspectes importants d'aquests materials des de l'escala microscòpica fins a la molecular i atòmica, així com la seua implicació directa en la seua aplicació com a catalitzadors i/o materials conductors. Com a primer objectiu, s'estudia la influència de la grandària de cristall i l'estructura zeolítica en la transformació selectiva de CO¿ cap a productes d'interès com a olefines i aromàtics quan es combina amb un catalitzador de ferro dopat amb potassi. D'una banda, l'estructura zeolítica tipus MFI (porus mitjà) permet maximitzar la formació de productes aromàtics, mentre que les zeolites tipus CHA (porus xicotet) i beta (porus gran) afavoreixen la formació d'olefines lleugeres en diferent proporció. La utilització de les zeolites àcides nanocristalines permet incrementar la formació d'olefines lleugeres i augmentar el temps de vida dels catalitzadors bifuncionals. Així mateix, s'estudia l'efecte del confinament a nivell molecular de diferents estructures zeolítiques de porus xicotet amb diferent tipus de cavitat per a la reacció de metanol a olefines (MTO), podent-se correlacionar la selectivitat cap a diferents olefines lleugeres amb un paràmetre teòric que depèn de les dimensions i la forma de les cavitats dels materials microporosos. En segon lloc, s'estudia l'estabilització de diferents espècies metàl·liques en posicions extra-xarxa dels materials zeolítics, controlant la seua formació des d'àtoms individuals a clústers i/o nanopartícules. L'estructura de la zeolita CHA permet encapsular nanopartícules de Pt a l'interior de les seues cavitats, actives i estables per a la reacció d'oxidació de CO fins i tot després de tractaments d'envelliment a elevades temperatures. D'altra banda, es racionalitza la formació de nanopartícules de germani disperses en diferents matrius zeolítiques híbrides aprofitant la labilitat del germani en la xarxa cristal·lina de les mateixes per a la seua aplicació com a materials conductors. Es realitza una optimització d'aquests materials híbrids orgànics-inorgànics basats en nanopartícules de Ge mitjançant diversos tractaments post-sintètics, maximitzant la dispersió de les nanopartícules i la formació d'espècies carbonoses per a, finalment, avaluar les seues propietats com a materials conductors. En últim lloc, s'utilitza eixa labilitat del Ge en posicions cristal·lines de les zeolites com a estratègia per a controlar a escala atòmica la incorporació selectiva de diferents heteroàtoms (Si i Sn). La síntesi de l'estructura ITT amb porus extra-grans està limitada a baixes relacions de Si/Ge, presentant per tant una limitada estabilitat hidrotermal. Per això, es du a terme una substitució isomòrfica d'àtoms de Ge per àtoms de Si, millorant l'estabilitat hidrotermal d'aquest material per a la seua aplicació en la reacció de craqueig catalític d'un gasoil de buit, possibilitant la seua regeneració i obtenint una selectivitat similar a dièsel i més propilè que amb la mostra d'origen. D'altra banda, s'incorpora selectivament Sn en l'estructura BEC (polimorf C de la zeolita beta) mitjançant tractaments post-sintètics als defectes estructurals generats després de l'eliminació d'àtoms de Ge, afavorint-se la formació de llocs "oberts" de Sn, que han demostrat ser més actius per a reaccions de molècules oxigenades en comparació als llocs "tancats" de Sn. Els avantatges catalítics del material Sn-BEC sintetitzat es demostren a la reacció Meerwein-Ponndorf-Verley-Oppenauer (MPVO), obtenint-se majors velocitats de reacció per lloc de Sn "obert" que amb la zeolita Sn-beta(F) convencional. / [EN] Zeolites are catalysts used in many chemical processes of industrial and environmental interest. The optimization of the physicochemical properties of these materials is essential to improve their efficiency and attractiveness to current and future technologies. This doctoral thesis aimed to control relevant aspects of the zeolites at the microscopic, molecular, and atomic scale that have a direct effect on their application as catalysts and conductive materials. With this in mind, several methodologies for the direct synthesis of zeolites and several post-synthetic treatments were proposed. Firstly, the influence of crystal size and zeolitic structure on the selective transformation of CO2 towards products of interest such as olefins and aromatics is studied when combined with an iron catalyst doped with potassium. On the one hand, the MFI-type zeolitic structure (medium pore) allows the formation of aromatic products to be maximized. Meanwhile, the CHA (small pore) and BEA (large pore) zeolites favour the production of light olefins in different proportions. The use of nanocrystalline acid zeolites allows to increase the production of light olefins and increases the lifetime of the bifunctional catalysts. Likewise, the effect of