No description available.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal.

La conception de molécules pour l’optique non linéaires (ONL) est devenue un centre de recherche de pointe pour les télécommunications, les technologies de l'information et le stockage de données optiques. Les molécules dipolaires substituées par des groupes donneur-accepteur ont été les chromophores les plus étudiés pour l’ONL. Cependant les molécules dipolaires diverses limitations telles que leur transparence optique, leur faible stabilité thermique et leur tendance à adopter un alignement antiparallèle à l'état solide. Récemment, une nouvelle classe de matériaux est apparue basé sur des symétries octupolaire qui ne possède pas de dipôle permanent, pour les applications ONL. Au niveau structural, la structure générique idéale pour des molécules tridimensionnelles avec une distribution de charges octupolaire est un cube avec des charges opposées alternées à chaque angle. À ce jour, aucune molécule représentant le cube vrai (déformé) avec huit charges alternées aux sommets et délocalisation des charges complètes entre les plans supérieurs et inférieurs n’a été décrite. Dans le cadre de cette thèse, des complexes de lanthanides III à partir de phthalocyanines de type ABAB présentant en alternance des groupes donneurs et accepteurs d'électrons ont été synthétisés représentant le premier réel octupole. Ces structures ont été caractérisé par UV-NIR, X-Ray et présentent les plus élevés hyperpolarisabilité quadratique jamais enregistré pour des molécules octupolaires. En outre, ce travail a été étendu à divers type de double-decker de lanthanides homoleptiques non-octupolaire basé sur des phthalocyanines AB3, A4, B4, T4. Il a été observé que ces complexes présentent aussi des mesures d’hyperpolarisabilité quadratique élevés, mais inferieur a celles trouvé pour la série de complexes Ln (ABAB)2 octupolaire, comme prévu. / The design of nonlinear optical (NLO) molecules has become a focus of current research in telecommunications, information technologies and optical data storage. Donor-acceptor substituted dipolar molecules have been the most investigated NLO chromophores. Dipolar molecules, however, have several limitations such as low optical transparency, low thermal stability and their strong tendency to adopt anti-parallel packing in the solid state. Recently, a new class of materials based on octupolar symmetries, which lack permanent dipole moments, has been proposed for NLO applications. At a structural level, it can be shown that the basic template for 3D octupolar molecules comes to a cube with alternating charges at the corners such as donor and acceptor substituent. Despite all the various structures reported, it is worth noting that no molecules actually representing the “real” octupolar cube have been obtained so far. In this thesis, we showed that the real octupolar cube can be demonstrated by lanthanide III complexes based on ABAB type phthalocyanine featuring alternating electron donor and electron acceptor groups. These structures are characterized by UV-NIR, X-Ray and exhibit highest quadratic hyperpolarizability ever reported for an octupolar molecule. Moreover, this work was extended to nonoctupolar lanthanide homoleptic double-decker complexes based on AB3, A4, B4, T4 type phthalocyanines. It was observed that these molecules present a quite large quadratic hyperpolarizability too, but smaller than the one obtained for the Ln(ABAB)2 series, as expected. / Doğrusal olmayan optic (NLO) özellik gösteren moleküllerin tasarımı telekomünikasyon, bilgi teknolojileri ve optic very depolama alanlarında güncel bir araştırma konusudur. Alıcı-verici grup bağlı iki kutuplu moleküller en çok araştırılmış NLO malzemeleridirler. Ancak, iki kutuplu moleküllerin düşük optic şeffaflık, düşük termal kararlılık ve katı halde parallel olmayan yığılmaları gibi çeşitli sınırlamaları vardır. Son zamanlarda, kalıcı dipol momentleri olmayan octupolar simetriye dayalı, yeni bir malzeme sınıfı NLO uygulamaları için ileri sürülmüştür. Yapısal olarak bu 3D octupolar moleküller için temel şablon, köşelerinde alıcı verici grupları içeren bir olarak gösterilir. Yapılan tüm çalışmalara ragmen, bugüne kadar gerçek küpü temsil edebilen bir yapı elde edilememiştir. Bu tezde, biz bu octupolar küpün electron alıcı ve verici grupları içeren ABAB tipi halkalı yapıya dayalı lantanid kompleksleri ile ortaya konabilecğini gösterdik. Bu yapılar UV-NIR ve X-Ray ile yapıları aydınlatıldı ve bugüne kadarki en yüksek 2. dereceden NLO değerleri elde edildi. Ayrıca, bu çalışma, çeşitli octupole olmayan AB3, A4, B4 ve T4 tipi lantanit çift katlı ftalosiyaninler sentezlenerek genişletildi. Ve oktupol olmayan moleküllerin 2. Dereceden NLO değerleri oldukça büyük ama beklendiği gibi oktupol Ln(ABAB)2 daha küçük olduğu gözlendi.

