Thesis (Ph.D.)--McMaster University (Canada), 1991. / Source: Dissertation Abstracts International, Volume: 53-01, Section: B, page: 0503. Supervisor: I. D. Brown.

This diploma thesis is solved for AtomTrace Company and describes mechanical design of modular system for elemental analysis using laser spectroscopy. Object of this thesis is to create at once compact and modular system, with addition of liquid analysis module. System described in this work came out from current solution and is capable of interaction of new and previous modules. New solution is more economical both in budget and mass, whole system is fully functional and liquid analysis module with flat jet has 40 % stability, as described in experiments. The benefit of this work is possible future integration of system or separate modules into the AtomTrace portfolio and industry applications.

Objects can be said to be structured when their representation also contains their parts. While OWL in general can describe structured objects, description graphs are a recent, decidable extension to OWL which support the description of classes of structured objects whose parts are related in complex ways. Classes of chemical entities such as molecules, ions and groups (parts of molecules) are often characterised by the way in which the constituent atoms of their instances are connected via chemical bonds. For chemoinformatics tools and applications, this internal structure is represented using chemical graphs. We here present a chemical knowledge base based on the standard chemical graph model using description graphs, OWL and rules. We include in our ontology chemical classes, groups, and molecules, together with their structures encoded as description graphs. We show how role-safe rules can be used to determine parthood between groups and molecules based on the graph structures and to determine basic chemical properties. Finally, we investigate the scalability of the technology used through the development of an automatic utility to convert standard chemical graphs into description graphs, and converting a large number of diverse graphs obtained from a publicly available chemical database. / Computer Science (School of Computing) / M. Sc. (Computer Science)

No description available.

<p dir="ltr">Dietary fibers have been observed to modulate the gut microbiome in ways that prevent and moderate human diseases and confer health benefits onto their human host. How dietary fibers do this is through their structure; gut microbes are equipped with a variety of differ- ent carbohydrate-active enzymes (CAZymes) that allow some to hydrolyze glycosidic bonds, thereby utilizing the dietary fiber. The more complex the dietary fiber, the more diverse the maintained gut microbiota may be, as specialist species may be required for complete hydrol- ysis. Therefore, increasing structural complexity of dietary fibers may increase gut microbial diversity and help prevent diseases. To understand if structural features impact the gut mi- crobiome, a set of resistant glucans varying in structures, including mixed-linkage -glucans, resistant maltodextrins (similar to type IV resistant starch) and polydextroses, which are comprised entirely of glucose, were used as substrates in an in vitro sequential batch fermen- tation using fecal microbiota form three healthy donors as inocula. I measured metabolic outputs, growth curves, and community structures by 16S rRNA amplicon sequencing, which I analyzed for through alpha and beta diversity differences and taxa that overrepresented and increased in each treatment. My results show that, depending on the donor and the resistant glucan, structure does significantly impact the concentrations of short-chain fatty acids (SCFAs) and other metabolites that are produced. Resistant glucan structure also impacts alpha and beta diversity to a degree and linear discriminant analysis (by LEfSe) results also support that specific species have preference towards substrates as well. Next, resistant glucans were supplemented into a high-fat diet, and compared these diets to a low- fat diet (LFD), high-fat diet with cellulose (HFD), and high-fat without cellulose (HWC) in a mouse study using C57BL/6J mice over 4 weeks. Increasing microbial diversity will not only increase diversity in the gut microbiome, but it will also provide protective effects in behavior such as helping to prevent anxiety. I measured weight, metabolic outputs, 16S community structure, changes in alpha and beta diversity, and differential abundances of OTUs and taxa by discriminant analysis Effect Size (LEfSe) and Metastats, and anxiety behaviors using open field and light/dark box tests. Microbial community structure was significantly different in treatment groups from controls. Anxiety for mice in tapioca dextrin 01 (TD01), tapioca dextrin 03 (TD03), and resistant maltodextrin (RMF) treatment groups were gen- erally increased, suggesting that the chemical structure of these resistant dextrins may alter the gut microbiome in ways that may influence behavior.</p><p dir="ltr">My overall results support the hypothesis that the fine structural features of dietary fibers do significantly impact the gut microbiome by selecting for specific microbiota, and may even impact cognition and behavior.</p>