confinement at the molecular level of different small-pore zeolitic structures with different types of cavities for the reaction of methanol to olefins (MTO) is studied. Using a theoretical parameter, it was finally possible to correlate the selectivity towards different light olefins with the type of cavities in the microporous materials. Secondly, the stabilization of different metallic species in extra-framework positions of the zeolitic materials is studied by controlling the formation from the individual atoms towards clusters and/or nanoparticles. The structure of the CHA zeolite allows Pt nanoparticles to be encapsulated inside its cavities, which continues being active and stable for the CO oxidation reaction even after aging treatments at high temperatures. On the other hand, the formation of germanium nanoparticles dispersed in different hybrid zeolitic matrices is rationalized by taking advantage of the lability of germanium in their crystalline framework for their application as conductive materials. The optimization of these hybrid organic-inorganic materials based on Ge nanoparticles is carried out through various post-synthetic treatments by maximizing the dispersion of the nanoparticles and the formation of carbonaceous species to evaluate their properties as conductive materials. Finally, the mentioned lability of Ge in crystalline positions is used as a strategy to control the selective incorporation of different heteroatoms (Si and Sn) at the atomic scale. The fact that the synthesis of the ITT structure with extra-large pores is limited to low Si/Ge ratios leads to reduced hydrothermal stability. Therefore, an isomorphic substitution of Ge atoms with Si atoms is carried out. It improved the hydrothermal stability of the material to be applied in the catalytic cracking of a vacuum gasoil, enabling its regeneration. Moreover, the modified material presents similar selectivity to diesel and yields more propylene as compared to the original sample. Also, Sn is selectively incorporated into the BEC structure (polymorph C of beta zeolite) through post-synthetic treatments in the structural defects generated after the elimination of Ge atoms, favouring the formation of "open" Sn sites. It has been shown that this kind of site is more active for reactions involving oxygenated molecules compared to the "closed" sites of Sn. The catalytic advantages of the synthesized Sn-BEC material are demonstrated in the Meerwein-Ponndorf-Verley-Oppenauer (MPVO) reaction. Higher reaction rates per "open" Sn site than with the conventional Sn-beta(F) zeolite were obtained. / Rodríguez Fernández, A. (2024). Diseño racional de materiales zeolíticos: efectos de confinamiento y control de centros metálicos en posiciones de red y extra-red en aplicaciones de interés [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/202870

In der vorliegenden Arbeit wurde die Reaktivität von außergewöhnlich Lewis-sauren festen Katalysatoren: Aluminiumchlorofluorid (ACF) und high-surface Aluminiumfluorid (HS-AlF3) unter moderaten Reaktionsbedingungen untersucht. Die Katalysatoren konnten erfolgreich für die Aktivierung von C-F- und C-Cl-Bindungen (CH3F, CH2F2, CHF3, CH3Cl, CH2Cl2 und ClCH2-CH2Cl) in der Anwesenheit von Silanen eingesetzt werden. Bei Hydrodehalogenierungsreaktionen in Batch-Reaktoren (NMR-Röhrchen) wurden höhere Umsätze mit ACF als mit HS-AlF3 erreicht. Dieser Befund lässt sich mit sterischen Effekten erklären. Die kleineren Mikroporen des ACFs sind besser geeignet für die Aktivierung von kleinen Molekülen als die Mesoporen von HS-AlF3. Die sterischen Aspekte wurden mit Hilfe von FTIR-Experimenten ausführlich untersucht. Unterschiedliche Beobachtungen wurden gemacht, wenn ein zusätzliches Substrat anwesend war, z.B. C6D6 zur Synthese des Friedel-Crafts-Produktes. HS-AlF3 führte zu höheren Umsätzen bei fluorierten Substraten, während bei chlorierten Substraten ACF sich als der bessere Katalysator erwies. Die Herausforderung bestand darin, die Katalysatoren unter sehr anspruchsvollen Bedingungen wie kurze Kontaktzeiten im Flow-Reaktor zu testen. Die Aktivierung von fluorierten und chlorierten Substraten war möglich. Der Unterschied in der Reaktivität der Katalysatoren war nicht so ausgeprägt wie bei Reaktionen in Batch-Reaktor. Aufgrund der kurzen Kontaktzeiten können nur kurze Diffusionswege ausgenutzt werden, was zu ähnlichen Reaktivitäten führt. Mit Hilfe von Experimenten im Flow-Reaktor als auch MAS NMR-, EA-, NH3-TPD-, XRD-, FTIR-, PulseTA®-Experimenten konnte der Mechanismus aufgeklärt werden. Der Katalysator muss zunächst mit Silan gesättigt werden, welcher eine Schutzfunktion hat und die Fluorierung des Katalysators unterdrückt. Ausserdem konnten die Katalysatoren erfolgreich für die Hydrosilylierungsreaktionen und weiterhin zu Deoxygenierung