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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
61

Reproductive Competition and Success in a Joint-Nesting Cuckoo

Robertson, Joshua K January 2016 (has links)
Joint-nesting species experience complex and diverse social environments which can influence individual reproductive success. When social groups are formed by non- relatives, competition for representation in incubated clutches can be intense and result in substantial reproductive losses. Because conflicts of this nature have direct impli- cations on fitness, resolutions and outcomes of such are of particular interest to evolu- tionary research. For this reason, I explored patterns of reproductive competition and skew in joint-nesting Smooth-billed Anis (Crotophaga ani). In chapter I, I show marked differences in multivariate bill and body size between sexes of Smooth-billed Anis (Cro- tophaga ani) despite reportedly reduced sexual dimorphism in co-operative breeders. I also show that multivariate bill size in males correlates with annual reproductive success and individual contribution to clutches from multiple parents. A similar trend is not observed in females, suggesting potential for sexual selection on male bill size. Together, these data provide evidence for morphological influences on reproductive fitness in joint- nesting species. In chapter II, I show that relative parental effort is positively correlated with reproductive fitness in social groups of Smooth-billed Anis. Nocturnal incubation is risky and is biased toward a single male - akin to Groove-billed (Crotophaga sulcirostris) and Greater Ani (Crotophaga major). I report heightened reproductive contribution by nocturnally incubating males when compared to other males within social groups. In chapter III, I tested whether social group size is correlated with endocrine markers of stress in adult male and female Anis. Using a novel enzyme linked immunosorbent as- say, I show that corticosterone (the primary glucocorticoid in birds) deposited in feathers is highest in birds from atypically large social groups. While the direct consequences of elevated corticosterone on reproductive fitness in Anis is yet unknown, these results suggest that breeding in large social settings is likely to be physiologically expensive. / Thesis / Master of Science (MSc)
62

SUCCESSFUL CO-TEACHING RELATIONSHIPS: A QUALITATIVE STUDY ON WHAT IT TAKES TO FORGE A SUCCESSFUL WORKING RELATIONSHIP

Fleming, Paige A. 19 April 2007 (has links)
No description available.
63

Étude de la réaction d’hydrogénation du CO sur des catalyseurs à base de cobalt supporté par DRIFTS operando / Study of CO hydrogenation reaction on supported cobalt catalysts by operando DRIFTS

Paredes-Nunez, Anaëlle 25 October 2016 (has links)
Notre dépendance à l'égard des combustibles fossiles et la diminution des ressources pétrolières nous imposent la recherche de sources renouvelables d'énergie et de produits chimiques. La synthèse Fischer-Tropsch permet de répondre à la demande en carburants propres et renouvelables grâce à l'utilisation de gaz de synthèse issu de la biomasse. L'objectif de ce travail est de contribuer à la compréhension du mécanisme de l'hydrogénation du CO sur des catalyseurs au cobalt et à l'identification du site actif par des études spectroscopiques DRIFTS operando. Ce système permet d'observer les différentes espèces adsorbées à la surface du catalyseur pendant la réaction : CO pontés et linéaires, formiates, carboxylates et hydrocarbures. Nos travaux ont montré qu'une fraction des formiates dits « rapides» peut expliquer la formation du méthanol dans nos conditions de réaction. L'ajout dans le mélange H2+CO d'un élément minéral typique de la biomasse, le chlore sous forme de trichloréthylène, a révélé que, l'activité diminuait. La bande des CO pontés étant la plus impactée et se déplaçant vers les hauts nombres d'onde, l'effet du chlore a été notamment associé à un effet électronique sur le cobalt. L'adsorption du chlore étant réversible, nous avons également étudié l'effet de l'étain. Ce métal n'adsorbe pas le CO dans nos conditions et peut s'adsorber à la surface du cobalt. L'étain empoisonne sélectivement la formation des CO pontés et limite fortement la chimisorption de l'hydrogène. Une relation linéaire entre la vitesse de formation des produits et la proportion de CO pontés est observée, révélant l'importance des CO pontés pour la réaction d'hydrogénation du CO / Our dependence on fossil fuels and the decrease of oil resources warrant the search for renewable energy sources and chemicals. Fischer-Tropsch synthesis enables meeting the requirements for cleaner and renewable fuels through the use of syngas obtained from biomass.The objective of this work was to contribute to the understanding of the mechanism of CO hydrogenation on cobalt-based catalysts and the identification of the active site by operando DRIFT spectroscopy. Different species were adsorbed on the surface of the catalyst under reaction conditions: bridged and linear CO, formates, carboxylates and hydrocarbons. Our resutls shows that so-called “fast formate” can account for the formation of methanol under our reaction conditions. The study of a typical biomass element, chlorine, revealed that the activity decreased under trichloroethylene,. The CO bridged band being the most affected band and shifting to higher wavenumber, the chlorine effect was partly associated with an electronic effect on cobalt. Chlorine adsorption being reversible, tin poisoning was also studied. This metal does not adsorb CO under our conditions. Tin addition to cobalt selectively poisons bridged CO and greatly limits the chemisorption of hydrogen. A linear relationship between the rate of formation of products and the proportion of CO bridged is observed, highlighting the importance of CO bridged
64

