No description available.

No description available.

This thesis presents surface science studies, investigating several aspects of titanium dioxide at the atomic scale. The greater part of this work is devoted to the preparation by chemical vapor deposition (CVD) of titanium(IV) tetraisopropoxide (TTIP) of ultrathin TiO2 or TiOx films on Au(111). Four ordered structures were growth and characterized. It was also demonstrated how the morphology of the film (wetting film vs island) can be tailored. The acquired knowledge about the CVD process was exploited to load nano porous gold with titania, enhancing its catalytic activity. The reactivity towards water adsorption of the titania structures on Au(111) was also investigated. Finally, part of this work concerned the studying of the behavior of water on the stoichiometric rutile TiO2(110) surface, combining the experiments with density-functional theory (DFT) calculations and (kinetic) Monte Carlo simulations. The main experimental techniques used in this work are low-energy electron diffraction (LEED), scanning tunneling microscopy (STM) and photoelectron spectroscopy (PES).

O objetivo deste trabalho é demonstrar a insuficiência do uso exclusivo do método literal de interpretação das isenções e sugerir critérios interpretativos e argumentativos adequados que permitam sem margem à arbitrariedade, mais intensamente promover os fins a que essas normas se destinam. Com base na disposição do artigo 111 do CTN, os dispositivos legais que se referem às isenções devem ser interpretados literalmente e, a análise de decisões dos Tribunais Superiores do País e da doutrina nacional demonstra que, na maior parte das vezes, a interpretação literal é adotada como forma de restringir a incidência das normas isencionais, sem levar em conta as finalidades que lhes são subjacentes. Assim, por meio de um método analítico voltado para a prática, ao analisar a estrutura e as principais características das normas isencionais, conclui-se que, tratando-se de normas com funções precipuamente extrafiscais, que se relacionam com a eficácia dos direitos fundamentais, o processo hermenêutico não pode ficar restrito à interpretação literal. Desse modo, cabe reconstruir o significado da disposição contida no art. 111, a fim de afastar a interpretação puramente literal das isenções e possibilitar ao intérprete o emprego de outros métodos interpretativos para a adequada aplicação das regras isencionais. Deve possibilitar, em especial, o uso do método sistemático-teleológico, já que as isenções não podem ser concedidas senão em razão de uma finalidade pública relevante (valores protegidos constitucionalmente), a qual precisa ser devidamente reconhecida e considerada pelo aplicador do Direito. O processo hermenêutico, no entanto, deve ser referendado por um processo lógico argumentativo que justifique a adoção de tais métodos. / The objective of this work is to demonstrate the insufficiency of the exclusive use of the literal method for interpretation of exemptions, and to suggest appropriate interpretative and argumentative criteria that allows no room for arbitrariness, and intensely promotes the purposes for which these standards are intended. Based on the provision of article 111 from CTN, the legal provisions that refer to exemptions must be interpreted literally and the analysis of decisions of the Higher Courts in the country with the national doctrine shows that, in most cases, the literal interpretation is adopted as a way to restrict the incidence of exemptions standards, with no regard to the purposes that are implied. Therefore, by means of an analytical method facing the practice, analyzing the structure and the main features of the exemption rules, it is concluded that in the case of standards as primarily extra tax which relates to the effectiveness of the fundamental rights, the hermeneutic process can not be restricted to literal interpretation. Thus, it is to establish the meaning of the provision in article 111, in order to avoid the purely literal interpretation of the exemptions and to enable the interpreter the use of other interpretative methods for the adequate application of exemption rules. It should allow, in particular, the use of systematic-teleological method, since the exemptions can not be granted, except by reason of a relevant public purpose (constitutionally protected values), which needs to be properly recognized and regarded by the jurisconsult. The hermeneutic process, however, must be approved by a logical-argumentative process that justifies the adoption of such methods.

