L’enjeu principal de cette recherche consiste à démontrer qu’il y a une pensée spécifique du sujet chez Kant. L’auteur repère le fondement de la subjectivité kantienne dans l’acte libre de se donner la loi. La loi éthique, c’est la loi que je me donne moi-même. Et pourtant, la loi est l’impératif qui s’adresse au moi à la deuxième personne : la loi s’adresse au moi comme l’impératif « tu dois ». En tant qu’impératif, la loi se présente comme ce qui m’est donné, et je me conçois comme celui qui est posé devant la loi. Cela veut dire que je m’éprouve, en me soumettant à la loi, comme un «toi » à qui la loi s’adresse, et que la loi apparaît comme provenant de l’autre ou du dehors. Ne peut-on pas alors dire que je me donne la loi comme si j’obéissais à la loi de l’autre qui m’appelle à la deuxième personne ? Ou bien, comme si je traitais comme un autre mon moi qui obéit à la loi ? Par l’autre, l’auteur pense à l’altérité interne dans l’acte d’auto-détermination par la loi. Bien que le moi n’a affaire qu’à lui-même dans l’auto-détermination par la loi, l’autre intervient dans la relation du moi qui donne la loi et du moi qui obéit. L’ipséité du moi constitue ainsi l’épreuve de l’altérité du moi. Que je m’éprouve dans l’auto-détermination par la loi, c’est cette épreuve de soi que l’auteur a essayé d’élucider avec Kant. / The purpose of this research aims at demonstrating that there is a specific conception of the Self in Kant. According to the author, the fundamental of the subjectivity in Kant can be found in the free will acting under the law that it gives to itself. For Kant the moral law is the law I give to myself. Nevertheless, the law is understood as an imperative that I give to myself by using the second person, that is to say that one is addressed by the moral law under the imperative form " you must ". It means that I consider myself as the "you" to whom the law is addressed. To me, the law is an imperative addressed by the other person, that is to say an imperative coming from outside. Thus, it might be possible to consider that when I give to myself the law it is the same as if I obey the other law, which is addressed to me with the second person? Or, shall we say that I consider myself as the other person who obeys the law? By the term “the other”, the author means the internal otherness existing in the action of self-determination resulting from the law. This is related to the question of identifying the enlightenment of the other’s status, which is involved in the action of self- determination given by the law. Although I have to deal with myself in the self-determination given by the law, the other is involved in the relation that opposes myself, when I give to myself the law, to me as the subject who obeys the law. The subjectivity might be interpreted as the test of the otherness existing in the Self. The fact that I consider myself as “the other” in the self-determination given by the law, can be seen as the test of the otherness existing in the Self and this is what the author aims at clarifying based on his works on Kant’s thoughts.

Made available in DSpace on 2016-08-18T18:19:28Z (GMT). No. of bitstreams: 1 Mauro Bogea Pereira.pdf: 2672209 bytes, checksum: 6ffa34d37be7c980ea311a6504843760 (MD5) Previous issue date: 2011-04-28 / FUNDAÇÃO SOUSÂNDRADE DE APOIO AO DESENVOLVIMENTO DA UFMA / In this work the electronic and structural properties of the hetero-nanotube bundles, composed of a CNT (6,0) encapsulated in a BNNT (14,0) (CNT (6,0)@BNNT (14,0)) and a BNNT (6,0) encapsulated in a CNT (14,0) (BNNT(6,0)@CNT (14,0)), under hydrostatic pressure. For this, we applied density functional theory and generalized gradient approximation to the exchange and correlation term, as implemented in SIESTA code. We observed that structural changes occur when pressure is applied. For the CNT(6,0)@BNNT(14,0) these changes begin when the pressure is close to 1,0 GPa for the outer tube, while for the inner tube the changes are observed around 10,0 GPa. In the case of BNNT(6,0)@CNT(14,0) the structure begins to be modified when the applied pressure is close to 3,0 GPa. The analysis of the band structure shown that the metallic character of the CNT(6,0)@BNNT(14,0) and the semiconductor character of the BNNT(6,0)@CNT(14,0) did not change when the pressure is applied. / Neste trabalho foram estudadas as propriedades eletrônicas e estruturais de bundles de hetero-nanotubos, compostos por um CNT (6,0) encapsulado em um BNNT (14,0) (CNT(6,0)@BNNT(14,0)) e por um BNNT (6,0) encapsulado em um CNT (14,0) (BNNT(6,0)@CNT(14,0)), submetidos a pressão hidrostática. Para tanto, fizemos uso da teoria do funcional da densidade e da aproximação do gradiente generalizado para tratar o termo de troca e correlação, implementados no programa computacional SIESTA. Observou-se que ocorrem alterações estruturais nos bundles a medida que a pressão é aplicada. Para o CNT(6,0)@BNNT(14,0) estas alterações têm início a pressões próximas de 1,0 GPa para o tubo externo, enquanto que para o tubo interno as alterações só começam a ser observadas próximo de 10,0 GPa. No caso do BNNT(6,0)@CNT(14,0) a estrutura só começa a ser modificada quando o pressão aplicada é próxima de 3,0 GPa. A análise da estrutura de bandas de energia das duas estruturas mostrou que o caráter eletrônico, metálico para os CNT(6,0)@BNNT(14,0) e semicondutor para os BNNT(6,0)@CNT(14,0), mantêm-se estáveis mesmo para os maiores valores de pressão aplicados.