Expression, régulation et caractérisation fonctionnelle des molécules de co-signalisation immunitaire, PD-L2 et CD277 dans l'activation lymphocytaire T / Expression and regulation of PD-L2, B7 family member and functional characterization on T cells

Messal, Nassima 20 January 2011 (has links)
Programmed death-1 (PD-1) et ses ligands PD-L1 et PD-L2 appartiennent à la famille B7 : CD28 des molécules de cosignalisation immunitaire. Leur interaction délivre un signal inhibiteur à l’activation lymphocytaire. Ces molécules sont impliquées non seulement dans le contrôle de la tolérance, mais aussi dans un mécanisme d’échappement tumoral et viral au système immunitaire. Les deux ligands de PD-1 : PD-L1 et PD-L2 montrent une expression tissulaire assez large, témoignant de leur rôle étendu aux différents stades de la réponse immunitaire. L’expression de PD-L1 est plus large que celle de PD-L2. PD-L1 est exprimé sur les cellules hématopoïétiques et non hématopoïétiques, PDL2 présente une expression assez restreinte aux CPAs professionnelles. L’expression de PD-L1 et PD-L2 est fortement régulée dans plusieurs cas pathologiques et notamment dans les cancers. La régulation de l’expression de PD-L2 qui fait l’objet de notre étude, représente une cible importante dans le domaine de l’immunothérapie. Notre projet porte sur l’analyse de l’expression, la régulation et la fonction de PD-L2 dans les LT, dans différents contextes physiologiques et pathologiques. Nous avons pu démontrer que PD-L2 qui avait été décrit chez la souris pour son expression restreinte aux CDs et aux macrophages, était de façon surprenante exprimé avec son homologue PD-L1 sur les LT après costimulation CD3+CD28. Nous l’avons confirmé ex vivo par activation par Staphylococcal enterotoxin E. Ce résultat montre que PD-L2 est bien induit sur des LT dans des conditions d’activation physiologique ou pathologique. Nous avons pu démontrer aussi une régulation négative de l’expression transcriptionnelle et protéique de PD-L1 et de PDL2 sous l’effet de la CyclosporineA (CsA). Cet effet est indépendant de l’action de l’IL-2. Nos données d’analyses bioinformatiques nous ont permis d’identifier les sites putatifs de fixation de facteurs de transcription au niveau du promoteur du gène pd-l2, qui peuvent être régulés par la CsA. L’analyse de la fonction de PDL2 sur les LT nous a permis de démontrer que la stimulation de PDL2 par des anticorps monoclonaux fabriqués dans le laboratoire inhibait l’activation T. Nos résultats démontrent pour la première fois une fonction de PDL2 et une signalisation « reverse siglaling » dans les LT potentiels. La caractérisation fonctionnelle et l’étude des voies de signalisation de PD-L2 que nous avons déjà étudié dans notre projet, représentent une piste importante à explorer. Cela permettrait de proposer de nouvelles stratégies permettant de lutter contre les mécanismes d’échappement tumoral. / PD-1 (programmed death-1) is a new CD28 families member, that deliver inhibitory signals that regulate the balance between T cell activation, tolerance, and immunopathology. (1) (ref octa).PD-1, is inducibly expressed on T cells. The PD-1 ligands PD-L1 (B7-H1) and PD-L2 (B7-DC) exhibit distinct patterns of expression: PD-L1 is expressed more broadly than is PD-L2. PD-L1 is expressed on resting and up regulated on hematopoietic, nonhematopoietic cells and cancer cell. However, PD-L2 is expressed only on professional antigen-presenting cells. In addition, it has been demonstrated that PD-L1 and PD-L2 are differentially regulated by Th1 and Th2 cytokines.Suggesting that PD-L2 is regulated differently in the former versus the latter, and this proved to be the case, both in transcription and promotion (2) (ref octa) However, little is known about the regulation of PD-L2 expression and nine is known about the expression of PD-L2 on T cells. In the present study, we observed in the first time, by flow cytometer and real time PCR (RT PCR) that PD-L2 expression is induced on ex vivo on activated CD4+ and CD8+ T cells, on in vitro on activated JURKAT T cell line and this expression is inhibited by the immunosuppressive drogue Cyclosporin A (CsA). In the second time we showed that PD-L2 is up regulated in vivo on Non hodchkin lymphoma, other up regulation of PD-L2 expression is observed on Vb8+ T cells after PBMC treatment with the Staphylococcal enterotoxin E (SEE) super antigen. Finally, we attributed a function to PD-L2 to be a co-inhibitory molecule for CD4+ T cells activation.
65