Dans un contexte où la demande énergétique ne cesse de croître et où les réserves pétrolières sont limitées, il est nécessaire de développer des sources énergétiques alternatives ainsi que de ransformer celles existantes afin de satisfaire les besoins croissants notamment dans les secteurs du transport et de la pétrochimie. Un des objectifs de l’IFP est de concevoir et d’améliorer des procédés de raffinages existants afin d’optimiser l’utilisation des ressources conventionnelles tout en les diversifiant afin de produire notamment du carburant à partir des produits lourds du pétrole. L'enjeu des prochaines décennies est de convertir efficacement des bruts lourds en produits légers valorisables tels que l'essence, le kérosène et le gazole. Pour cela, il est indispensable de disposer d'une connaissance précise des produits présents dans la charge, principalement des asphaltènes, afin d'adapter le catalyseur utilisé et obtenir les meilleurs résultats de conversion possibles. L’objectif de la thèse visait à obtenir une meilleure caractérisation physico-chimique des asphaltènes en solution. Le manuscrit décrit une nouvelle application de la technique RMN DOSY (Diffusion Ordered Spectroscopy) à la caractérisation des produits lourds du pétrole. Des asphaltenes de cinq origines différentes ont été analysées sur une large gamme de concentration afin d’étudier leur agrégation en solution. Les résultats révèlent l’existence de deux familles d’agrégats en régime semidilué : une famille diffusant rapidement appelée nanoagrégats et un type d’agrégats diffusant plus lentement nommée macroagrégats dans ce manuscrit. L’influence du solvant a été étudiée sur une charge analysée dans le toluène, le tetra-hydrofurane et le chloroforme. Des informations physiques moyennes sur la taille et la masse moléculaire des nanoagrégats des asphaltènes ont été calculées à partir de leur diffusion en solution. Il a ainsi été possible de mettre en évidence des familles de produits caractérisées par une structure et une masse moléculaire en une seule expérience. Le manuscrit propose également une discussion sur le caractère continental ou/et archipel des asphaltènes. L’hypothèse de départ est basée sur la co-existence des deux types d’asphaltènes avec un caractère archipel (ou continental) plus ou moins marqué suivant l’origine des échantillons / New energy supplies need to be developed to face the growing worldwide energy demand. Heavy oils have attracted attention since their represent an important energy reserve. The problem to deal with during their upgrading is the presence of asphaltenes, representing the heaviest and the most resistant fraction of the crude oil. It is worth getting a better understanding into the physico-chemistry of asphaltenes to develop new catalysts and new conversion processes. The manuscript describes a new application of Diffusion Ordered Spectroscopy (1H-DOSY) NMR experiment. It is evaluated as a potential tool to investigate the physico-chemistry of asphaltenes from five different origins in just one experiment. Asphaltenes were studied over a wide range of concentrations in different solvents to get a deeper insight into their aggregation behaviour. For the first time, two different aggregates were observed in the semi-dilute regime and reported in this manuscript. Average size and molecular weight are estimated from diffusion measurements at infinite dilution. Based on different results, a discussion about continental and archipelago type is also provided. Asphaltenes are expected to be a distribution of the two types of asphaltenes with a more pronounced archipelago (or continental) type depending on the origin of the sample

Nesta tese serão discutidos alguns aspectos químicos, fotoquímicos e fotofísicos importantes no desenvolvimento de fotossensibilizadores para aplicação em terapia fotodinâmica (TFD). Os estudos abrangeram a investigação de 29 espécies, sendo que 20 delas continham um anel porfirínico convencional e 9 eram porfirinas duplamente N-confusas. As primeiras foram sintetizadas para apresentarem diferentes números e tipos de substituintes catiônicos coordenados à posição meso do anel porfirínico, mais especificamente as meso(N-4-piridil)fenilporfirinas e as meso(N-3-piridil)fenilporfirinas contendo um, dois (em trans), dois (em cis), três e quatro grupos [Ru(bipy)2Cl]+ ou CH3+ (figura 1). Em contraste com as porfirinas convencionais. as outras 9 estruturas consistiram das formas protonadas, neutras e desprotonadas de porfirinas que exibem dois anéis pirrólicos adjacentes voltados para fora do anel porfirínico, mais especificamente a base livre (H2N2CP) e os respectivos complexos de prata (AgHN2CP) e de cobre (CuHN2CP). Esta peculiaridade estrutural permite coordenar metais de transição