Neste trabalho à feita uma revisÃo das principais propriedades da molÃcula de poliacetileno sob o ponto de vista da teoria de campos. A seguir, estuda-se duas cadeias de poliacetileno acopladas usando o mesmo formalismo e verifica-se que esse sistema apresenta um gap em sua estrutura de bandas. Esse gap de energia à calculado em termos de uma massa efetiva quantizada que depende do acoplamento entre as cadeias de poliacetileno. Quando o acoplamento cessa o gap desaparece e recupera-se o resultado prÃvio de uma simples cadeia nÃo dimerizada. Mostra-se que entÃo hà uma quebra da simetria quiral. O comportamento do poliacetileno acoplado tambÃm à analisado quando existem sÃlitons em sua estrutura. Um formalismo à desenvolvido para mostrar que hà um fenÃmeno oscilatÃrio de natureza quÃntica anÃlogo Ãs oscilaÃÃes de Bloch. A condutividade do sistema à tambÃm calculada. / We review in this work the principal properties of single polyacetylene chain from a theoretical field formalism. Then, we study a coupled polyacetylene chain using the same formalism and verify that this system presents a gap in its electronic band structure. This energy gap is calculated in terms of a quantized effective mass that depends on the coupling between the polyacetylene chains. As the coupling decreases the gap vanishes and we restore the previous results of one single polyacetylene chain not dimerized. We show that there is a chiral broken symmetry. We study also the behavior of coupled polyacetilene in presence of solitons. A formalism is developed to show that there is an oscillatory phenomenon of quantum character analogous to Bloch oscillations. The conductivity of the system is also calculated.

As especiarias e as ervas aromáticas se apresentam na forma de folhas, flores, gomos, sementes, cascas ou rizomas secos de diferentes plantas. Podemos defini-las como produtos de origem vegetal aromatizados que se volatilizam com facilidade quando incorporados em pequena quantidade aos produtos alimentares, e contribuem para o seu aroma, sabor e cor ou ainda para sua conservação. Atualmente as pessoas procuram as especiarias por suas propriedades funcionais, compostos bioativos e qualidades sensoriais. Um grande problema é a redução da quantidade destes compostos durante toda a cadeia produtiva, a partir da colheita, processamento, armazenamento e distribuição. Há muito tempo, pesquisadores e indústrias estão concentrados no aprimoramento dos processos na cadeia produtiva, buscando garantir a segurança sanitária e alimentar, a conservação dos alimentos por mais tempo e o aumento de sua vida útil, sem alterar, de forma drástica, suas propriedades. Devido às produções artesanais e à falta do cumprimento das boas práticas em sua cadeia produtiva, as especiarias podem conter alta carga microbiológica, acarretando sérias complicações à saúde do consumidor. Para diminuir esses problemas, frequentemente é utilizado o processamento por radiação. Com o exposto, os objetivos deste trabalho foram: Analisar as propriedades antifúngicas dos óleos das especiarias irradiadas com doses médias (2,5; 5; 7,5 e 10 kGy); Estudar os efeitos de doses médias (5 e 10 kGy) e altas (20 e 30 kGy) de radiação gama de 60Co nos compostos bioativos das especiarias - cravo, canela e noz-moscada; Identificar os compostos dos óleos; Identificar o compostos voláteis no headspace dos óleos e das especiarias in natura; Identificar os compostos da parte não volátil da noz-moscada e Identificar os compostos quirais da canela. Ao comparar as amostras controle (não irradiadas) com as processadas nas doses descritas, em relação às propriedades antifúngicas dos óleos, foi possível verificar a eficácia e posteriormente que a irradiação não interferiu em sua eficiência; Em relação aos demais testes deste trabalho, os compostos foram identificados e na maioria dos testes o processo de irradiação não interferiu de forma significativa na quantidade dos compostos. / Spices and aromatic herbs are divided into leaves, flowers, bud, seeds bark or dry roots from different plants and it is possible to define them as products of highly flavored vegetal origin that volatize easily when incorporated in small quantities to food products and contribute to its aroma, flavor, color or even to its preservation. Nowadays, people look for its functional properties, bioactive compounds and sensory qualities. A big problem is the reduction of the quantity of these compounds throughout the production chain from the harvest process, storage and distribution. For a long time researchers and industries have concentrated on perfecting the processes of the production chain seeking to guarantee the sanitary and food safety, preserving foodstuffs for a long period and an increase in its lifespan without drastically altering its properties. Due to homemade products and the lack of compliance with good practices in its production chain, the spices can contain a high amount of microbiology causing serious complications to the health of the consumer and the radiation processing is often used for reduce these problems. With this finding, the objectives of this work were: Analyze the oil antifungal properties of spices irradiated with average doses (2.5; 5; 7.5 and 10 kGy); Study the average doses (5 and 10 kGy) and high dose (20 and 30 kGy) effects of gamma radiation 60Co in the bioactive compounds of the spices - cloves, cinnamon and nutmeg; Identify the oils compounds; Identify the volatile compounds in the headspace of the oils and the in natura spices. Identify the compounds of the nonvolatile part of the nutmeg; Identify the chiral compounds of the cinnamon. Comparing the control samples (not irradiated) with the processed at the described doses, regarding the oil antifungal properties it was possible to verify the efficiency and later that the irradiation did not interfered in its efficiency; Regarding to the others tests in this work, the compounds were identified and most of the tests the irradiation did not interfere significantly with the compounds amount.