Desenvolvimento de novos sistemas de eletrocatalisadores nano-dispersos 20%Pt-(2% Pt-Ce0,9W0,102)/C tolerantes ao monóxido de carbono( CO) para ânodos de PEMFC / Development of new systems of nano-disperse 20%Pt-(2%Pt-Ce0,9W0,1O2)/C electrocatalysts tolerant to carbon monoxide (CO) for PEMFCs anodes

Nandenha, Júlio 23 August 2011 (has links)
O material (pó) de nanofase de Ce0,9W0,1O2 foi sintetizado por coprecipitação de oxalatos de cério (IV) e cátions de tungstênio (IV). A redução da platina (2%) foi feita pelo método da redução por álcool, utilizando uma solução de ácido hexacloroplatínico (H2PtCl6.6H2O) como fonte do metal, óxido de cério dopado com tungstênio (Ce0,9W0,1O2) utilizado como suporte e, uma solução de etilenoglicol/água (75/25, v/v) como solvente e agente redutor. Os materiais 2%Pt-Ce0,9W0,1O2 foram misturados em Pt/C E-TEK 20%, utilizando-se processo de mistura física para produzir os eletrocatalisadores de 20%Pt-(2%Pt-Ce0,9W0,1O2)/C. Os eletrocatalisadores obtidos foram caracterizados por espectroscopia de energia dispersiva de raios X (EDX) acoplado à microscopia eletrônica de varredura (MEV), análises de difração de raios X (DRX), e microscopia eletrônica de transmissão (MET). O conjunto eletrodos-membrana (MEAs) foram preparados para o ânodo com cargas iguais a 0,401, 0,364, 0,328 mg Pt cm-2 de eletrocatalisadores 20%Pt-(2%Pt-Ce0,9W0,1O2)/C produzidos. No cátodo foi usada uma carga de 0,4 mg Pt cm-2 de eletrocatalisador Pt/C ETEK. A polarização anódica foi realizada para oxidação de H2/CO (100 ppm de CO). A tolerância ao CO foi estudada utilizando o processo eletroquímico (stripping de CO e medidas de curvas de polarização). Os resultados obtidos mostraram que a oxidação de CO adsorvido a CO2 na superfície de platina ocorre em potenciais menos positivos mostrando tolerância ao CO adsorvido nestes eletrocatalisadores (20%Pt-(2%Pt-Ce0,9W0,1O2)/C (50:50, 60:40 e 70:30)) a uma temperatura de 85 ºC e com pressão absoluta de 2 bar para ânodo e cátodo, comparado com Pt/C E-TEK 20%. / The nanophase material (powder) of Ce0,9W0,1O2 was synthesized via coprecipitation of oxalates of cerium (IV) and tungsten cations. The reduction of platinum (2%) was made by the method of alcohol reduction, using an acid solution hexachloroplatinic (H2PtCl6.6H2O) as metal source, cerium oxide doped with tungsten (Ce0,9W0,1O2) used as support and the solution of ethylene glycol/water (75/75, v/v) as solvent and reducing agent. The 2%Pt-Ce0,9W0,1O2 materials were mixed in Pt/C E-TEK 20% using physical mixing process to produce the 20%Pt-(2%Pt-Ce0,9W0,1O2)/C electrocatalyst. The materials were characterized by energy dispersive X-ray spectroscopy (EDX) coupled to scanning electron microscopy (SEM), X-ray difratometry analysis (XRD) and transmission electronic microscopy (TEM). The membrane electrodes assembly (MEAs) were prepared with loads equal to 0.401, 0.364, 0.328 mg Pt cm-2 for 20%Pt(2%Pt-Ce0,9W0,1O2)/C electrocatalysts produced. In the cathode a load of 0.4 mg Pt cm-2 of commercial Pt/C ETEK electrocatalyst was used. The anodic polarization was carried out for oxidation of the mixture H2/CO(100 ppm CO). The CO tolerance was studied using electrochemical process (CO stripping and measurements of polarization curves). The results showed that the oxidation of CO adsorbed to CO2 on the surface of platinum occur at less positive potentials showing tolerance to CO adsorbed on these 20%Pt-(2%Pt-Ce0,9W0,1O2)/C (50:50, 60:40 and 70:30) electrocatalysts at a temperature of 85 ºC and absolute pressure of 2 bar for anode and cathode, compared with Pt/C E-TEK 20%.
66