por meio de dois átomos de carbono e dois de nitrogênio, estabilizando fortemente íons metálicos em estados de oxidação anormalmente elevados como Ag3+ e Cu3+. Os dois nitrogênios pirrólicos externos ao anel são susceptíveis tanto a protonação quanto a desprotonação, possibilitando a modulação das propriedades eletrônicas desses compostos por simples alteração no pH do meio. De um modo geral, a acidificação das amostras perturbou mais significativamente suas propriedades fotoquímicas que a desprotonação. Em especial, as espécies neutras metaladas apresentaram bandas bastante intensas na região fototerapêutica de 600 a 750 nm, além de um elevado rendimento quântico de formação de oxigênio singlete (&#934;&#916; &#62; 0,90 para o complexo Ag(III)). Todavia, um processo de fotodecomposição atribuído ao ataque do 1O2 formado, também foi observado. Ambos os processos, &#934;&#916; e fotodecomposição, parecem ser modulados pelo metal coordenado no centro do anel. Tanto a coordenação de Ag(lII) como Cu(lII) aumentou o &#934;&#916;, provavelmente devido ao efeito do metal pesado sobre o cruzamento interssistema. Todavia, verificou-se que o derivado AgHN2CP é muito menos reativo que o CuHN2CP e a base livre. Os motivos deste comportamento ainda não são completamente compreendidos, mas é evidente que o complexo de Ag(lII) apresenta melhores propriedades fotodinâmicas que as demais. Em comparação com as porfirinas duplamente N-confusas, as demais 20 porfirinas catiônicas são muito mais solúveis em água. Neste caso, o enfoque dos experimentos foi direcionado às aplicações biológicas propriamente ditas. Assim, além das propriedades fotofísicas associadas à formação de oxigênio singlete (1O2), também foram exploradas a influência do número dos substituintes periféricos sobre a ligação e danos fotooxidativos provocados em eritrócitos, lipossomos, mitocôndrias e células cancerígenas. Os resultados de &#934;&#916; mostraram ser inversamente proporcionais ao número de cargas positivas, para as porfirínas contendo grupos N-4metilpiridíniom. Estas diferenças foram consistentes com os efeitos de agregação, causados pela formação de dímeros ou oligômeros, no caso das espécies mais hidrofóbicas. Os coeficientes de partição em n-octanol/água (logPOA) corroboraram estes resultados, apresentando uma dependência inversamente proporcional ao número de cargas positivas ou proporcional ao número de resíduos fenila. As eficiências de ligação à bicamada lipídica mitocondrial, lipossomal e celular e os processos de peroxidação lipídica fotoinduzidos mostraram uma dependência proporcional aos valores de logPOA, exceto para as porfirinas contendo complexos de rutênio. O comportamento não linear neste último caso pode estar associada a dissociação da ligação rutênio-porfirina, devido a elevada força iônica das soluções fisiológicas utilizadas. Neste caso, a descoordenação dos complexos periféricos deve promover uma drástica diminuição da solubilidade do composto. Por este motivo os experimentos foram conduzidos somente com as espécies metiladas. No caso, de mitocôndrias isoladas verificou-se que a interação também apresenta uma razoável participação do potencial de membrana. De fato, quando a mitocôodria estava energizada foi observado um acréscimo de 15% no acúmulo da 3P2cMe em comparação com à mitocôndria desacoplada. Para as demais porfirinas houve um menor acúmulo com o aumento do número de resíduos N-3-metilpirídínio. Em todos os experimentos, um comportamento diferenciado foi observado no caso dos isômeros dicatiônicos. A espécie com cargas dispostas nas posições cis (3P2cMe) apresentou praticamente o dobro de eficiência que o correspondente isômero trans (3P2tMe). Este comportamento parece consistente com uma maior penetração da primeira espécie na bicamada lipídica, proporcionado pelo caráter antipático de sua estrutura química. Os resultados apresentados neste estudo mostraram que estas séries de meso-porfirinas catiônicas constituem sistemas bastante interessantes para a compreensão dos efeitos estruturais envolvidos na ação fotodinâmica dos compostos sobre membranas lipídicas, devido à possibilidade de modulação da relação hidrofilicidade/lipofilicidade, sem alterar significativamente a eficiência na formação de 1O2. Além disso, a disposição espacial das cargas positivas na estrutura do fotossensibilizador demonstrou ser extremamente crítica no processo de ancoragem do mesmo na membrana celular ou mitocondrial e consequentemente em causar efeitos fotooxidativos mais eficientemente. As porfirinas contendo grupos 3-metilpiridínio apresentam vantagens sobre as 4-metilpiridínio, normalmente estudas, por serem mais hidrofílicas, terem menor tendência de agregação e possuírem similar atividade fotodinâmica. Em especial, a estrutura anfipática da 3P2cMe associada a sua elevada formação de 1O2 e estabilidade lhe conferem uma interessante potencialidade como agente fototerapêutico. / In this thesis the chemical, photochemical and photophysical relevant aspects for the development of new photosensitizers for photodynamic therapy applications are discussed. 