(in English) Present dissertation deals with historical-linguistic analysis of the eighteen German written documents in interval of the years 1364 - 1517, that are divided into two six royal and twelve municipal documents, whose contents is connected with the town Loket. The first part of the work is specialized in general introduction of the condition of research in this field of history, diplomatic materials of the town, history of the town and the issues of chanceries. The second part is based on documentary materials and it incorporated the analysis of macro and micro- structure. The macro-structure analysis is based on, according to using formulae, model structure of analysed documents, that is consequently used as a starting structure for analysis of micro-structure. Micro-structure analysis provides the way, which the linguistic means are in particular parts formulated. From results of my work is evident, that the structure of the documents keeps the reliable example that is a bit different from initial structure. Structure of the royal documents shows, in contrary to the municipal documents, bigger stability both in arrangement and using formulae as well as their language formulations. Klíčová slova (anglicky): German Language, History-Linguistics, Documents, History (until 1526), Bohemia

Thesis. (M.Tech. (Chemistry)) -- Vaal University of Technology, 2011. / Bis(acetylacetonato)oxovanadium(IV), Manganese(III) acetylacetonate, Co-Zn and Co-Al were prepared as catalyst precursors for the synthesis of carbon materials in a catalytic chemical vapor deposition (CCVD) reactor. The carbon materials produced were characterized with Raman spectroscopy, Scanning electron microscope (SEM), Energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), High resolution transmission electron microscopy (TEM) and Thermogravimetric analysis, (TGA). Carbon material prepared from bis(acetylacetonato)oxovanadium(IV) catalyst precursor showed the presence of carbon spheres with average diameter of 104μm together with small traces of carbon nanotubes or amorphous carbon. Synthesis of bis(acetylacetonato)oxovanadium(IV) catalyst precursor yielded approximately 92% of carbon material. Carbon material prepared from Manganese(III) acetylacetonate catalyst precursor showed the presence of carbon spheres with diameter of 87.5μm. Synthesis of Manganese(III) acetylacetonate catalyst precursor yielded approximately 97% of carbon material. Carbon material produced from Co-Zn and Co-Al catalyst precursors showed the presence of carbon nanotubes with small amounts of amorphous carbon. The use of Co-Zn catalyst precursor yielded approximately 80% of carbon nanotubes, whereas Co-Al catalyst precursor yielded approximately 98% of carbon nanotubes. / Vaal University of Technology; NRF; SASOL

Memoria (licenciado en ciencias jurídicas y sociales) / Esta investigación tiene la intención de realizar un análisis acerca de la idoneidad de la regulación del Caudal ecológico mínimo como una norma de protección ambiental respecto de los objetivos establecidos en el art. 129 bis 1 del Código de Aguas: la preservación de la naturaleza y protección del medio ambiente. Así, en este trabajo se contextualiza la política hídrica vigente en Chile, las problemáticas que ésta enfrenta y la incorporación del Caudal ecológico mínimo dentro de este contexto como una norma destinada a la protección del desarrollo de los ecosistemas. En el primer capítulo, se efectúa un análisis de la historia de los principales cuerpos normativos que regulan las aguas en Chile (Constitución Política de la República, el Código Civil y el Código de Aguas), para luego realizar una revisión de los tratados internacionales ratificados por Chile que han abarcado la materia, con el fin de contextualizar la política hídrica nacional. En el segundo capítulo se estudia la configuración del Caudal ecológico mínimo en la regulación, la que abarca desde la discusión parlamentaria hasta la posterior formulación de norma, analizando los objetivos que esta persigue y su aplicación. Por último, en el tercer capítulo, se desarrollan críticas acerca de la idoneidad de la norma, se analiza la reforma al Código de Aguas en curso respecto del art. 129 bis 1 y, finalmente, se da una propuesta sobre consideraciones necesarias para establecer una nueva regulación.