Oxidação eletroquímica de monóxido de carbono sobre nanopartículas de platina não suportadas e influência do suporte na atividade eletrocatalítica de eletrocatalisadores suportados / Electrochemical oxidation of carbon monoxide on unsupported platinum nanoparticles and the influence of the support in the electrocatalitic activity of supported electrocatalysts

Ciapina, Eduardo Gonçalves 10 March 2010 (has links)
Este trabalho descreve um estudo da reação de oxidação eletroquímica de uma monocamada de monóxido de carbono (CO) adsorvido (Stripping de CO) sobre materiais eletrocatalíticos não suportados bem como a influência do suporte nas propriedades estruturais e eletroquímicas dos eletrocatalisadores suportados. Os eletrocatalisadores estudados foram platina (Pt) não suportada bem como Pt suportada em carbono Vulcan (Pt/C) e em óxidos de rutênio (Pt/RuO2) e estanho (Pt/SnO2). Os materiais foram caracterizados por Difratometria de Raios X (DRX), Espectroscopia por Dispersão de Energia de Raios X (EDX), Microscopia Eletrônica de Transmissão (MET) e Espectroscopia de Absorção de Raios X (XAS). Os resultados encontrados para duas amostras de Pt não suportada mostraram que os materiais são compostos de aglomerados de nanopartículas de Pt com cerca de 10 nm e revelam múltiplos picos de oxidação de CO em meio de ácido perclórico 0,1 mol L-1, tanto em condições potenciodinâmicas quanto potenciostáticas. Foi demonstrado que o stripping de CO potenciodinâmico pode fornecer evidências acerca do tamanho de partícula e que partículas maiores apresentam os menores sobrepotenciais para a reação em questão. A partir de experimentos de oxidação de CO sob condições potenciostáticas e com o auxílio de um modelo para a reação, foram encontrados os valores das constantes de velocidade para cada processo, cujo comportamento em função do potencial revelou diferenças entre os dois materiais estudados, o que também sugere mudanças no mecanismo da reação ou na isoterma de adsorção das espécies envolvidas. No caso dos eletrocatalisadores suportados Pt/C, Pt/RuO2 e Pt/SnO2, o suporte pode influenciar nas propriedades estruturais e eletrônicas, como evidenciado pelos experimentos de XAS, como também se apresentar como um co-catalisador para a reação de oxidação de CO, como encontrado para os materiais Pt/RuO2 e Pt/SnO2, visto que apresentaram menores sobrepotenciais para a oxidação de CO se comparados com Pt/C. Tal fato pode ser comprovado também por meio dos estudos nos quais Pt não suportada foi posteriormente ancorada nos diferentes suportes estudados, onde se destacou o material Pt + RuO2, que apresentou o menor sobrepotencial para a reação. De maneira comparativa, foi estudada a reação de oxidação de etanol sobre os catalisadores suportados e os resultados mostraram que os óxidos de rutênio e estanho aumentam as densidades de correntes amostradas a partir de saltos potenciostáticos. / This work describes a study of carbon monoxide monolayer electrochemical oxidation (CO stripping) on unsupported electrocatalysts as well as the influence of the support on the structural and electrochemical properties of the supported electrocatalysts. The materials studied comprised unsupported platinum (Pt) nanoparticles, Pt nanoparticles supported on high surface area carbon (Pt/C), and Pt nanoparticles supported on ruthenium oxide (Pt/RuO2) and on tin oxide (Pt/SnO2). All materials were characterized by X-Ray Diffraction (XRD), Energy Dispersive X-Ray Spectroscopy (EDX), Transmission Electron microscopy (TEM), and X-Ray Absorption Spectroscopy (XAS). The results for two samples of unsupported Pt nanoparticles revealed the materials are formed by agglomerates of Pt nanoparticles of about 10 nm with slight differences between the samples, and the CO stripping electrochemical oxidation in 0.1 mol L-1 HClO4 showed multiple oxidation peaks in both potentiodynamic and potentiostatic conditions. It was demonstrated that potentiodynamic CO stripping can give evidences about the particle size, in which larger particles present smaller overpotentials for the reaction. From potentiostatic CO electro-oxidation, aided by a mathematical model of the reaction, it was found the reaction rate constant for each process and its behavior as a function of the potential revealed differences between the two samples, also suggesting differences in the mechanism of the reaction or in the adsorption isotherm for the involved species. In the case of the supported electrocatalysts Pt/C, Pt/SnO2, and Pt/RuO2, the support seems to influence in the structural and electronic properties, as probed by XAS experiments, as well as to participate as a co-catalyst in the CO oxidation, as in the case of Pt/SnO2 and Pt/RuO2, once they presented lower overpotentials for CO oxidation if compared to Pt/C. This fact was also confirmed by studies using mixtures of unsupported Pt nanoparticles and the different supports described, in which the system Pt + RuO2 presented the lowest overpotential for the reaction. From a comparative point of view, ethanol electrochemical oxidation was also investigated on the different prepared materials and the results showed that RuO2 and SnO2 as the catalyst supports increase the current density at a given potential in the potential step experiments.
67

Taxonomia de Acanthobothrium Blanchard, 1848, Rhinebothrium Linton, 1890 e Anindobothrium Marques, Brooks & Lasso, 2001 parasitas das espécies anfi-Americanas de Himantura (Chondrichthyes: Myliobatiformes) / Taxonomy of Acanthobothrium Blanchard, 1848, Rhinebothrium Linton, 1890 and Anindobothrium Marques, Brooks & Lasso, 2001 parasites from amphi-American species of Himantura (Chondrichthyes: Myliobatiformes)