20 conventional porphyrins species and 9 doubly Nconfused porphyrins species were investigated. The first series contains variable number (1 to 4) of cationic groups, [Ru(bipy)2CI]+ or CH3+ (figure 1), bound to the meta or para-pyridil N-atoms of meso-phenylpyridylporphyrins. On the other hand, the protonated, neutral and deprotonated doubly N-confused porphyrins possess two rotated adjacent pyrrol rings, such that they have two coordinating camon atoms. Consequently, transition metal ions in unusually high oxidation states such as Ag(lII) and Cu(lII) can be stabilized by this structure, while the outer pyrrol N-atoms are susceptible to protonation and deprotonation reactions, allowing the modulation of their electronic properties simply by controlling the pH of the solution. In general, the protonation perturbed more significantly the photochemical properties than the deprotonation. The neutral species exhibit intense absorption bands in the phototherapeutical range (600 to 750 nm), associated with a high singlet oxygen sensitization quantum yield (&#934;&#916;&#62; 0,90 for the Ag(lII) complex). Furthermore, a photodecomposition process due to the reaction with 1O2 was also identified. Both &#934;&#916; and photodecomposition are influenced by the metal ion coordinated to the doubly N-confused porphyrin ring. The coordination of Ag(lIl) and Cu(lII) increased &#934;&#916;, probably due to the enhancement of intersystem crossing quantum yield associated with the heavy atom effects. However, AgHN2CP is much more stable than CuHN2CP or the free-base, but the reasons are not clear and should be further investigated. The above results clearly evidence the superior properties of the Ag(lIl) complex as photosensitizer for PDT applications. The 20 cationic pyridylporphyrin derivatives are much soluble in water and experiments directed to biological applications could be carried out. Accordingly, in addition to the quantum yield for singlet oxygen generation(1O2), the effect of the stereochemistry and number and position of the electrically charged substituents on the binding constants and photooxidative damage on erythrocytes, lipossomes, mitochondria and HeLa cells were evaluated. The &#934;&#916; values were constant in the case of the N-3-methylpyridinium derivatives but inversely proportional to the number of positive charges for the N-4-methylpyridinium derivatives. This was assigned to an increase of aggregation of the sensitizers as the number of meso-phenyl rings and the lipophylicity increase. The partition coefficients in n-octanol/water (logPOA) corroborate that assertion showing a linear correlation with increasing of the number of phenyl groups. The binding efficiency towards the mitochondrial, lipossomal and cellular membrane and the photo-induced lipidic peroxidation processes were directly proportional to the logPOA, except for the ruthenated porphyrins. This last behavior may be associated with the dissociation reactions of the rutheniumpyridylporphyrin bond in the physiologic solution. Accordingly, those experiments were carried out only with the methylpyridynium derivatives. For the first time, we showed inequivocally that the interaction of the methyllated porphyrins with mitochondria are significantly influenced by the membrane potential. In fact, when the mitochondria was energized a 15% increase was observed in the binding constants of 3P2cMe in comparison with teh results with decoupled mitochondria. Also, the amount of bond porphyrin sensitizer decreased as the number of methylpyridynium groups was increased, following the same tendency as above. The behavior of the cis (3P2cMe) and trans (3P2tMe) isomers didn\'t follow the general tendency for the other derivatives in a series, such that the binding constants of the cis isomers were always about twice higher than for the trans, which were much higher than predicted by the general behavior. This means that they can associate more strongly and penetrate deeper in the membrane than the more charged porphyrin derivatives. In particular, the cis species is amphiphilic, i.e. possess an adequate structure for that interaction. The results presented in this thesis showed conclusively that the two series of meso-phenylpyridylporphyrins are adequate for the investigation of the effect of the stereochemistry on the bonding ability and photodynamic properties of those photosensitizers. This is particularly true due to the possibility of modulating the ratio between hydrophobicitylhydrophylicity and the stereochemistry without influencing significantly the quantum yield for 1O2 generation. The meta- series showed an advantage over the conventionally used para- series of methylpyridynium porphyrins because it is more soluble and shows lesser tendency to aggregate. In condusion, the amphiphilic 3P2cMe is the species with the highest potentiallity as por sensitizer because of its high binding constants, low tendency to associate and high &#934;&#916;.