O objetivo deste trabalho foi avaliar a influência de diferentes aminas terciárias no grau de conversão, na contração de polimerização, na taxa de contração, na microdureza Knoop, na estabilidade de cor e na transmitância de luz de resinas experimentais, contendo, em peso, BisGMA e TEGDMA (3:1), 0,25% de canforquinona (CQ) e 1% de amina (DMAEMA, CEMA, DMPT, DEPT ou DABE). A influência de diferentes protocolos de fotoativação também foi investigada. O grau de conversão foi avaliado através de FTIR-ATR e a contração pelo método do disco aderido. A partir da diferenciação numérica dos dados de contração em relação ao tempo, obteve-se a taxa de contração de polimerização. A estabilidade de cor e a transmitância foram avaliadas em diferentes períodos de envelhecimento artificial. Os resultados foram avaliados pelos testes de ANOVA, Tukey e T3 de Dunnett (&#945; = 0,05). As propriedades estudadas variaram em função da amina. O grau de conversão e a contração de polimerização variaram na sequência: CQ < DEPT < DMPT &#8804; CEMA &#8776; DABE < DMAEMA. O grau de conversão e a contração também foram influenciados pelo protocolo de fotoativação, sendo observadas correlações positivas entre o grau de conversão e a contração e entre o grau de conversão e a taxa de contração. A cor variou na sequência: DMAEMA < DEPT < DMPT < CEMA < DABE. A transmitância variou na sequência: DEPT &#8776; DABE < DABE &#8776; DMPT &#8776; CEMA < DMPT &#8776; CEMA &#8776; DMAEMA, sendo mais evidente para o comprimento de onda de 400nm. Não foram observadas correlações entre o grau de conversão e as propriedades ópticas. A resina contendo DMAEMA apresentou maior grau de conversão, contração, taxa de contração e dureza, além de melhor estabilidade nas propriedades ópticas. / The aim of this work was to evaluate de influence of different tertiary amines on degree of conversion (DC), shrinkage-strain, shrinkage-strain-rate, Knoop microhardness, and colour and transmittance stabilities of experimental resins containing BisGMA / TEGDMA (3:1 wt), 0,25wt% camphorquinone, 1wt% amine (DMAEMA, CEMA, DMPT, or DABE). Different light-curing protocols were also evaluated. DC was evaluated with FTIR-ATR and shrinkage-strain with the bonded-disc method. Shrinkage-strain-rate data were obtained from numerical differentiation of shrinkage-strain data with respect to time. Colour stability and transmittance were evaluated during different periods of artificial aging, according to ISO 7491:2000. Results were evaluated with ANOVA, Tukey and Dunnetts T3 tests (&#945; = 0.05). The studied properties varied according to amines. DC and shrinkage-strain were maximum at the sequence: CQ < DEPT < DMPT &#8804; CEMA &#8776; DABE < DMAEMA. Both DC and shrinkage were also influenced by the curing protocol, with positive correlations between DC and shrinkage-strain and DC and shrinkage-strain-rate. Colour varied in the sequence: DMAEMA < DEPT < DMPT < CEMA < DABE. Transmittance varied in the sequence: DEPT &#8776; DABE < DABE &#8776; DMPT &#8776; CEMA < DMPT &#8776; CEMA &#8776; DMAEMA, being more evident at the wavelength of 400nm. No correlations between DC and optical properties were observed. The resin containing DMAEMA showed higher DC, shrinkage-strain, shrinkage-strain-rate and microhardness, in addition with better optical properties.