Trevisan, Bruna 13 July 2016 (has links)
Estudos co-evolutivos requerem uma base taxonômica e filogenética robusta para estabelecerem de forma inequívoca as relações entre as linhagens envolvidas. Neste sentido, a presente contribuição identificou as linhagens de parasitas marinhos das espécies anfi-Americanas de Himantura Müller & Henle, considerado o suposto grupo-irmão dos potamotrigonídeos - arraias Neotropicais restritas ao sistemas fluviais da America do Sul. O objetivo do presente estudo foi contribuir com o alicerce taxonômico necessário para a elucidar as associações históricas entre as arraias de água doce, seu suposto grupo-irmão marinho, e suas faunas helmintológicas. Neste sentido, este estudo aborda a diversidade de três gêneros de cestóideos, cujas linhagens são compartilhadas entre arraias marinhas e potamotrigonídeos: Acanthobothrium Blanchard, 1948, Anindobothrium Marques, Brooks & Lasso, 2001 e Rhinebothrium Linton, 1890. Cada um destes grupos é abordado em um capítulo individualmente. Os resultados deste estudo incluem a descrição de 11 espécies novas, dentre as quais, sete são parasitas de H. schmardae (Werner) e 4 parasitas de H. pacifica (Beebe & Tee-Van), além da redescrição de três espécies previamente conhecidas para H. schmardae. Todas as descrições e redescrições foram baseadas em um número de indivíduos sem precedentes na taxonomia dos grupos e incluíram dados sobre microscopia eletrônica de varredura dentro dos padrões atuais de descrições taxonômicas. Este estudo também abordou as relações filogenéticas das linhagens de Acanthobothrium e Anindobothrium. Em ambos os casos, dados moleculares revelam congruência entre as relações de parentesco de seus membros e aqueles evidenciados para seus hospedeiros. Os dados parasitológicos apresentados corroboram hipóteses recentes que postulam que potamotrigonídeos compartilham um ancestral comum com as linhagens anfi-Americanas de Himantura. Por fim, algumas abordagens utilizadas neste estudo ilustram os benefícios de integrar diferentes bases de dados no refinamento taxonômico destes grupos dentro do conceito do que hoje reconhecemos como taxonomia integrativa / Studies on the co-evolution require accurate taxonomic and phylogenetic information to unambiguously establish associations within the lineages involved. Therefore, the present study identified marine parasite lineages from amphi-American species of Himantura Müller & Henle, H. schmardae (Werner) and H. pacifica (Beebe & Tee-Van). These hosts are considered the sister-group of potamotrygonids, which are Neotropical freshwater stingrays restricted to river systems in South America. Our motivation was the contribution on sound taxonomic grounds, in order to elucidate the historical associations among freshwater batoids, their alleged marine sister-group and their cestode parasites. To achieve this goal, we documented the fauna of three genera of cestodes, whose lineages can be found both in marine and freshwater stingrays, namely Acanthobothrium Blanchard, 1948, Anindobothrium Marques, Brooks & Lasso, 2001 and Rhinebothrium Linton, 1890. Each chapter addresses each genus separately. Our results consist of descriptions of 11 species new to science, among which seven are found parasitizing H. schmardae and 4 infecting H. pacifica. Furthermore, redescriptions are provided for three species detected in H. schmardae. All descriptions and redescriptions were based on an unprecedented number of specimens and included data obtained from histology, ligth microscopy and scanning electron microscopy. In addition to the taxonomic approach, we evaluated the phylogenetic relationships of Acanthobothrium and Anindobothrium. Molecular data from both genera revealed the congruence between the known patterns of host relationships and their parasites. The parasitological data presented in this study supports the recent hypothesis that potamotrygonids and amphi-American species of Himantura share a common ancestor. Moreover, the combined approach applied in this study illustrates the benefits of integrating different data sources for the taxonomic refinement of these groups within the concept of integrative taxonomy
68

Estudo da eletro-oxidação da mistura H2/CO utilizando eletrocatalisadores à base de Pt/C e Céria dopada com Ítria ou Rutênio para aplicação em células a combustível de membrana polimérica condutora de prótons / Study of electro-oxidation the mix H2/CO using Pt/C Etek and yttria or ruthenium doped ceria electrocatalysts for proton exchange membrane fuel cell