Nesta tese serão discutidos alguns aspectos químicos, fotoquímicos e fotofísicos importantes no desenvolvimento de fotossensibilizadores para aplicação em terapia fotodinâmica (TFD). Os estudos abrangeram a investigação de 29 espécies, sendo que 20 delas continham um anel porfirínico convencional e 9 eram porfirinas duplamente N-confusas. As primeiras foram sintetizadas para apresentarem diferentes números e tipos de substituintes catiônicos coordenados à posição meso do anel porfirínico, mais especificamente as meso(N-4-piridil)fenilporfirinas e as meso(N-3-piridil)fenilporfirinas contendo um, dois (em trans), dois (em cis), três e quatro grupos [Ru(bipy)2Cl]+ ou CH3+ (figura 1). Em contraste com as porfirinas convencionais. as outras 9 estruturas consistiram das formas protonadas, neutras e desprotonadas de porfirinas que exibem dois anéis pirrólicos adjacentes voltados para fora do anel porfirínico, mais especificamente a base livre (H2N2CP) e os respectivos complexos de prata (AgHN2CP) e de cobre (CuHN2CP). Esta peculiaridade estrutural permite coordenar metais de transição por meio de dois átomos de carbono e dois de nitrogênio, estabilizando fortemente íons metálicos em estados de oxidação anormalmente elevados como Ag3+ e Cu3+. Os dois nitrogênios pirrólicos externos ao anel são susceptíveis tanto a protonação quanto a desprotonação, possibilitando a modulação das propriedades eletrônicas desses compostos por simples alteração no pH do meio. De um modo geral, a acidificação das amostras perturbou mais significativamente suas propriedades fotoquímicas que a desprotonação. Em especial, as espécies neutras metaladas apresentaram bandas bastante intensas na região fototerapêutica de 600 a 750 nm, além de um elevado rendimento quântico de formação de oxigênio singlete (&#934;&#916; &#62; 0,90 para o complexo Ag(III)). Todavia, um processo de fotodecomposição atribuído ao ataque do 1O2 formado, também foi observado. Ambos os processos, &#934;&#916; e fotodecomposição, parecem ser modulados pelo metal coordenado no centro do anel. Tanto a coordenação de Ag(lII) como Cu(lII) aumentou o &#934;&#916;, provavelmente devido ao efeito do metal pesado sobre o cruzamento interssistema. Todavia, verificou-se que o derivado AgHN2CP é muito menos reativo que o CuHN2CP e a base livre. Os motivos deste comportamento ainda não são completamente compreendidos, mas é evidente que o complexo de Ag(lII) apresenta melhores propriedades fotodinâmicas que as demais. Em comparação com as porfirinas duplamente N-confusas, as demais 20 porfirinas catiônicas são muito mais solúveis em água. Neste caso, o enfoque dos experimentos foi direcionado às aplicações biológicas propriamente ditas. Assim, além das propriedades fotofísicas associadas à formação de oxigênio singlete (1O2), também foram exploradas a influência do número dos substituintes periféricos sobre a ligação e danos fotooxidativos provocados em eritrócitos, lipossomos, mitocôndrias e células cancerígenas. Os resultados de &#934;&#916; mostraram ser inversamente proporcionais ao número de cargas positivas, para as porfirínas contendo grupos N-4metilpiridíniom. Estas diferenças foram consistentes com os efeitos de agregação, causados pela formação de dímeros ou oligômeros, no caso das espécies mais hidrofóbicas. Os coeficientes de partição em n-octanol/água (logPOA) corroboraram estes resultados, apresentando uma dependência inversamente proporcional ao número de cargas positivas ou proporcional ao número de resíduos fenila. As eficiências de ligação à bicamada lipídica mitocondrial, lipossomal e celular e os processos de peroxidação lipídica fotoinduzidos mostraram uma dependência proporcional aos valores de logPOA, exceto para as porfirinas contendo complexos de rutênio. O comportamento não linear neste último caso pode estar associada a dissociação da ligação rutênio-porfirina, devido a elevada força iônica das soluções fisiológicas utilizadas. Neste caso, a descoordenação dos complexos periféricos deve promover uma drástica diminuição da solubilidade do composto. Por este motivo os experimentos foram conduzidos somente com as espécies metiladas. No caso, de mitocôndrias isoladas verificou-se que a interação também apresenta uma razoável participação do potencial de membrana. De fato, quando a mitocôodria estava energizada foi observado um acréscimo de 15% no acúmulo da 3P2cMe em comparação com à mitocôndria desacoplada. Para as demais porfirinas houve um menor acúmulo com o aumento do número de resíduos N-3-metilpirídínio. Em todos os experimentos, um comportamento diferenciado foi observado no caso dos isômeros dicatiônicos. A espécie com cargas dispostas nas posições cis (3P2cMe) apresentou praticamente o dobro de eficiência que o correspondente isômero trans (3P2tMe). Este comportamento parece consistente com uma maior penetração da primeira espécie na bicamada lipídica, proporcionado pelo caráter antipático de sua estrutura química. Os resultados apresentados neste estudo mostraram que estas séries de meso-porfirinas catiônicas constituem sistemas bastante interessantes para a compreensão dos efeitos estruturais envolvidos na ação fotodinâmica dos compostos sobre membranas lipídicas, devido à possibilidade de modulação da relação hidrofilicidade/lipofilicidade, sem alterar significativamente a eficiência na formação de 1O2. Além disso, a disposição espacial das cargas positivas na estrutura do fotossensibilizador demonstrou ser extremamente crítica no processo de ancoragem do mesmo na membrana celular ou mitocondrial e consequentemente em causar efeitos fotooxidativos mais eficientemente. As porfirinas contendo grupos 3-metilpiridínio apresentam vantagens sobre as 4-metilpiridínio, normalmente estudas, por serem mais hidrofílicas, terem menor tendência de agregação e possuírem similar atividade fotodinâmica. Em especial, a estrutura anfipática da 3P2cMe associada a sua elevada formação de 1O2 e estabilidade lhe conferem uma interessante potencialidade como agente fototerapêutico. / In this thesis the chemical, photochemical and photophysical relevant aspects for the development of new photosensitizers for photodynamic therapy applications are discussed. 