Ce travail a consisté à élaborer de nouveaux verres moléculaires transporteurs de trou dérivés du carbazole pour remplacer le spiro-OMeTAD (matériau de référence) dans les cellules solaires hybrides à colorant tout solide. Nous avons synthétisé différents dérivés du carbazole 3, 6, 9 substitués, établi leurs principales propriétés physico-chimiques et les avons utilisés en DSSC solide. Nous avons mis en évidence l'intérêt de greffer des groupements bis(4-méthoxyphényl)amines en positions 3, 6 et des aryles en position 9 du carbazole pour obtenir des matériaux performants. Finalement, cette structure type établie a permis de développer un concept innovant de synthèse de dérivés de carbazole ouvrant la voie à l'élaboration d'une large famille de verres moléculaires et permettant la préparation aisée de structures complexes performantes dans les DSSC solide. Nos meilleurs matériaux ont donné, en dispositifs sans optimisation, des performances comparables à celles du spiro-OMeTAD permettant d'entrevoir à terme la préparation de dispositifs à sensibilisateur pérovskite de rendements supérieurs à 15% / The aim ot this work has been to prepare new hole transporting molecular glasses based on carbazole moieties as an alternative to spiro-OMeTAD (standard material) in solid state dye sentitized solar cells (ssDSSC). We have synthesized several 3, 6, 9 substituted carbazole derivatives and have established their physical and chemical properties prior using them in photovoltaic devices. We have demonstrated the interest of grafting functional groups as bis(4-methoxyphenyl)amines on 3, 6 positions and aryl substitutes on the 9 position of carbazole to obtain efficient materials. Finally, this latter chemical structure has been used as a building block to develop an innovative concept of synthesis of carbazole based materials, smoothing the way to easy synthesis of a wide family of efficient molecular glasses for ssDSSC. Our best materials exhibit similar power conversion efficiency compare to the standard spiro-OMeTAD. According to these preliminary results, we expect reaching power conversion efficiencies over 15% with our carbazole based hole transporting materials associated with peroskite sensitizer.

Dans cette thèse, nous avons décrit de nouvelles méthodes pour la préparation de polymères et de produits chimiques à partir de ressources renouvelables:Premièrement, nous avons défini une nouvelle méthode de préparation de sulfonamides, utilisant des nitro-aromatiques et des sels de sulfinate de sodium, dans une solution aqueuse de bisulfite de sodium, en tant qu’agent réducteur non toxique. Le produit a été séparé par une simple filtration. La réaction montre une chimio-sélectivité complète, seuls les substrats nitro déficitaire en électrons sont réactifs. Cependant, et contrairement à la littérature, les sels de sulfinate de sodium aromatiques et aliphatiques se sont révélés réactifs dans nos conditions. De plus, nous avons utilisé cette méthode pour préparer de manière écologique le catalyseur de zinc décrit par Karamé et al. et utilisé pour la cycloaddition du dioxyde de carbone avec des époxydes, afin d'accéder aux monomères de polycarbonates pour la préparation de polyuréthane non isocyanate.Ensuite, nous avons étudié la préparation de bis-carbonate de mannitol à partir de mannitol, en utilisant le carbonate de diméthyle comme réactif et comme solvant. Le carbonate de glycérol a été utilisé comme co-solvant en raison de ses propriétés de solubilisation intéressantes. La possibilité de synthèse des monomères diamines entièrement renouvelables a également été étudiée en utilisant des derives des sucres comme la furfurylamine et le 5-méthylfurfural. Nous avons également etudier l’aminolyse du bis-carbonate du mannitol avec la furfurylamine à la température ambiante. De plus, nous avons comparé la stabilité de ce carbonate avec les monomères carbonates commerciaux en utilisant une analyse gravimétrique thermique.Enfin, nous avons préparé le diester de 4,4'-oxydipentanoate de diéthyle à partir de lévulinate d'éthyle par éthérification réductrice sans solvant, catalysée par du triflate de cuivre, en utilisant du tétraméthydisiloxane comme agent réducteur. En outre, nous avons prouvé que ce nouveau monomère était utilisable dans la préparation des polyesters et des polyamides, dans des conditions de polycondensation classiques, en utilisant le propane diol et l’hexaméthylène diamine comme monomères modèles / In this thesis, we describe new methods for the preparation of polymers and chemicals from renewable resources: First we have defined new