O objetivo desse estudo foi avaliar o efeito da distância da ponta fotoativadora na profundidade de polimerização da resina composta por meio de testes de microdureza Vickers e da análise do grau de conversão pelo método FT-Raman. O aparelho de luz halógena (500 mW/cm2) e o LED (900 mW/cm2) foram utilizados na sua intensidade convencional. O laser de argônio, na potência de 250 mW. Os tempos de fotoativação foram de 40 segundos para a luz halógena, 20 segundos para o LED e 20 e 30 segundos para o laser. E as distâncias da ponta fotoativadora foi padronizada com anéis de 3, 6 e 9 mm de altura. A resina composta micro-híbrida foi inserida em porção única, em matrizes de polipropileno pretas com as espessuras de 1 a 4 mm. Os corpos-de-prova foram armazenados por uma semana a seco, a 37ºC em recipientes protegidos da luz. Os dados da microdureza e do grau de conversão foram analisados separadamente por meio da análise de variância e teste de Tukey, com nível de significância de 5% e depois correlacionados pelo teste de correlação de Pearson. Os resultados obtidos permitiram concluir que: o aumento da distância da fonte de luz promoveu uma diminuição nos valores de microdureza e no grau de conversão para todos os tipos de fontes de luz estudados e o mesmo ocorreu com o aumento da espessura de resina composta diminuindo também os valores de microdureza e grau de conversão. Houve uma alta correlação entre a análise PDM (porcentagem de dureza máxima) e a análise do grau de conversão e entre o teste de microdureza e a análise do grau de conversão. As fontes de fotoativação estudadas promoveram grau de conversão e microdureza correspondentes entre si, desde que a espessura da resina fosse de 1 mm de espessura e a que a fonte estivesse a uma distância máxima de 3 mm. / This study evaluated the influence of curing tip distance on cure depth of a composite resin, measuring the Vickers microhardness and determining the degree of conversion, using FT-Raman spectroscopy. The halogen light (500 mW/cm2) and the LED (900 mW/cm2) were used with conventional intensity of power and the argon laser with 250mW. The exposure time was 40 seconds to halogen light, 20 seconds to LED and 20 and 30 seconds to Argon laser. And the curing tip distances used (0, 3, 6 e 9 mm) were controlled by metals rings. The composite was placed in one increment, in a black polipropilen matrix with thickness of the 1 to 4 mm. The specimens were stored for one week in dry stove, for 37ºC in containers protect from the light. The values of microhardness and degree of coonversion were analyzed separately by ANOVA (Analysis of variance) and Tukey test, with significance level for 5%. Then, the correlation was analyzed by Pearson test. The results obtained conclude that: the increased of tip distance produced a decreased in microhardness and degree of conversion values; the microhardness and degree conversion values decreased as the thickness increased; it showed a higher correlation between the qualities of polymerization and the degree of conversion and between the microhardness test and the degree of conversion. The present study suggests that the units of polymerization studied produced microhardness and degree of conversion values that corresponded to each other, only with 1mm of thickness and using a tip distance of 3 mm, at most.