La notion d’éthique apparaît chez Emmanuel Lévinas à travers la critique de l’ontologie de Martin Heidegger et de la phénoménologie d’Edmund Husserl. Dans cette dimension de l’éthique, deux catégories s’imposent : le Même et l’Autre. Elles jouent toutes deux un rôle primordial. Pourtant, chez Lévinas, apparaît une tendance ontologique, lorsqu’il doit penser la notion du Même et de l’Autre, puisque ces deux notions renvoient à une certaine appropriation de l’être et de l’étant. Ainsi, dans notre recherche sur la pensée de Lévinas, nous essaierons d’expliciter son ontologie. Pour cela, nous commencerons par décrire la conception lévinasienne du monde et du corps. Puis, sur le fondement du monde et du corps, nous décrirons la notion de la subjectivité par le biais d’autres notions comme « l’il y a », la sensibilité, le langage, le temps et Dieu. Nous expliquerons alors leur rapport fondateur en tant que celui-ci constitue la notion de la subjectivité. Ces notions, en effet, justifient notre intérêt porté à l’ontologie de Lévinas et à ses éléments canoniques que sont les ontologies du Même et de l’Autre. A la suite de notre interrogation sur ces deux ontologies, nous décrirons le rôle fondateur de l’ontologie de l’Autre dans le domaine de l’éthique. Enfin, nous expliciterons le sens de l’éthique grâce à l’analyse des notions de mauvaise conscience et de volonté qui permettent de comprendre plus avant l’ontologie de l’Autre. / In Emmanuel Levinas’s work, the concept of ethics appears through a critique of the ontology of Martin Heidegger and the phenomenology of Edmund Husserl. In the dimension of ethics the two categories of the Same (Même) and Other (Autre) play primordial roles. At the same time, we find in Levinas’s philosophical discourse an ontological tendency whenever he must consider the concepts of Same and Other, because they recourse to a certain appropriation of existence and the existent. Thus, in our research on Levinas’s thought, we have tried to clarify his ontology in all of its specificity. To bring this specificity to light, we start by describing the concepts of the world and the body. Then, based on these two notions, we describe the notion of subjectivity with other principal concepts such as “the there is” (“l’il y a”), sensitivity, language, time, and God. Their fundamental relationship is explained in a way such that they produce subjectivity. These considerations effectively build up to our principal interest, which is to focus directly upon the particular ontology of Levinas, with its constitutive parts of Same and Other. Drawing upon the philosophical outcomes of our interrogation of these notions, we describe the fundamental role of the ontology of the Other for the meaning of the ethics. The final sections of the text continue this theme by considering the concepts of the guilty conscious and the will.

Made available in DSpace on 2014-10-09T12:42:28Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:02:00Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:40:47Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:00Z (GMT). No. of bitstreams: 1 02947.pdf: 6721410 bytes, checksum: 6b8fd88ede9d8533a129cf94a67a4313 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:92/02990-0

Submitted by Claudinei Pracidelli (cpracide@ipen.br) on 2015-12-22T09:27:04Z No. of bitstreams: 0 / Made available in DSpace on 2015-12-22T09:27:04Z (GMT). No. of bitstreams: 0 / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

O objetivo deste trabalho é demonstrar a insuficiência do uso exclusivo do método literal de interpretação das isenções e sugerir critérios interpretativos e argumentativos adequados que permitam sem margem à arbitrariedade, mais intensamente promover os fins a que essas normas se destinam. Com base na disposição do artigo 111 do CTN, os dispositivos legais que se referem às isenções devem ser interpretados literalmente e, a análise de decisões dos Tribunais Superiores do País e da doutrina nacional demonstra que, na maior parte das vezes, a interpretação literal é adotada como forma de restringir a incidência das normas isencionais, sem levar em conta as finalidades que lhes são subjacentes. Assim, por meio de um método analítico voltado para a prática, ao analisar a estrutura e as principais características das normas isencionais, conclui-se que, tratando-se de normas com funções precipuamente extrafiscais, que se relacionam com a eficácia dos direitos fundamentais, o processo hermenêutico não pode ficar restrito à interpretação literal. Desse modo, cabe reconstruir o significado da disposição contida no art. 111, a fim de afastar a interpretação puramente literal das isenções e possibilitar ao intérprete o emprego de outros métodos interpretativos para a adequada aplicação das regras isencionais. Deve possibilitar, em especial, o uso do método sistemático-teleológico, já que as isenções não podem ser concedidas senão em razão de uma finalidade pública relevante (valores protegidos constitucionalmente), a qual precisa ser devidamente reconhecida e considerada pelo aplicador do Direito. O processo hermenêutico, no entanto, deve ser referendado por um processo lógico argumentativo que justifique a adoção de tais métodos. / The objective of this work is to demonstrate the insufficiency of the exclusive use of the literal method for interpretation of exemptions, and to suggest appropriate interpretative and argumentative criteria that allows no room for arbitrariness, and intensely promotes the purposes for which these standards are intended. Based on the provision of article 111 from CTN, the legal provisions that refer to exemptions must be interpreted literally and the analysis of decisions of the Higher Courts in the country with the national doctrine shows that, in most cases, the literal interpretation is adopted as a way to restrict the incidence of exemptions standards, with no regard to the purposes that are implied. Therefore, by means of an analytical method facing the practice, analyzing the structure and the main features of the exemption rules, it is concluded that in the case of standards as primarily extra tax which relates to the effectiveness of the fundamental rights, the hermeneutic process can not be restricted to literal interpretation. Thus, it is to establish the meaning of the provision in article 111, in order to avoid the purely literal interpretation of the exemptions and to enable the interpreter the use of other interpretative methods for the adequate application of exemption rules. It should allow, in particular, the use of systematic-teleological method, since the exemptions can not be granted, except by reason of a relevant public purpose (constitutionally protected values), which needs to be properly recognized and regarded by the jurisconsult. The hermeneutic process, however, must be approved by a logical-argumentative process that justifies the adoption of such methods.