Lulio, Ligia Cristina D'Aloia 06 August 2012 (has links)
As formulações de eletrocatalisadores Pt:(Ce0,9Y0,1O2)+Pt/C Etek, Pt:(Ce0,9Ru0,1O2)+Pt/C Etek, Pt:Ce0,9Y0,1O2/C e Pt:Ce0,9Ru0,1O2+RuO2/C foram preparados pelo método da redução por álcool e caracterizados por difração de raios X (DRX) e microscopia eletrônica de transmissão (MET). A tolerância ao CO foi estudada utilizando o stripping de CO e medidas de curvas de polarização em células unitárias alimentadas com misturas de H2/CO no ânodo e oxigênio no cátodo, na temperatura de 80ºC e pressão absoluta de 2 bar para ânodo e cátodo. Os testes em células a combustível tipo PEMFC mostraram que a oxidação do CO adsorvido a CO2 na superfície da platina ocorre em potenciais menos positivos quando comparado com o catalisador comercial, Pt/C Etek, mostrando tolerância ao CO adsorvido nos eletrocatalisadores de Pt:Ce0,9Y0,1O2/C e Pt:(Ce0,9Ru0,1O2+RuO2)/C. / Pt:(Ce0,9Y0,1O2)+Pt/C Etek, Pt:(Ce0,9Ru0,1O2)+Pt/C Etek, Pt:Ce0,9Y0,1O2/C e Pt:Ce0,9Ru0,1O2+RuO2/C electrocatalysts, were prepared by an alcohol reduction process. The electrocatalysts were characterized by X-Ray Difratometry (XRD) end Transmission Electronic Microscopy (TEM). the CO tolerance was studied using CO stripping and measurements of polarization curves single-cell fed with H2/CO mixture at the anode and oxygen at the cathode, at a temperature of 85ºC and absolute pressure of 2 bar for anode and cathode. The results showed that the oxidation of CO adsorbed to CO2 on the surface of platinum occur at less positive potentials compared to Pt/C Etek showing the tolerance to CO adsorbed on these Pt:Ce0,9Y0,1O2/C e Pt:(Ce0,9Ru0,1O2+RuO2)/C electrocatalysts.
69

Estudos estruturais da SEPT8 e análise de suas interações com SEPT5 e SEPT7 / Structural studies of SEPT8 and analysis of its interaction with SEPT5 and SEPT7

Morais, Sinara Teixeira do Brasil 29 May 2014 (has links)
Septinas são proteínas que ligam GTP e interagem entre si formando heterocomplexos, os quais formam filamentos e estruturas de maior nível de organização. Tais filamentos, além de se mostrarem importantes durante a citocinese também podem estar envolvidos em outros processos celulares tais como determinação da polaridade celular e reorganização do citoesqueleto. As septinas, inicialmente descobertas em Saccharomyces cerevisiae, já foram identificadas também em fungos, algas-verdes, mamíferos, porém nunca em plantas. Tipicamente, septinas apresentam três domínios estruturais compostos por um domínio central de ligação ao GTP flanqueado por um N-terminal variável e um C-terminal que pode conter sequências do tipo coiled-coil. Este trabalho teve como objetivo a caracterização do domínio de ligação a GTP da septina 8 humana (SEPT8G) por meio de estudos biofísicos. Nesse sentido, SEPT8G foi eficientemente produzida em E. coli, tendo seu estado dimérico em solução confirmado por cromatografia de exclusão molecular. Diferentemente das