Objetivo: Este estudo se propõe a verificar a influencia do tipo de luz fotopolimerizadora na força de retenção de pinos intra-radiculares, tanto na técnica direta como na direta indireta. Métodos: 40 raízes de dentes bovinos com comprimento de 12 mm foram tratadas endodonticamente e divididas aleatoriamente em 4 grupos de acordo com a técnica de obtenção dos pinos e luz fotopolimerizadora (n=10): grupo 1 (técnica direta associada à lâmpada halogena); grupo 2 (técnica direta ao LED); grupo 3 (técnica direta-indireta associada à lampada halógena); e grupo 4 (técnica direta-indireta associada ao LED). A força de retenção foi determinada através do teste de tração usando Universal Testing Machine (Instron). Todos os dados foram analisados usando one-way analysis of variance (ANOVA) com a significância de p<0.05 e complementadas com teste de Tukey. Após o teste, as interfaces adesivas onde ocorreram as falhas foram examinadas e classificadas. Resultado: Os grupos 3 (246,05N ± 29,51) e 4 (241,60N ± 28,95) não apresentaram força de retenção estatisticamente diferente mas foram maiores que os grupos 1 (142,30N ± 25,60) e 2 (178,56N ± 25,67). A maior parte das fraturas ocorreu na interface dentina/resina. Conclusão: Com base nos resultados obtidos, concluímos que o método direto-indireto proporcionou a melhor retenção dos pinos de fibra de vidro. / Objectives: The purpose of this study is to verify the influence of light curing type on retention force of direct technique and direct-indirect technique. Methods: Fourth bovine single root teeth with 12mm of length were used in this study. The roots were endodontically treated and randomly divided in four groups according to the light curing unit and technique used: group 1(direct technique, halogen lamp), group 2(direct technique, LED), group 3(direct-indirect technique, halogen lamp), group 4(direct-indirect technique, lamp). The retention force was determined sing a Universal Testing Machine (Instron). All data were analyzed using one-way analysis of variance (ANOVA) and Tukey test. After the test, the failure was examined and classified according to the fracture place: post/ resin; resin/dentin; mix. Results: Group 3 (246,05N ± 29,51) and 4(241,60N ± 28,95)4 (95,18N) did not show statistically difference but presented higher retention force than group 1 (142,30N ± 25,60) and 2 (178,56N ± 25,67). Most of fracture occurred in interface between dentin/resin. Conclusion: Based on the obtained results, it was concluded that adhesive cementation technique influenced in the retention of glass fiber post.

Carbenoides são intermediários altamente reativos que desempenham um papel fundamental em estratégias sintéticas modernas. Essas espécies são muito semelhantes aos carbenos no estado singleto, visto que possuem um caráter ambifílico e reagem por um mecanismo concertado, levando a produtos estereoespecíficos. Estudos preliminares demonstraram a versatilidade de um carbenoide misto de magnésio e lítio (ClCH2 MgCl·LiCl) na reação com diversos aldeídos aromáticos, alifáticos e heterocíclicos. Desta maneira, o objetivo deste trabalho foi estudar a quimiosseletividade de tal reagente e investigar a aplicação deste na síntese diasterosseletiva do (2S,3S)-N-Boc-3amino-1,2-epóxi-4-fenilbutano e seu diastereoisômero de configuração (2R,3S). Para a primeira parte do trabalho, selecionamos alguns aldeídos contendo grupos funcionais, tais como, ésteres, nitrilas, cetonas, amida, entre outros. De maneira geral, o carbenoide de magnésio mostrou-se muito eficiente e quimiosseletivo, levando a 14 cloridrinas funcionalizadas em bons rendimentos isolados, contudo, quando grupos doadores de elétrons estavam presentes na posição 4 do anel, o aldeído apresentou uma diminuição de reatividade e impossibilitou a obtenção do produto desejado. Por fim, estudos preliminares visando à preparação dos epóxidos de configuração (2S,3S) e (2R,3S) foram também realizados e os resultados são discutidos de forma detalhada no texto. / Carbenoids are a class of highly reactive intermediate compounds that play a key role in modern synthetic strategies. These species show a state very similar to that of singlet state carbenes since they have an ambiphilic character and react by a concerted mechanism, something that allows them to afford stereospecific products. Previous studies demonstrated the versatility of a mixed magnesium and lithium carbenoid (ClCH 2 MgCl·LiCl) in the reaction with a number of aromatic, aliphatic and heterocyclic aldehydes. In this way, the objective of this work was to study the chemoselectivity of such reagent and investigate its application in the diastereoselective synthesis of (2S,3S)-N-Boc-3-amino-1,2-epoxy-4-phenylbutane and its diastereoisomer of configuration (2R,3S). For the first part of the work we selected some aldehyde containing functional groups such as esters, nitriles, ketones and amide, among others. In summary, the magnesium carbenoid proved to be very efficient and chemoselective, leading to 14 functionalized chlorohydrins in good isolated yields. Nevertheless, when electron donating groups were present at the position 4 of the substrates ring, the resulting aldehyde showed a decrease in reactivity, which precluded us to obtain the desired product. Finally, preliminary studies aiming the preparation of the epoxides of configuration (2S,3S) and (2R,3S) were also investigated and the results are discussed in detail in the text.