A malária é a doença que mais mortes causa no mundo. O uso de fármacos antimaláricos representa a solução mais eficaz para o combate e controle da doença e o interesse pelo desenvolvimento de novos fármacos é grande devido a problemas de resistência. Existe uma grande variedade de fármacos antimaláricos, sendo que muitos deles são quirais, vendidos e administrados como mistura racêmica. Nas últimas décadas, houve um aumento no interesse quanto aos aspectos farmacodinâmicos e farmacocinéticos de fármacos quirais, devido ao conhecimento de que um dos isômeros pode ser mais ativo ou mais tóxico que o outro. Sendo assim, tem-se a necessidade do desenvolvimento de métodos analíticos enantiosseletivos, e a eletroforese capilar tem emergido como uma técnica de separação quiral com alto poder de resolução. Além disso, a inexistência de métodos oficiais para fármacos antimaláricos e os poucos estudos que relatam aplicações na análise de formulações farmacêuticas, demandam o desenvolvimento e validação de novos métodos para tal finalidade. Este trabalho tem como objetivo o desenvolvimento de dois métodos analíticos, não quiral e quiral, para a determinação de fármacos antimaláricos em formulações farmacêuticas por eletroforese capilar. O método não quiral utilizou eletroforese capilar de zona, sendo otimizado para a separação de 7 fármacos antimaláricos (cloroquina, hidroxicloroquina, primaquina, quinidina, quinina, quinacrina e mefloquina) com um eletrólito composto por 45 mmol L-1 de tampão citrato, pH 4,50, e apresentou um tempo de análise de 10 minutos, permitindo a separação dos diastereoisômeros quinina e quinidina sem a adição de aditivos. O método quiral utilizou eletroforese capilar de zona modificada por ciclodextrina e foi otimizado para separação enantiosseletiva de cloroquina, mefloquina, hidroxicloroquina, primaquina, quinina e quinidina com um eletrólito composto por 50 mmol L-1 de tampão citrato, e 2% de S-β-CD, pH 2,7. A separação dos fármacos antimaláricos e seus enantiômeros foi alcançada com tempo de análise de 12 minutos. Os métodos desenvolvidos foram validados de acordo com os protocolos oficiais, apresentando características adequadas e foram aplicados na determinação de cloroquina, hidroxicloroquina e mefloquina em formulações farmacêuticas. Como figuras de mérito para o método não quiral, tem-se: linearidade (R2 > 0,99), LD (7,43 - 24,4 µmol L-1), LQ (22,5 - 73,8 µmol L-1), precisão intermediária (0,76 - 1,7% RSD), recuperação (97,8 - 102,2%). Para o método quiral, tem-se: linearidade (R2 > 0,99), LD (7,43 - 9,58 µmol L-1), LQ (22,8 - 29,0 µmol L-1), precisão intermediária (0,50 - 1,8% RSD), recuperação (97,7 - 102,5%). Um ensaio de robustez para ambos os métodos foi realizado para comparar os resultados obtidos aplicando-se pequenas variações de tensão e temperatura. Observou-se que não existe uma diferença significativa entre os resultados, a um nível de confiança de P = 95 %. / Malaria is a disease that causes a large number of deaths worldwide. The use of antimalarial drugs is the most effective solution to combat and control the disease and interest in the development of new antimalarial drugs is still of great importance due to resistance issues. There is a wide variety of antimalarial drugs, many of which are chiral, sold and administered as racemic mixtures. In recent decades there has been an increased interest regarding the pharmacodynamic and pharmacokinetic aspects of chiral drugs, due to the knowledge that one of the isomers can be more active or more toxic than the other. Thus, there is a need for the development of enantioselective analytical methods, and capillary electrophoresis has emerged as a chiral technique separation with high resolving power. Moreover, the lack of official methods for antimalarial drugs and the few studies reporting applications in the