Design and Development of Carbon-Carbon and Carbon-Heteroatom Bond Forming Reactions” is divided into two sections. Section-A, contains two chapters, describes the catalytic ability of iodine for cross coupling reactions. Section-B, divided into three chapters, presents the azidation of organic scaffolds under oxidative conditions. Section A Chapter 1 presents a C-H functionalization of tetrahydroisoquinolines using iodine as a catalyst under aerobic conditions.1 This methodology employs Cross Dehydrogenative Coupling (CDC) strategy as a key step, which is highly atom economical as it doesn’t require pre-functionalized starting materials.2 Owing to the importance of tetrahydroisoquinoline moiety which is present in the umpteen natural products, considerable attention has been put up to functionalize tetrahydroisoquinoline scaffold.3 Iodine a non-metal which is non-toxic was found to catalyze the C-H functionalization of tetrahydroisoquinolines with a variety of nucleophiles such as coumarin, alkyl phosphite, phenols, indoles, acetone and dialkyl malonoates were coupled to it. Significant mechanistic study has been carried out to find the possible intermediate and support the mechanistic proposal. A few representative examples are highlighted in Scheme 1.1 Synopsis Scheme 1: A CDC coupling of tetrahydroisoquinoline with variety of nucleophiles Chapter 2 describes the Cross Hetero Dehydrogenative Coupling (CHDC) reactions of amines, alcohols and sulfoximines with various phosphites.4 Phosphoramidates and phosphate esters are structural scaffolds that are present in a variety of biologically active molecules.5 The conventional methods for synthesizing phosphoramidates/phosphate esters largely involve treating alcohol/amine with appropriate phosphorus halides which generates stoichiometric amount of halogen waste.6 Due to the usage of stoichiometric reagents and difficulties associated with the reported methods, there is a need for developing a protocol which is catalytic and mild. Therefore, we developed a method which employs catalytic amount of iodine and aq. H2O2 as a sole oxidant under milder conditions. Using this methodology, variety of phosphoramidates, phosphorous triesters and sulfoximine derived Synopsis Scheme 2: Phosphorylation of amines, alcohols and sulfoximines phosphoramidates have been synthesized with great efficiency and environmentally benign conditions. A few representative examples are highlighted in Scheme 2.4 Section B Chapter 1 of Section B demonstrates a mild way of synthesizing quaternary azides from α-substituted active methylene compounds which will serve as surrogates for several unnatural amino acid derivatives.7 Azidation has emerged as one of the efficient methods to introduce nitrogen atom in to the organic molecules.8 Azides are versatile functional groups which can be converted to amine, amide, and nitro compounds by simple modification. Moreover, azides are potential handle for “click” chemistry and provide late stage modifications in drug candidates, biomolecules and polymers, etc.9 Azidation of 1,3-dicarbonyl compounds is challenging, as both azides and 1,3-dicarbonyl compounds are nucleophilic in nature. In this section of the thesis, azidation of 1,3-dicarbonyl compounds has been carried out using tetrabutyl ammonium iodide (TBAI) as a catalyst, aq. TBHP as an oxidant and TMSN3 as a azide source. This method uses water as a solvent under mild reaction conditions to generate Synopsis quaternary azides in good to excellent yields. This operationally simple, practical, mild and green method provides an opportunity for synthesizing a variety of azidated β-keto esters, amides and ketones in good yields, Scheme 3.7 The application of this methodology has been demonstrated by synthesising a few triazole and pyrazolone derivatives. Scheme 3: Azidation of 1,3-dicarbonyl compounds Chapter 2 of Section B comprises the azidation and peroxidation of β-napthol derivatives using dearomatization strategy. Azidation and peroxidation are efficient ways to introduce nitrogen and oxygen into organic molecules, which serve as surrogates for amines and alcohol functional groups. In the present study, the azidative or peroxidative dearomatization of naphthol derivatives have been described. The azidation of β-napthol derivatives has been achieved by using CuBr (5 mol %) as a catalyst, TMSN3 as an azide source and aq. TBHP as an oxidant. Whereas, the peroxidation β-napthol derivatives has been accomplished using CuBr (5 mol %) in the presence of aq. TBHP at ambient reaction conditions.10 The products obtained are naphthalenone derivatives, which serve as valuable Synopsis synthetic intermediates and has potential handle for further functionalization.11 Several α-amino or α-peroxy naphthalenones are synthesized using this method in good yields. The usefulness of the methodology has been illustrated by synthesizing a few chiral azides and peroxides in good yields and with moderate enantioselectivity Scheme 4.10 Scheme 4: Dearomatizative azidation and peroxidation of 2-naphthols Chapter 3 reveals the azidation of indole at C-2 position by employing CuBr (10 mol %) as a catalyst and aq. TBHP as an oxidant in acetonitrile under reflux conditions (Scheme 5).12 The C-H functionalization of indole at C-2 position is one of pivotal methods, since it paves a way for synthesizing a variety of indolo-alkaloids.13 Azide is a versatile functionality which can be converted to several other nitrogen containing functional groups such as Synopsis Scheme 5: Azidation of indoles amine, amide, triazole, etc.9 A variety of functional groups were tolerated under the reaction conditions, and furnished the azidated product in good to excellent yields. Through radical inhibition study, we presume that the reaction may be proceeding through radical mechanism. In Scheme 5, a few representative examples are depicted.