A presente dissertação trata de um estudo teórico-experimental sobre a perda de pressão em canais de diâmetro reduzido durante escoamento bifásico de refrigerantes halogenados. Trocadores de calor baseados na ebulição convectiva, em condições de micro-escala são amplamente estudados devido à intensificação da troca de calor proporcionada e a possibilidade de compactação de sistemas de resfriamento. Proporcionam também a redução do inventário de refrigerante e do material utilizado no processo de fabricação do trocador. Porém, o incremento da transferência de calor é acompanhada pelo aumento da perda de pressão, parâmetro também fundamental para o desempenho do sistema. Para o projeto satisfatório e otimizado destes dispositivos são necessários métodos de previsão de transferência de calor e perda de pressão. Entretanto, no caso de canais de diâmetro reduzido, tais ferramentas não encontram-se disponíveis e trocadores de calor baseados em escoamentos bifásicos no interior de canais de diâmetro reduzido vêm sendo desenvolvidos heuristicamente. Desta forma, inicialmente neste estudo, realizou-se uma revisão crítica da literatura envolvendo critérios de transição entre padrões de escoamento, fração de vazio superficial, perda de pressão no interior de canais com diâmetro reduzido durante escoamento bifásico e os principais métodos de estimativa da perda de pressão para macro e micro-escala. Resultados experimentais para perda de pressão levantados neste estudo em condições adiabáticas para os fluidos R245fa e R134a e tubo com 1,1 mm de diâmetro interno foram descritos e comparados aos métodos preditivos encontrados na literatura. Finalmente um novo método da previsão da perda de pressão foi proposto baseado na correlação de Müller-Steinhagen e Heck (1986), ajustando os valores do coeficiente e do expoente com base nos resultados experimentais levantados. / A theorical and experimental study on two-phase pressure drop inside micro-scale channels has been developed. Recently, the study of flow boiling in micro-scale channel have received special attention from academia and industry due to several advantages that they offer such as minimization of fluid inventory, high degree of compactness of the heat exchangers, better performance and the capacity of dissipate extremely high heat fluxes. The significant heat transfer coefficient enhancement provided by micro-scale channels comes together with a huge pressure drop penalty that impacts the efficiency of the overall cooling system. So, accurate predictive methods to evaluate the pressure drop are necessary for the appropriate design of the system and for its optimization. In the present study, firstly, a critical review on studies from literature was performed that covers criteria of transition between micro- and macro-scale flow boiling, void fraction, frictional pressure drop on micro-scale channels and the leading frictional pressure drop predictive methods. Experimental pressure drop results were acquired under adiabatic conditions for R245fa and R134a fluids and internal diameter tube of 1.1 mm. Then, the leading pressure drop predictive methods were compared against the present database. Also a new correlation based on Muller-Steinhagen e Heck (1986) method was proposed in this work by adjusting new empirical constants based on the present database together with previous results obtained by Tibiriçá et al. (2011) for a 2.3 mm ID tube.

No description available.