20 conventional porphyrins species and 9 doubly Nconfused porphyrins species were investigated. The first series contains variable number (1 to 4) of cationic groups, [Ru(bipy)2CI]+ or CH3+ (figure 1), bound to the meta or para-pyridil N-atoms of meso-phenylpyridylporphyrins. On the other hand, the protonated, neutral and deprotonated doubly N-confused porphyrins possess two rotated adjacent pyrrol rings, such that they have two coordinating camon atoms. Consequently, transition metal ions in unusually high oxidation states such as Ag(lII) and Cu(lII) can be stabilized by this structure, while the outer pyrrol N-atoms are susceptible to protonation and deprotonation reactions, allowing the modulation of their electronic properties simply by controlling the pH of the solution. In general, the protonation perturbed more significantly the photochemical properties than the deprotonation. The neutral species exhibit intense absorption bands in the phototherapeutical range (600 to 750 nm), associated with a high singlet oxygen sensitization quantum yield (&#934;&#916;&#62; 0,90 for the Ag(lII) complex). Furthermore, a photodecomposition process due to the reaction with 1O2 was also identified. Both &#934;&#916; and photodecomposition are influenced by the metal ion coordinated to the doubly N-confused porphyrin ring. The coordination of Ag(lIl) and Cu(lII) increased &#934;&#916;, probably due to the enhancement of intersystem crossing quantum yield associated with the heavy atom effects. However, AgHN2CP is much more stable than CuHN2CP or the free-base, but the reasons are not clear and should be further investigated. The above results clearly evidence the superior properties of the Ag(lIl) complex as photosensitizer for PDT applications. The 20 cationic pyridylporphyrin derivatives are much soluble in water and experiments directed to biological applications could be carried out. Accordingly, in addition to the quantum yield for singlet oxygen generation(1O2), the effect of the stereochemistry and number and position of the electrically charged substituents on the binding constants and photooxidative damage on erythrocytes, lipossomes, mitochondria and HeLa cells were evaluated. The &#934;&#916; values were constant in the case of the N-3-methylpyridinium derivatives but inversely proportional to the number of positive charges for the N-4-methylpyridinium derivatives. This was assigned to an increase of aggregation of the sensitizers as the number of meso-phenyl rings and the lipophylicity increase. The partition coefficients in n-octanol/water (logPOA) corroborate that assertion showing a linear correlation with increasing of the number of phenyl groups. The binding efficiency towards the mitochondrial, lipossomal and cellular membrane and the photo-induced lipidic peroxidation processes were directly proportional to the logPOA, except for the ruthenated porphyrins. This last behavior may be associated with the dissociation reactions of the rutheniumpyridylporphyrin bond in the physiologic solution. Accordingly, those experiments were carried out only with the methylpyridynium derivatives. For the first time, we showed inequivocally that the interaction of the methyllated porphyrins with mitochondria are significantly influenced by the membrane potential. In fact, when the mitochondria was energized a 15% increase was observed in the binding constants of 3P2cMe in comparison with teh results with decoupled mitochondria. Also, the amount of bond porphyrin sensitizer decreased as the number of methylpyridynium groups was increased, following the same tendency as above. The behavior of the cis (3P2cMe) and trans (3P2tMe) isomers didn\'t follow the general tendency for the other derivatives in a series, such that the binding constants of the cis isomers were always about twice higher than for the trans, which were much higher than predicted by the general behavior. This means that they can associate more strongly and penetrate deeper in the membrane than the more charged porphyrin derivatives. In particular, the cis species is amphiphilic, i.e. possess an adequate structure for that interaction. The results presented in this thesis showed conclusively that the two series of meso-phenylpyridylporphyrins are adequate for the investigation of the effect of the stereochemistry on the bonding ability and photodynamic properties of those photosensitizers. This is particularly true due to the possibility of modulating the ratio between hydrophobicitylhydrophylicity and the stereochemistry without influencing significantly the quantum yield for 1O2 generation. The meta- series showed an advantage over the conventionally used para- series of methylpyridynium porphyrins because it is more soluble and shows lesser tendency to aggregate. In condusion, the amphiphilic 3P2cMe is the species with the highest potentiallity as por sensitizer because of its high binding constants, low tendency to associate and high &#934;&#916;.