No description available.

Colonization within Indigenous territories has impacted Indigenous governance structures and women in leadership in different ways. In order to best understand the violence, displacement and oppression that Coast Salish women face today we need to focus on the ways that the state has attacked the powerful role that si´em slheni´ (honoured and respected woman) held within her socio-political societies prior to contact. I use an historical institutional analysis to draw out the ways that history has impacted Coast Salish people. I also utilize Diane Million’s Felt Theory (2008) by weaving Coast Salish women’s stories, experiences, and understandings of colonization within their own ancestral territories. The research question at hand is: How have Coast Salish si´em slhunlhéni´ (honoured and respected women) been impacted due to colonization historically and how are these impacts still affecting our slhunlhéni´ and our communities today? In asking this question, I hope to urge the reader to engage a territorially-based approach in dealing with the violence and displacement that Indigenous women in Canada face today. I aim to do so by illustrating what an approach based in Coast Salish history and governance would look like. I argue that if we do not choose to take up a territorial based approach, we are only furthering the erasure and silencing of Indigenous womanhood denying its resurgence. I highlight how settler statecraft has played out in Coast Salish territory and explore the myriad of ways that racist ideologies and colonial violence have taken shape within Coast Salish territories. To do so, I examine the different ways that the state has attempted to control and pathologize coastal people and illustrate the shift that has occurred in moving from Coast Salish economies to capitalism. Ultimately, I demonstrate the multi-faceted approach taken by legislative discrimination that was fueled by ideological racism that the settler colonial project depends upon in order to maintain control over Indigenous lands, waters, and people. By examining these issues, I highlight how the settler project was able to weaken slhunlhéni´ role and therefore firmly establish itself within Coast Salish territories Finally, I turn to present day reality in Coast Salish territory and argue that while there are ways the state, settlers and Indigenous people living within Coast Salish territories are attempting to address the wrongs of colonization, Coast Salish women’s voices and roles are being left out of decolonial discourse and actions. In order to liberate Coast Salish women, we need to turn back to our ancestral ways and for those who are not a descendant to these territories one must work to understand what your responsibility is to the local people and women of these lands. In this way, centering a territorially based approach to governance in all acts of resurgence and decolonial action allows for Coast Salish women to maintain authority, therefore empowering these women. Centering local laws and governance will center Indigenous women, lifting them from the displaced positions they find themselves in today. / Graduate