This dissertation attempts to extend the classes of halogen-containing systems which may be studied using solid-state nuclear magnetic resonance (SSNMR). As line shape broadening due to the quadrupolar interaction (QI) scales inversely with the applied field, high-field magnet technology is indispensable for this research. Combining advanced radiofrequency pulse sequences with high-field wideline data acquisition allowed for the collection of very broad SSNMR signals of all quadrupolar halogen nuclei (i.e., 35/37Cl, 79/81Br and 127I) within a reasonable amount of experimental time. The initial systems for study were of the MX2 variety (M = Mg, Ca, Sr, Ba; X = Cl, Br, I). In total, 9 anhydrous compounds were tested. The effects of hydrate formation were tested on 7 additional compounds. Systematic trends in the observed δiso values (and to a lesser extent, Ω and CQ) were found to be diagnostic of the extent of hydration in these materials. Resolving power was successfully tested using SrBr2, which possesses 4 magnetically unique sites. The composition of CaBr2•xH2O was convincingly determined using SSNMR data and the hydration trends noted above. The sensitivity of the QI to the local bonding environment (e.g., bond distance changes of less than 0.05 Å) was used to refine (when coupled with gauge-including projector augmented-wave density functional theory (GIPAW DFT) quantum chemical computations) the structure of MgBr2, and was used to correct prior NMR data for CaCl2 (earlier accounts had been performed upon a CaCl2 hydrate). During NMR data analysis of certain iodine-containing materials, it was found that standard fitting software (which uses perturbation theory) could not reproduce the observations. Proper analysis required the use of exact simulation software and allowed for the observation of high-order quadrupole-induced effects (HOQIE). This motivated further studies using rhenium-185/187 nuclei, where it was expected that HOQIE would be more dramatic. The observed rhenium SSNMR spectra possessed additional fine structure that had never been observed before experimentally, nor would be expected from currently-available perturbation theory analysis software. Lastly, preliminary results are shown where 127I SSNMR is used to study important supramolecular systems, and the composition of the popular synthetic reagent ‘GaI’ is elucidated.

Noncovalent interactions are of great importance in studies on crystal design and drug discovery. One such noncovalent interaction, halogen bonding, is present between a covalently bound halogen atom and a Lewis base. A halogen bond is a directional interaction caused by the anisotropic distribution of charge on a halogen atom X covalently bound to A, which in turn forms a positive region called σ-hole on the A–X axis. Utilization of halogen bonds in lead optimization have been rarely considered in drug discovery until recently and yet more than 50% of the drug candidates are halogenated. To date, the halogen bond has not been subjected to practical molecular mechanical-molecular dynamics (MM-MD) study, where this noncovalent interaction cannot be described by conventional force fields because they do not account for the anisotropic distribution of the charge density on the halogen atoms. This problem was solved by the author and, for the first time, an extra-point of positive charge was used to represent the σ-hole on the halogen atom. This approach is called positive extra-point (PEP) approach. Interestingly, it was found that the performance of the PEP approach in describing halogen bond was better than the semiempirical methods including the recent halogen-bond corrected PM6 (PM6-DH2X) method. The PEP approach also gave promising results in describing other noncovalent halogen interactions, such as C–X···H and C–X···π-systems. The PEP resulted in an improvement in the accuracy of the electrostatic-potential derived charges of halogen-containing molecules, giving in turn better dipole moments and solvation free energies compared to high-level quantum mechanical and experimental data.With the aid of our PEP approach, the first MM-molecular dynamics (MM-MD) study of inhibitors that form a halogen bond with a receptor was performed for tetrahalobenzotriazole inhibitors complexed to cyclin-dependent protein kinase (CDK2). When the PEP approach was used, the calculated MM-generalized Born surface area (MM-GBSA)//MM-MD binding energies for halobenzimidazole and halobenzotriazole inhibitors complexed with protein kinase CK2 were found to correlate well with the corresponding experimental data, with correlation coefficients R2 of greater than 0.90. The nature and strength of halogen bonding in halo molecule···Lewis base complexes were studied in terms of molecular mechanics using our PEP approach. The contributions of the σ-hole (i.e., positively charged extra-point) and the halogen atom to the strength of this noncovalent interaction were clarified using the atomic parameter contribution to the molecular interaction approach. The molecular mechanical results revealed that the halogen bond is electrostatic and van der Waals in nature. The strength of the halogen bond increases with increasing the magnitude of the extra-point charge. The van der Waals interaction’s contribution to the halogen bond strength is most favorable in chloro complexes, whereas the electrostatic interaction is dominant in iodo complexes.The failure of the PM6 semiempirical method in describing noncovalent halogen interactions —not only halogen bonds, but also hydrogen bonds involving halogen atoms— was reported and corrected by the introduction of a second and third generation of noncovalent halogen interactions correction. The developed correction yielded promising results for the four examined noncovalent halogen interactions, namely: C–X···O, C–X···N, C–X···π-system, and C–X···H interactions.