Carbon nanotubes are molecular-scale tubes of graphitic carbon that possess many unique properties. They have high tensile strength and elastic modulus, are thermally and electrically conductive, and can be structurally modified using well established carbon chemistries. There is global interest in taking advantage of their unique combination of properties and using these interesting materials as components in nanoscale devices and composite materials. The goal of this research was the correlation of the mechanical properties of coiled carbon nanotubes with their chemical structure. Individual nanocoils, grown by chemical vapor deposition, were attached to scanning probe tip using the arc discharge method. Using a scanning probe microscope the nanocoils are repeatedly brought into and out of contact with a chemically-modified substrate. Precise control over the length (or area) of contact with the substrate is achievable through simultaneous monitoring the cantilever deflection resonance, and correlating these with scanner movement. The mechanical response of nanocoils depended upon the extent of their compression. Nonlinear response of the nanocoil was observed consistent with compression, buckling, and slip-stick motion of the nanocoil. The chemical structure of the nanocoil and its orientation on the tip was determined using scanning and transmission electron microscopy. The mechanical stiffness of eighteen different nanocoils was determined in three ways. In the first, the spring constant of each nanocoil was computed from the slope of the linear response region of the force-distance curve. The assumptions upon which this calculation is based are: 1) under compression, the cantilever-nanocoil system can be modeled as two-springs in series, and 2) the nanocoil behaves as an ideal spring as the load from the cantilever is applied. Nanocoil spring constants determined in this fashion ranged from 6.5x10-3 to 5.16 TPa for the CCNTs understudy. In the second, the spring constant of the nanocoil was computed from measuring the critical force required to buckle the nanocoil. The critical force method measured the force at the point where the nanocoil-cantilever system diverges from a linear region in the force curve. Nanocoil spring constants determined in this fashion ranged from 1.3x10-5 to 10.4 TPa for the CCNTs understudy. In the third, the spring constant of each nanocoil was computed from the thermal resonance of the cantilever-nanocoil system. Prior to contact of the nanocoil with the substrate, the effective spring constant of the system is essentially that of the cantilever. At the point of contact and prior to buckling or slip-stick motion, the effective spring constant of the system is modeled as two springs in parallel. Nanocoil spring constants determined in this fashion ranged from 2.7x10-3 to 0.03 TPa for the CCNTs understudy. Using the thermal resonance of the cantilever system a trend was observed relating nanocoil structure to the calculated modulus. Hollow, tube-like nanostructures had a higher measured modulus than solid or fibrous structures by several orders of magnitude. One can conclude that the structure of carbon nanocoils can be determined from using their mechanical properties. This correlation should significantly contribute to the knowledge of the scientific and engineering community. It will enable the integration of carbon nanocoils in microelectromechanical (MEMS) or nanoelectromechanical systems (NEMS) as resonators, vibration dampers, or any other application in which springs are used within complex devices.