analysis of pharmaceutical formulations, demands the development and validation of new methods for this purpose. This work aims at the development of two analytical methods, non-chiral and chiral, for the determination of antimalarial drugs in pharmaceutical formulations by capillary electrophoresis. The non-chiral method used capillary zone electrophoresis, being optimized for the separation of 7 antimalarial drugs (chloroquine, hydroxychloroquine, primaquine, quinidine, quinine, quinacrine and mefloquine) with an electrolyte consisting of 45 mmol L-1 of citrate buffer, pH 4.50, and had an analysis time of 10 minutes, allowing separation of isolated diasteroisomers quinine and quinidine without any additives. The chiral method used capillary zone electrophoresis modified by cyclodextrin and was optimized for enantioselective separation of chloroquine, mefloquine, hydroxychloroquine, primaquine, quinine and quinidine with an electrolyte consisting of 50 mmol L-1 citrate buffer and 2% S-β-CD, pH 2.7. The separation of the antimalarial drugs and their enantiomers was achieved in less than 12 minutes. The proposed methods were validated following official protocols, with adequate results and were used for determination of chloroquine, hydroxychloroquine, and mefloquine in pharmaceutical formulations. Figures of merit for the non-chiral method include: linearity (R2> 0.99), LD (7.43 to 24.4 µmol L-1), LQ (22.5 to 73.8 µmol L-1), intermediary precision (0.76 to 1.7% RSD), and recovery (from 97.8 to 102.2%). For the chiral method, we have: linearity (R2> 0.99), LD (7.43 to 9.58 µmol L-1), LQ (22.8 to 29.0 µmol L-1), intermediary precision (0.50 to 1.8% RSD), and recovery (from 97.7 to 102.5%). For both methods a robustness test was performed to compare the results obtained by applying slight variations in voltage and temperature. It was observed that there is no significant difference between the results, a confidence level P = 95%.

A interação forte a baixas energias pode ser abordada por meio de lagrangianas efetivas. Nesse contexto, o modelo de Skyrme representa uma forma de descrever bárions, que emergem como sólitons topológicos de uma lagrangiana mesônica quiral. A interação nucleon-nucleon (NN) é comumente tratada neste modelo de maneira aproximada, através do chamado Ansatz Produto (AP), cujo problema mais sério é não reproduzir a atração de alcance intermediário no canal escalar-isoescalar do potencial NN. O objetivo deste trabalho é construir um novo ansatz para o cálculo da interação NN no modelo de Skyrme. Para isso, analisamos o AP, investigando as causas deste problema fenomenológico, e concluímos que deve-se à componente azimutal de seu campo piônico. A partir disto, construímos o Ansatz Novo (AN), com o qual calculamos o novo potencial. Comparando os resultados com outros potenciais existentes, mostramos que o AN constitui uma solução plausível para o problema. / Strong interactions at low energies can be treated by means of effective lagrangians. In this context, the Skyrme model is regarded as a way to describe baryons as topological solitons from a chiral mesonic lagrangian. In the framework of this model, nucleon-nucleon (NN) interaction is usually derived in the sudden approximation, by means of the so called Product Ansatz (PA). Its most serious problem is the absence of the intermediate range attraction in the scalar-isoscalar channel of the NN potential. We construct a new ansatz to derive the NN interaction in the Skyrme model. At first, we analise the PA and investigate the causes of its phenomenological problem. We conclude it is due to the azimuthal component of its pionic field. With this result we build the New Ansatz (NA) and calculate the new potential. Comparisons of the results with other existent potentials show that NA constitutes a plausible solution to the problem.