Recent research has shown that small hydrogen bonding catalysts can catalyze the hetero Diels-Alder reaction. In this thesis such hydrogen bonding catalysts in conjunction with varying functional groups and their effect on the hetero Diels-Alder reaction have been investigated. The influence of the different solvents has been investigated as well. The activation barriers for the different region- and stereo isomeric pathways have been compared in order to determine the stereo specificity of the reactions. These calculations have been done using the B3LYP functional for the geometry optimizations and then M06-2X for single point calculations. For the solvated cases the cPCM model and the M06-2X functional were used. It was shown that for the catalyzed systems bulkier groups in the endo position tend to have a lower activation barrier, allowing for control over the stereoselectivity. Electron withdrawing groups have an activating effect and are also synergistic with the hydrogen bonding catalysts. The solvent with the lowest dielectric constant gave the lowest activation barrier.

Furo[3,4-c] pyranone is a unique bicyclic molecular structure found in bioactive sesquiterpene isobolivianine and in artificial cytotoxic stilbene derivatives. The structure of furo[3,4-c] pyranone is analogous to cyclopenta[c] pyran structure found in potent cytotoxic iridoids like catapol. Chiral substrates for intramolecular hetero-Diels-Alder (IHDA) reaction have been synthesized in yields ranging from 39% to 81%. These compounds undergo [4+2] cycloaddition via ambimodal/ bispericyclic process to give a mixture of furo[3,4-c] pyranone in yields ranging 40-70% and aryl tetralin lactone derivatives. Density functional theory (DFT) calculations have been performed to gain insight into the mechanism leading to the formation of these compounds. Podophyllotoxins are aryl tetralin lignans with great potential as lead compounds for anti-cancer and antibiotic agents. The bioactivity of these compounds is attributed to their unique stereochemistry that is not easy to synthesize. Chiral substrates for intramolecular dehydro-Diels-Alder (IDDA) reaction have been synthesized in moderate yields. These novel compounds have been used to synthesize aryl tetralin lactone cores by IDDA reaction. This work demonstrates the potential utility of asymmetric IHDA and IDDA reactions in the total synthesis of bioactive compounds featuring furo[3,4-c] pyranone core and aryl tetralin lactones found in anticancer podophyllotoxins.

The study focuses on the manners of representations of Czechs and other nations/ethnicities in the journalist work of Karel Havlíček Borovský before and after the 1848-9 revolution. Its methodology is based on concepts and approaches elaborated in the area of literary imagology. The theoretical part of the study deals with the issue of emergence of images, their stereotypical components and the mutual relations between self-image and hetero-image. It also describes the features, functions and the process of formation of national stereotypes. The following chapter describes the development of national-political tendencies emerging in the Czechs lands and corresponding to five different concepts of a nation (Austrianness, Germanness, Slavness, Bohemism and Czechness). The following chapter depicts the course of the revolution, where tensions between the individual national-political tendencies were increasing, and Havlíček's work before and during the revolution. The next chapter analyses the individual stereotypical character features of Czechs and other nations in Havlíček's journalist work in 1846-50. This imagological analysis shows that when constructing the Czech character, Havlíček uses older stereotypical qualities of Slavs (justice, peacefulness, their fundamental democratic nature,...