The aim of master´s thesis is to get acquainted with the design and materials used in selected automotive light source – tungsten halogen lamp. Further, the thesis focused on the theory and appropriate selection of the thermal measurement method on a real sample. Subsequently, a model of the light source and its simulation in the ANSYS – Maxwell 3D and Mechanical programs are created. Finally, the results of the thermal simulation and the non-contact measurement of the tungsten halogen lamp are evaluated

This master’s thesis deals with the possibilities of illumination of motor vehicles. Thesis is divided into two sections, from which the first discusses precisely the possibilities of lighting of motor vehicles at the present time. What are the modern lighting techniques, that can be found on the market and what is their impact on safety enhancement in road traffic. Second section is about the practical measurement of low and high beam afterglow. This measurement is being compared between two types of headlamps, namely halogen headlights and xenon headlights. Part of the measurement is as well measurement of illumination intensity precisely for these headlights. The output of measurement is the creation of own illumination intensity diagrams and afterglow diagrams of particular headlights, in comparison to isolux diagrams provided by the headlights manufacturer. Consequently are solved the issues about utilization of the isolux diagrams in expert praxis.

Ces travaux de thèse ont pour but l’étude théorique et la caractérisation d’interactions non-covalentes par des méthodes QCT (Quantum Chemical Topology), qui sont des outils interprétatifs de chimie quantique. Plusieurs interactions furent étudiées du point de vue de la densité électronique (calculs DFT), notamment des interactions intramoléculaires entre atomes halogènes ainsi que des liaisons halogène inter- et intramoléculaires. L’analyse topologique QTAIM complétée par la décomposition énergétique IQA (Interacting Quantum Atoms) nous a permis de dévoiler la nature physique des interactions étudiées, i.e. la part d’interaction électrostatique et la part d’échange (covalence). Il a été montré que l’échange tient un rôle majeur dans la stabilisation de telles interactions et permet de rationnaliser les différentes topologies observées en terme de compétition entre canaux d’échange primaires et secondaires. Aussi, la formation et la rupture d’une liaison hydrogène au cours de transferts de protons a été étudiée grâce à la décomposition de grandeurs globales (de DFTConceptuelle) en contributions monoatomiques ; le schéma de décomposition proposé se base sur la partition QTAIM et la décomposition énergétique IQA. Cette approche permet de suivre l’évolution, le long d’un chemin réactionnel, de la contribution de chaque atome à la réactivité du système. Une nouvelle façon de caractériser les barrières d’énergie potentielle et les états de transition a ainsi été proposée. / This work aims to theoretically investigate and characterize non-covalent interactions by means of Quantum Chemical Topology (QCT) methods, which are quantum chemistry interpretative tools. Several interactions were studied from the point of view of the electron density (DFT calculations), including intramolecular interactions between halogen atoms as well as inter- and intramolecular halogen bonds. The QTAIM topological analysis complemented by the Interacting Quantum Atoms (IQA) energy decomposition revealed the physical nature of those interactions, i. e. the part of electrostatics and the part of exchange (covalency). It has been shown that exchange plays a significant role in stabilizing such interactions and enables rationalizing the different topologies observed in terms of competition between primary and secondary exchange channels. Also, the formation and breaking of a hydrogen bond during proton transfer reactions has been analyzed by utilizing an atomic decomposition of global quantities (from Conceptual DFT), the new decompositionscheme being based on the QTAIM partition and the IQA energy decomposition. This approach allows following the contribution of every atom to the reactivity of the whole system along a reaction path, introducing a new way of characterizing energy barriers and transition.