abstract: Chiral symmetry and its anomalous and spontaneous breaking play an important role in particle physics, where it explains the origin of pion and hadron mass hierarchy among other things. Despite its microscopic origin chirality may also lead to observable effects in macroscopic physical systems -- relativistic plasmas made of chiral (spin-$\frac{1}{2}$) particles. Such plasmas are called \textit{chiral}. The effects include non-dissipative currents in external fields that could be present even in quasi-equilibrium, such as the chiral magnetic (CME) and separation (CSE) effects, as well as a number of inherently chiral collective modes called the chiral magnetic (CMW) and vortical (CVW) waves. Applications of chiral plasmas are truly interdisciplinary, ranging from hot plasma filling the early Universe, to dense matter in neutron stars, to electronic band structures in Dirac and Weyl semimetals, to quark-gluon plasma produced in heavy-ion collisions. The main focus of this dissertation is a search for traces of chiral physics in the spectrum of collective modes in chiral plasmas. I start from relativistic chiral kinetic theory and derive first- and second-order chiral hydrodynamics. Then I establish key features of an equilibrium state that describes many physical chiral systems and use it to find the full spectrum of collective modes in high-temperature and high-density cases. Finally, I consider in detail the fate of the two inherently chiral waves, namely the CMW and the CVW, and determine their detection prospects. The main results of this dissertation are the formulation of a fully covariant dissipative chiral hydrodynamics and the calculation of the spectrum of collective modes in chiral plasmas. It is found that the dissipative effects and dynamical electromagnetism play an important role in most cases. In particular, it is found that both the CMW and the CVW are heavily damped by the usual Ohmic dissipation in charged plasmas and the diffusion effects in neutral plasmas. These findings prompt a search for new physical observables in heavy-ion collisions, as well as a revision of potential applications of chiral theories in cosmology and solid-state physics. / Dissertation/Thesis / Doctoral Dissertation Physics 2019

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Une échelle de taille contenant 20 substituants usuels en chimie a été construite à partir des barrières de rotations de N-aryl-thiazoline-2-thiones. L’énergie d’activation ΔG≠rot qui est mesurée reflète l’encombrement stérique du substituant en ortho du cycle benzénique. Les perturbations électroniques, et les facteurs externes tels que la température ou le solvant sont négligeables. La grande sensibilité du modèle proposé conduit au classement suivant Me > Cl et CN > OMe > OH. Ces classements divergents décrits dans la littérature seront discutés. Une limitation du modèle proposé concerne les substituants très volumineux comme le CF3 et l’iPr qui apparaissent plus petit qu’ils ne le sont en réalité à cause d’un encombrement stérique dans l’état fondamental qui abaissent la valeur de la barrière de rotation. / A steric scale of 20 recurrent groups was established from comparison of rotational barriers on N-(o-substituted-aryl)-thiazoline-2-thione atropisomers. The resulting energy of activation ΔG≠rot reflects the spatial requirement of the ortho substituent borne by the aryl moiety, electronic aspects and external parameters (temperature and solvent) generating negligible contributions. Concerning divergent rankings reported in literature, the great sensitivity of this model allowed to show unambiguously that a methyl appears bigger than a chlorine, and gave the following order in size: CN > OMe > OH. For the very bulky CF3 and iPr groups, constraints in the ground state decreased the expected ΔG≠rot values resulting in a minimization of their apparent sizes.

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Design of targeted functional solid-state materials for desired applications remains a scientific challenge. To overcome this hurdle, numerous synthetic strategies have been devised. It has been shown that molecules and/or clusters with pre-selected shapes, molecular building blocks (MBBs), can be utilized as units of chemical construction toward a final structure composed of those units. Typically, in metal-organic structures metal-ligand directed assembly of the MBBs, via coordination chemistry in situ, leads to the final structure. The strength of the MBB formed and, consequently, the overall rigidity of the framework are essential in their use as porous materials for applications. Lack of rigidity, i.e. instability, will ultimately lead to the collapse of the open framework upon evacuation, resulting in inaccessible pores. This phenomenon has been demonstrated repeatedly in labile metal-organic materials (MOMs) constructed via flaccid metal-nitrogen coordination (MNx) between nitrogen-based ligands and metal ions. The structures of simple metal-carboxylate clusters are welldocumented, but only recently have they been targeted for the construction of MOMs. They often possess multiple metal-oxygen coordination bonds (M(CO2)x) that result in the generation of rigid nodes with fixed geometry. Our research group has utilized heterofunctional organic linkers, taking advantage of both pyridine- and carboxylate-based functions (MNy(CO2)z), which has allowed the construction of single-metal-ion-based MBBs resulting in stabile, rigid MOMs with targeted topologies. In this dissertation, I will discuss our single-metal-ion-based design strategy and the utilization of heterofunctional ligands for MNy(CO2)z coordination of single-metal ions. I have employed this strategy to specifically target threeconnected MOMs from 3,5-pyridinedicarboxylate and MNy(CO2)z coordination of various single-metal ions, especially chiral framworks such as (10,3)-a. In addition, I have explored the MOM diversity that can be obtained via various ligand modifications, including isomerism, expansion, and functionalization. I also will show that other heterofunctional ligands can be utilized to target novel MOMs, specifically via M(CO)y(CO2)z coordination, and, resultantly, I have achieved metal-ligand directed organic synthesis and mixed-metal MOMs with magnetic tunability. I have also explored applications for MOMs, including H2 storage, and studied the barriers to rotation of the H2 molecules inside MOMs using inelastic neutron scattering to better understand the MOM-H2 interactions.