L'hydrogène est envisagé comme vecteur énergétique pour le futur. En effet, son utilisation par oxydation dans les piles à combustible ne produit que de la vapeur d'eau et permet la production d'électricité et de chaleur. L'oxydation partielle des hydrocarbures, réaction exothermique, peut être une alternative ou un complément au vaporeformage (endothermique) pour la génération d'hydrogène. L'intérêt du propane, par rapport au méthane, est qu'il se liquéfie à une pression relativement faible. L'objectif de ce travail est l'étude cinétique de l'oxydation partielle catalytique du propane. C'est une réaction complexe : son mécanisme comporte des réactions catalytiques de surface couplées à des réactions en phase gazeuse par l'intermédiaire de radicaux. La réaction a été étudiée dans un réacteur auto-agité catalytique. Dans un premier temps une étude expérimentale a été réalisée sans catalyseur. Un mécanisme homogène a pu ainsi être validé. Ensuite, cette même réaction a été étudiée en présence de pastilles d'oxyde de cérium. Un mécanisme hétérogène a été écrit en utilisant le formalisme d'Eley-Rideal et celui de Langmuir-Hinshelwood. Les données cinétiques ont été estimées selon une méthode originale basée sur la théorie de Benson. En comparant les résultats expérimentaux et ceux issus de la simulation (effectués avec Chemkin®/Chemkin Surface®), un mécanisme hétéro-homogène a été validé sur un large domaine de conditions opératoires / Hydrogen is proposed as an energy vector for the future. Indeed, its energetic use by oxidation in fuel cells produces water vapor only. The partial oxidation of hydrocarbons, an exothermic reaction, can be an alternative or a complement to the steam cracking (endothermic) for hydrogen generation. Propane can be an interesting hydrocarbon for hydrogen production since it can be easily stored in liquid phase and distributed. The aim of this work is the kinetic study of the catalytic partial oxidation of propane. The reaction is complex: catalytic reactions are coupled to reactions in gas phase by the intermediary of radicals. The reaction was studied in a catalytic jet stirred reactor. At first, an experimental study was carried out without a catalyst. A homogeneous mechanism could be validated. Afterwards, this same reaction has been studied in presence of cerium oxide pellets. A heterogeneous mechanism was written using the formalism of Eley-Rideal and that of Langmuir-Hinshelwood. The kinetics parameters are estimated by methods derivated from Benson's techniques. Comparing experimental results and those from the simulation (carried out by Chemkin®/Chemkin Surface®), a hetero-homogeneous mechanism was validated in our experimental conditions

Im Rahmen der Dissertation wurden molekularstrahlepitaktische Verfahren zur Züchtung von Hetero-und Quantenstrukturen auf der Basis der Gruppe II-Oxide entwickelt. Insbesondere wurde ein Wachstumsregime weit entfernt vom thermischen Gleichgewicht etabliert, welches die Mischung von CdO und MgO mit ZnO in phasenreiner Wurtzitstruktur ermöglicht, wobei die Gleichgewichtslöslichkeitsgrenzen dramatisch überschritten werden. In den Mischkristallen kann die Bandlücke kontinuierlich von 2.2 bis 4.4 eV eingestellt werden. Das Wachstum verläuft in einem zweidimensionalen Modus und resultiert in atomar glatten Ober- und Grenzflächen. Ausgeprägte RHEED- Intensitätsoszillationen erlauben die atomlagengenaue Kontrolle der Schichtdicken und somit die Realisierung wohl-defi- nierter Einzel- und Mehrfachquantengrabenstrukturen. Diese zeichnen sich durch eine hohe Photolumineszenzquantenausbeute im gesamten sichtbaren Spektralbereich aus. Laseraktivität kann vom UV bis zum grünen Wellenlängenbereich bei Zimmertemperatur erzielt werden. Das Potenzial dieser Quantenstrukturen in Hinblick auf ihre Anwendung in opto-elektronischen Bauelementen wird diskutiert. / This work focuses on the development of the novel growth approaches for the fabrication of Group II-oxide materials in the form of epitaxial films and heterostructures. It is shown that molecular-beam epitaxial growth far from thermal equilibrium allows one to overcome the standard solubility limit and to alloy ZnO with MgO or CdO in strict wurtzite phase up to mole fractions of several 10 %. In this way, a band-gap range from 2.2 to 4.4 eV can be covered. A clear layerby- layer growth mode controlled by oscillations in reflection high-energy electron diffraction makes it possible to fabricate atomically smooth heterointerfaces and well-defined quantum well structures exhibiting prominent band-gap related light emission in the whole composition range. On appropriately designed structures, laser action from the ultraviolet down to green wavelengths and up to room temperature is achieved. The properties and potential of the "state-of-the-art" materials are discussed in relation to the advantages for their applications in various optoelectronic devices.