method for the preparation of sulfonamides, using nitro aromatics and sodium sulfinate salts, in aqueous sodium bisulfite solution as a non toxic reducing agent. The product was separated by simple filtration and the reaction show full chemoslectivity, only electron poor nitro substrates are reactive. However, in contrast with the literature, aromatic and aliphatic sodium sulfinate salts were found reactive under our conditions. In addition, we have used this method to prepare, in a green way, the active zinc catalyst reported by Karamé et al. for the cycloaddition of carbon dioxide with epoxydes, in order to access to polycarbonates monomers for non-isocyanate polyurethane preparation.Then, we have investigated the preparation of high purity mannitol bis-carbonate from mannitol using dimethyl carbonate as a reagent and as a solvent. Glycerol carbonate was used as co-solvent due to its interesting solubilization properties. The possibility of the synthesis of fully renewable diamine monomers was also investigated using furfurylamine and 5-methylfurfural derivated from sugars. We have also uncovered its high reactivity toward uncatalyzed aminolysis with furfurylamine at room temperature. Furthermore, we have compared the stability of this carbonate with existing commercial monomers using thermal gravimetric analysis.Finally, we prepared the diethyl 4,4'-oxydipentanoate diester from renewable ethyl levulinate was prepared by solventless reductive etherification, catalyzed by copper triflate, using tetramethydisiloxane as safe and low-cost reducing agent. Besides, we have proved the usability of this new monomer in the preparation of sustainable polyesters and polyamides, under classical polycondensation conditions, using propane diol and hexamethylene diamine as model monomers

Doctor of Philosophy(PhD), / This thesis describes the synthesis of terminal and internal amino and amidoalkynes and their hydroamination (cyclisation) catalysed by the complex (bis(N-methylimidazol-2-yl)methane)dicarbonylrhodium(I) tetraphenylborate (1). A series of analogous palladium complexes were also prepared and investigated for catalytic hydroamination. The scope of the rhodium(I) complex (1) for the intramolecular hydroamination of more complex amino and amidoalkyne substrates was investigated. This was made possible with the synthesis of aliphatic substrates, namely, 4 pentyn 1 amide (3) and 5 hexyn 1 amide (4) and a number of aromatic substrates, namely, 1, 4 diamino-2, 5 diethynylbenzene (5), 1, 4-diamino-2, 5 bis(phenylethynyl)benzene (6), 2, 3-diamino-1, 4-diethynylbenzene (7), 2, 3-diamino-1, 4-bis(phenylethynyl)benzene (8), 1, 5-bis(acetamido)-2, 4-diethynylbenzene (9), N-(acetyl)-2-ethynylbenzylamine (10) and N-(acetyl)-2-(phenylethynyl)benzylamine (11). The rhodium(I) complex (1) catalytically cyclised the aliphatic 4 pentyn 1 amide (3) regioselectively to the 6 membered ring, 3, 4 dihydro 2 pyridone (64) as the sole product. Attempts to cyclise 5 hexyn 1 amide (4) to produce either the 6 or 7 membered ring were unsuccessful. Compounds 5, 6, 7 and 8 were doubly cyclised to 1, 5 dihydro pyrrolo[2, 3 f]indole (71), 1, 5-dihydro-2, 6-diphenyl-pyrrolo[2, 3 f]indole (73), 1, 8-dihydro-pyrrolo[2, 3 g]indole (74) and 1, 8-dihydro-2, 7-diphenyl-pyrrolo[2, 3 g]indole (75) respectively. The aromatic amides with terminal acetylenes 9 and 10 cyclised to give 1, 7 diacetyl pyrrolo[3, 2 f]indole (76) and N (acetyl) 1, 2 dihydroisoquinoline (77) respectively. However, attempts to cyclise 11 were unsuccessful. Thus the rhodium(I) complex (1) successfully catalysed via hydroamination both terminal and internal acetylenic amine and amide substrates, to give pyridones, indoles and isoquinolines. Cationic and neutral palladium complexes incorporating the bidentate heterocyclic nitrogen donor ligand bis(N-methylimidazol-2-yl)methane (bim; 2) were synthesised: [Pd(bim)Cl2] (15), [Pd(bim)2][BF4]2 (17) [Pd(bim)(Cl)(CH3)] (14), [Pd(bim)(CH3)(NCCH3)][BF4] (16). All of the complexes were active as catalysts for the intramolecular hydroamination reaction, using the cyclisation of 4 pentyn 1 amine (21) to 2 methyl 1 pyrroline (22) as the model test reaction. Percentage conversions, turnover numbers and reaction profiles for each complex were compared to the rhodium(I) complex (1). These studies have shown that the catalytic activity was not significantly dependent on the bim donor ligand or the choice of metal. Substitution of the bim (2) ligand with the COD ligand and the use of methanol as the solvent did impact significantly on the efficiency of the hydroamination reactions.