von Ketonen eingesetzt werden. / This thesis investigated the reactivity of extraordinarily lewis-acidic solid catalysts under moderate reaction conditions: aluminium chorofluoride (ACF) und high-surface aluminium fluoride (HS-AlF3).The catalysts could be successfully applied in the activation of C-F and C-Cl bonds (CH3F, CH2F2, CHF3, CH3Cl, CH2Cl2 und ClCH2-CH2Cl) in the presence of silanes. Higher conversions were reached for hydrodehalogenation batch-reactions (NMR tubes) with ACF than for HS-AlF3. This finding can be explained by steric effects. The smaller micropores of ACF are better suited for the activation of small molecules than mesopores of HS-AlF3. Steric aspects were examined extensively by FTIR experiments. Different observations were made in cases where an additional substrate was present, for example C6D6 led to the formation of the Friedel-Crafts product. In this case HS-AlF3 showed higher conversions of fluorinated substrates, while for chlorinated substrates ACF was found to be more efficient. The challenge of this work was to optimize conditions under which the catalysts are not only efficient in batch reactors with long contact times but also under short contact times in flow reactors. Experiments demonstrated that fluorinated and chlorinated substrates can be activated under such conditions. The difference in reactivity of both catalysts was not as extensive as for reactions in a batch reactor. Short contact times require short diffusion pathways, thus more similar reactivities. Experiments in a flow reactor, supported by further analyses by MAS NMR, EA, NH3-TPD, XRD, FTIR and PulseTA® led to the elucidation of the catalytic mechanism. The catalyst must first be saturated by silane, which inhibits and protects the catalyst from fluorination. The catalysts were also successfully applied for hydrosilylation reactions and deoxy-genation of ketones.

[pt] Esta tese busca relacionar mística cristã, que é o fundamento da própria teologia, e literatura fantástica compreendendo esta como lugar tanto da teologia como da experiência mística. Afirmamos, portanto, que a literatura fantástica constitui uma forma de expressão da mística cristã. O que há em comum entre as definições desses conceitos é a dimensão do mistério que ambos compartilham. Pois, por um lado, a mística nos lembra da inefabilidade divina, diante da qual toda expressão da linguagem, embora necessária à sistematização da fé, revela-se insuficiente, uma vez que a experiência de Deus ultrapassa os limites do conhecimento racional-lógico da realidade. Por outro lado, a literatura fantástica introduz no mundo cotidiano a dimensão do insólito, do fantástico, do maravilhoso que enriquece a própria vida. Ambas traduzem experiências que são inquietantes e fundamentais à vida humana. Estas experiências inquietantes estão intimamente vinculadas à dimensão teológica e mística da existência. Por isso, a literatura fantástica é capaz de transmitir experiências profundamente humanas, incluindo as experiências teológicas e místicas. A partir dessa relação, o objetivo é investigar a experiência pessoal e algumas obras ficcionais do escritor irlandês C. S. Lewis a fim de perceber como, seja em sua vida, seja em sua produção literária, Lewis aborda questões vinculadas à mística cristã e à teologia por meio do uso da literatura fantástica. / [en] This thesis seeks to relate Christian mystique, which is the foundation of theology itself, and fantastic literature comprising this as a place of both theology and mystical experience. We affirm, therefore, that the fantastic literature constitutes a form of expression of the Christian mystique. What is common in the definitions of these concepts is the dimension of the mystery they both share. For, on the one hand, mystique reminds us of the divine ineffability, in the face of which every expression of language, though necessary to the systematization of faith, is insufficient, since the experience of God goes beyond the limits of rational-logical knowledge reality. On the other hand, fantastic literature introduces into the everyday world the dimension of the unusual, the fantastic, the wonderful that enriches life itself. Both translate experiences that are disturbing and fundamental to human life. These disturbing experiences are intimately linked to the theological and mystical dimension of existence. That is why fantastic literature is able to convey profoundly human experiences, including theological and mystical experiences. From this relationship, the aim is to investigate the personal experience and some fictional works of the Irish writer C. S. Lewis in order to realize how, in his life or in his literary production, Lewis addresses issues related to Christian mystique and theology through the use of fantastic literature.