outras septinas já reportadas, mesmo dimérica a SEPT8G apresentou-se na forma apo. Ensaios de atividade GTPásica foram realizados, confirmando a incapacidade dessa septina em hidrolisar o GTP. Ainda, análises de estabilidade térmica por Dicroísmo Circular revelaram que a presença do íon magnésio leva à diminuição de sua estabilidade estrutural. Baseando-se em resultados prévios de interação obtidos pela técnica do duplo-híbrido em leveduras, estudos voltados à análise da interação entre as septinas 7 e 8 e, posteriormente, entre as septinas 5, 7 e 8 foram realizados. A co-purificação do complexo formado pelas septinas 7 e 8 mostrou-se dependente da região C-terminal completa de SEPT7 de modo que, quando ausente, a interação mostrou-se expressivamente prejudicada. Já o complexo formado pelas septinas 5/7/8 foi obtido contendo as três proteínas em frações equimolares e solúveis, disponibilizando assim um novo heterocomplexo de septinas para ensaios funcionais e estruturais. / Septins are GTP-binding proteins that interact with each other to form heterocomplexes, which form filaments and higher order structures. These filaments are important for cytokinesis and may be involved in other cellular processes such as the determination of cell polarity and cytoskeleton reorganization. The septins, initially discovered in Saccharomyces cerevisiae, have also been identified in fungi, green algae, mammals but not in plants. Typically, septins have three structural domains comprising a central GTP binding domain flanked by a variable N-terminal and a C-terminal which can contain coiled-coil structures. This work sought to characterize the GTP-binding domain of the human septin 8 (SEPT8G) through biophysical studies. Accordingly, SEPT8G was efficiently produced in E. coli, and its dimeric state in solution was confirmed by size exclusion chromatography. Compared to other septins previously reported, the dimeric SEPT8G presented itself as an apo-protein. GTPase activity assays were performed, confirming the inability of this septin to hidrolyse GTP. Additionally, thermal stability analyses by Circular Dichroism showed that the presence of the magnesium ion leads to a decrease of structural stability. Considering previous results of septins interactions from yeast two-hybrid experiments, we have analyzed the interaction between the septins 7, 8 and subsequently among septins 5, 7 and 8. Co-purification of the complex formed by the septins 7 and 8 showed to be dependent on the complete SEPT7 C-terminal region so that, when absent, the interaction was significantly impaired. The obtained complex formed by septins 5/7/8 contained the three proteins in soluble and equimolar fractions, providing a new septin heterocomplex for functional and structural studies.
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Co-pirólise de polipropileno pós-consumo com gasóleo / Co-pyrolysis of polypropylene residues with gas-oil