Submitted by Erika Demachki (erikademachki@gmail.com) on 2015-10-20T17:56:33Z No. of bitstreams: 2 Dissertação - Estefânia Viano da Silva - 2014.pdf: 4645592 bytes, checksum: f3321dacb1ccfd2f2b017d08f8e3b578 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Erika Demachki (erikademachki@gmail.com) on 2015-10-20T17:58:09Z (GMT) No. of bitstreams: 2 Dissertação - Estefânia Viano da Silva - 2014.pdf: 4645592 bytes, checksum: f3321dacb1ccfd2f2b017d08f8e3b578 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2015-10-20T17:58:09Z (GMT). No. of bitstreams: 2 Dissertação - Estefânia Viano da Silva - 2014.pdf: 4645592 bytes, checksum: f3321dacb1ccfd2f2b017d08f8e3b578 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2014-06-26 / The mushrooms have been used as food and medicine for thousands of years. Among them, Grifola frondosa (“Maitake”) may be on the most versatile and promising medicinal mushrooms for use as a dietary supplement. Besides the high nutritional value, they are a good source of compounds such as carbohydrates that can act as biological response modifiers. In this work, β-D-glucans (PSF2-GfM and MRSF2K-GfM fractions) and heteropolysaccharides unusual in the literature (MEPF3CW-GfM and PF2K-GfM fractions) were isolated from the mycelium, grown in solid culture, of the G. frondosa, by successive aqueous and alkaline extractions, followed by fractionation through freeze-thawing, precipitation of soluble material with a Fehling solution, and dialysis using a membrane with an exclusion limit of 1000 kDa. The chemical structures were established based on monossacharide composition, periodate oxidation, methylation analysis, HPSEC-MALLS and NMR studies. The branched β-D-glucans (GLC-GfM) found were similar to those previously described for the fungus, which contains a (13)- linked β-Glcp main-chain, substituted at O-6 by single-unit -Glcp side-chains, on the average of one to every third residues of the backbone, but with different molar masses and water solubility. In adittion, novel heteropolymers were obtained. One was a fucomannogalactan (FMG-GfM), with a molar mass of 175 x 103 g mol-1, was shown to have a main chain of (1→6)-linked α-D-Galp and 3-O-Me-α-DGalp, both of which are partially substituted at O-2, principally, by 3-O-α-D-Manp-α-LFucp groups. The other was a fucoxylomannan (FXM-GfM) (Mw 202 x 103 g.mol-1), which consisted of backbone of (13)-linked α-D-Manp units, totally substituted at O-4 mainly by 4-O-α-L-Fucp-β-D-Xylp disaccharide. Thus, the polymers obtained from Grifola frondosa may could be good candidates for evaluation of its biological effect, considering the results obtained for others similar mushrooms polysaccharides. / Os cogumelos têm sido usados como alimentos e remédios por milhares de anos. Entre eles, o “Maitake” (Grifola frondosa) pode ser um dos cogumelos medicinais mais versáteis e promissores para o uso como um suplemento dietético. Além do valor nutricional elevado, eles são uma boa fonte de compostos, como os carboidratos, que podem agir como modificadores de resposta biológica. Neste trabalho, foram isolados do micélio (cultivado em meio sólido) de G. frondosa as β-D-glucanas (frações PSF2KGfM e MRSF2K-GfM) e heteropolissacarídeos (frações MePF3CW-GfM e PF2K-GfM) não comumente encontrados na literatura, por sucessivas extrações aquosas e alcalinas, seguido por fracionamento através do processo de congelamento/degelo, precipitação das frações solúveis em água com solução de Fehling e diálise em membranas com limite de exclusão de 1000 kDa. A estrutura química foi determinada através das análises de composição mossacarídica, oxidação com periodato de sódio, metilação, HPSEC-MALLS e RMN. As β-D-glucanas (GLC) isoladas foram similares àquelas previamente descritas para este fungo, as quais contém uma cadeia principal formada por unidades de 3-O-β-D-Glcp, podendo ser substituídas em O-6 por terminais não redutores de β-Glcp (1 ramificação a cada três unidades da cadeia principal), distinguindo-as quanto à solubilidade em água e tamanho (massa molar). Além destas, foram obtidos novos heteropolímeros. Um deles foi uma fucomanogalactana (FMGGfM), com uma massa molar de 175 x 103 g mol-1, a qual possui um core constituído por unidades de 6-O-α-D-Galp e 6-O-(3-O-Me-α-D-Galp), sendo ambas parcialmente substituídas em O-2 por 3-O-α-D-Manp-α-L-Fucp. O outro heteropolissacarídeo isolado consiste em uma fucoxilomanana (FXM-GfM) (Mw 202 x 103 g.mol-1) formada por unidades de α-D-Manp unidas por ligações glicosídicas do tipo (13) as quais se encontram ramificadas em O-4 principalmente pelo dissacarídeo 4-O-α-L-Fucp-β-DXylp. Considerando os efeitos terapêuticos apresentados por moléculas similares descritas para macrofungos, estes podem ser bons candidatos para avaliação do efeito biológico.