Dans le but de développer des matériaux et des dispositifs avec de nouvelles propriétés, l’élaboration de monocouches auto-assemblées (SAM) est un sujet d'intérêt croissant dans le domaine des nanosciences. Les SAM sont des agrégats bidimensionnels formés par des molécules régulièrement espacées sur une surface et liées entre elles par des forces non covalentes. Le domaine des biocapteurs électrochimiques pour la reconnaissance des brins d'ADN est parmi les applications les plus récentes des SAM. Dans ce cadre, nous avons mené une étude théorique des mécanismes fondamentaux engagés lors de l’adsorption de la molécule quinone Jug-C4-thiol sur la surface Au (111). Les résultats ont été confrontés aux mesures expérimentales accessibles réalisées par l’équipe « nano 2D » au laboratoire ITODYS (Université Paris7). Tout d’abord, la théorie de la fonctionnelle de la densité PBE et PBE-D2 a été utilisée pour étudier les mécanismes mis en jeu (physisorption ou chimisorption) lors de l’adsorption de la molécule isolée à la surface de Au (111) et déterminer le site le plus favorable pour chaque mécanisme. La nature de la liaison entre la molécule et la surface de a été finement analysée à l’aide de calculs de densité d’états (DOS) et de différences de densités de charge. Ensuite, l'assemblage de la molécule quinone Jug-C4-thiol sur la surface Au (111) a été étudié. Cet assemblage des molécules a été initié par la formation de configurations de dimère à travers la formation de liaisons intermoléculaires (liaison hydrogène et π-stacking, …). Les spectres infrarouges des configurations les plus stables ont été simulés et confrontés à l’expérience. Et enfin, le mécanisme d’échange entre des molécules « hôtes » (alcanethiols C12H25SH préalablement assemblés sur la surface) et « invitées » (Jug-C4-thiols) a été exploré avec les outils théoriques. L’analyse des résultats a mis en évidence des informations structurales et énergétiques importantes sur la formation de la monocouche moléculaire mixte. / In order to develop materials and devices with new properties, the development of self- In order to develop materials and devices with new properties, the development of self-assembled monolayers (SAM) is a topic of growing interest in the field of nanoscience. SAM are two-dimensional aggregates formed by molecules regularly spaced on a surface and bonded together by non-covalent forces. The field of electrochemical biosensors for DNA strand recognition is among the most recent applications of SAM. In this context, we conducted a theoretical study of the fundamental mechanisms involved in the adsorption of the quinone Jug-C4-thiol molecule on the Au (111) surface. The results were compared to the accessible experimental measurements from the "nano 2D" team at the ITODYS laboratory (Paris 7 University). First, the density functional theory at PBE and PBE-D2 levels was used to study the mechanisms involved (physisorption or chemisorption) during the adsorption of the isolated molecule on the surface of Au (111) and access to the most favorable site for each mechanism. The nature of the binding between the molecule and the surface was finely analyzed using density of states (DOS) calculations and differences in charge densities.Then, the assembly of the quinone Jug-C4-thiol molecule on the Au (111) surface was studied. This assembly of molecules was initiated by the formation of dimer configurations through the formation of intermolecular bonds (hydrogen bonding and π-stacking, etc.). The infrared spectra of the most stable configurations were simulated and compared with the experiment. And finally, the mechanism of exchange between "host" molecules (C12H25SH alkanethiols previously assembled on the surface) and "invited" molecules (Jug-C4-thiols) was explored with the theoretical tools. The analysis of the results revealed important structural and energetic informations on the formation of the mixed molecular monolayer.