Luiz Carlos Fonte Nova de Assumpção 30 June 2008 (has links)
O presente trabalho buscou avaliar o processo de co-pirólise de resíduos de polipropileno com gasóleo, variando a temperatura e a quantidade de polipropileno no meio reacional. A co-pirólise é uma rota promissora, uma vez que minimiza o impacto ambiental causado pela disposição do plástico de maneira inadequada, evita seu acúmulo em lixões e permite um melhor aproveitamento de um recurso natural não-renovável, o petróleo, matéria-prima importante para a geração de energia e obtenção de produtos químicos. As amostras de polipropileno e gasóleo foram submetidas à co-pirólise térmica em atmosfera inerte, em sistema de leito fixo, sob fluxo constante de nitrogênio, variando a temperatura de 400C a 500C e a quantidade de PP no meio reacional de 0,1 a 1,0 g. A influência do gasóleo no meio foi avaliada pelos testes na ausência de PP. Os líquidos pirolíticos obtidos foram caracterizados por cromatografia gasosa modificada, com o objetivo de avaliar a geração de frações na faixa da destilação do diesel. De uma maneira geral, pôde-se observar que o aumento da quantidade de PP no meio reacional favorece a redução do rendimento de líquido pirolítico e o aumento da quantidade de sólido gerado, efeito inverso ao do aumento da temperatura. Com relação ao rendimento geral de produtos na faixa de destilação do diesel na co-pirólise, a adição de PP ao meio não interfere muito no resultado. Já o aumento de temperatura favorece o aumento do rendimento de produtos nessa faixa de destilação. Os resultados obtidos comprovam o potencial da co-pirólise como método de reciclagem química de artefatos de polipropileno pós-consumo / In this study, the process of co-pyrolysis of polypropylene (PP) residues with gas-oil was evaluated, varying the temperature and the amount of polypropylene fed to the reactor. The co-pyrolysis is a promising route to minimize the environmental impact caused by the inadequate disposal of plastics, preventing its accumulation in landfields and giving a better use of the non renewable raw material (oil). The polypropylene samples and gas-oil were submitted to the thermal co-pyrolysis in an inert atmosphere, varying the temperature from 400C to 500C and the amount of PP from 0,1 to 1,0g. The influence of the gas-oil was evaluated carrying the co-pyrolysis in the absence of PP. The pyrolysed liquids produced by this thermal treatment were characterized by modified gaseous chromatography in order to evaluate the yield in the range of distillation of diesel. As a result, the increase of PP amount lead to a reduction in the yield of the pyrolytic liquid and to an increase of the amount of solid generated. The effect of temperature increase showed an inverse result. The addition of PP in the reactor showed little influence in the yield of diesel in the co-pyrolysis. On the other hand, an increase in temperature favors the increase of products in this range of destillation. The results show that plastic residue co-pyrolysys is a potential method for chemical recycling of plastic products

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