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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.
41

An Approach on Learning Multivariate Regression Chain Graphs from Data

Moghadasin, Babak January 2013 (has links)
The necessity of modeling is vital for the purpose of reasoning and diagnosing in complex systems, since the human mind might sometimes have a limited capacity and an inability to be objective. The chain graph (CG) class is a powerful and robust tool for modeling real-world applications. It is a type of probabilistic graphical models (PGM) and has multiple interpretations. Each of these interpretations has a distinct Markov property. This thesis deals with the multivariate regression chain graph (MVR-CG) interpretation. The main goal of this thesis is to implement and evaluate the results of the MVR-PC-algorithm proposed by Sonntag and Peña in 2012. This algorithm uses a constraint based approach used in order to learn a MVR-CG from data.In this study the MRV-PC-algorithm is implemented and tested to see whether the implementation is correct. For this purpose, it is run on several different independence models that can be perfectly represented by MVR-CGs. The learned CG and the independence model of the given probability distribution are then compared to ensure that they are in the same Markov equivalence class. Additionally, for the purpose of checking how accurate the algorithm is, in learning a MVR-CG from data, a large number of samples are passed to the algorithm. The results are analyzed based on number of nodes and average number of adjacents per node. The accuracy of the algorithm is measured by the precision and recall of independencies and dependencies.In general, the higher the number of samples given to the algorithm, the more accurate the learned MVR-CGs become. In addition, when the graph is sparse, the result becomes significantly more accurate. The number of nodes can affect the results slightly. When the number of nodes increases it can lead to better results, if the average number of adjacents is fixed. On the other hand, if the number of nodes is fixed and the average number of adjacents increases, the effect is more considerable and the accuracy of the results dramatically declines. Moreover the type of the random variables can affect the results. Given the samples with discrete variables, the recall of independencies measure would be higher and the precision of independencies measure would be lower. Conversely, given the samples with continuous variables, the recall of independencies would be less but the precision of independencies would be higher.
42

RESÍDUOS DE BIFENILOS POLICLORADOS EM ARROZ E FEIJÃO DO ESTADO DO RIO GRANDE DO SUL / RESIDUES OF POLYCHLORINATED BIPHENYL IN RICE AND BEANS IN THE STATE OF RIO GRANDE DO SUL

Cocco, Roberta 12 September 2011 (has links)
Conselho Nacional de Desenvolvimento Científico e Tecnológico / Polychlorinated biphenyls (PCBs) were commercially produced between 1929 and the mid 1980s with industrial purposes. The same properties that interested industrially, as chemical inertness, high dielectric constant, resistance to burning; were also responsible for the spreading of the PCBs in all of the environmental compartments, mainly due to the inadequate discard of equipments that contained PCBs (electronics), contaminating the water and the soil. They are persistent and non-biodegradable compounds that get accumulated in the environment, influencing all of the organisms in the food chain, and consequently all the food that is part of this chain. Human exposure to PCBs is the result of the large consumption of contaminated food, and also by inhalation and dermal absorption in hazardous environments, being the ingestion by contaminated food the main route of exposure. From conducted studies, its harmful effects to humans were found. Cereals and legumes deserve special attention in our diet, because, besides being essential food of easy acquisition, they are part of the general population s daily diet. Among these, rice and beans. For this reason, and because of the existence of environmental contamination by PCBs, it becomes of great interest to detect polychlorinated biphenyl residues in these foods. Because of this, combined with the persistence of the PCBs and their maleficent effects to humans, the general aim of this study was to identify and quantify indicator PCB residues in rice and bean samples obtained of the state of Rio Grande do Sul, in the year 2010. It is also intended to calculate the estimated daily ingestion of PCB residues from the contamination existing in rice and beans, and determination of fat content to correlate with levels of PCBs. The determination of the PCB residues was performed by gas chromatograph coupled to mass spectrometry (GC-MS), in the electron impact mode, after the extraction of the compound through the QuEChERS method. In the rice samples, average values of 0,05 ng g-1 for the PCB 28, 0,67 ng g-1 for the PCB 52, 0,24 ng g-1 for the PCB 101, 0,27 ng g-1 for the PCB 118, 1,28 ng g-1 for the PCB 138, 1,43 ng g-1 for the PCB 153 and 0,45 ng g-1 for the PCB 180. The PCB 52 was the most frequent, being found in 72,7% of the rice samples, followed by the PCBs 153 (54,5%), 138 (50,0%), 101 and 180 (13,6%), 118 (9,0%) and 28 (0,0%). In the beans samples, average values of 0,14 ng g-1 were found for the PCB 52, 1,63 ng g-1 for the PCB 101, 1,33 ng g-1 for the PCB 118, 0,92 ng g-1 for the PCB 138 and 0,05 ng g-1 for the PCBs 28, 153 and 180. The PCB 118 was the most frequent, being detected in 22,2% of the beans samples, followed by the PCBs 138 (11,0%), 52 and 101 (5,5%), and 28, 153 and 180 (0,0%). It was also observed that rice presented higher PCB average levels than beans. The estimated daily intake of PCBs, this was 7.82 ng kg-1 and 3.14 ng kg-1 body weight per day, for rice and beans, respectively. In relation to the percentage of fat rice had a fat content of 0.32% and 1.10% for beans. However, it is extremely important studies of this nature, because through this research it was concluded that there are still PCB residues in food of Rio Grande do Sul. / Bifenilos Policlorados (PCBs) foram produzidos comercialmente entre 1929 e meados de 1980 para propósitos industriais. As mesmas propriedades que despertaram o interesse industrial, tais como: inércia química, alta constante dielétrica, resistência à queima; foram responsáveis pelo espalhamento dos PCBs em todos os compartimentos ambientais, principalmente devido ao descarte inadequado de equipamentos que os continham (eletro-eletrônicos), contaminando a água e o solo. São compostos persistentes e não biodegradáveis que se acumulam no meio ambiente influenciando todos os organismos da cadeia alimentar, e conseqüentemente todos os alimentos que fazem parte desta cadeia. A exposição humana aos PCBs é o resultado do amplo consumo de alimentos contaminados, como também pela inalação e absorção dérmica em ambientes de risco, sendo a ingestão através de alimentos contaminados a principal via de exposição. A partir de estudos realizados, constatou-se o seu efeito nocivo aos seres humanos. Os cereais e as leguminosas merecem grande destaque em nossa alimentação, pois além de serem alimentos essenciais e de fácil aquisição, fazem parte da alimentação diária da população em geral. Dentre esses, cita-se o arroz e o feijão. Por esta razão e pela existência de contaminação ambiental por PCBs, torna-se de grande interesse detectar resíduos de bifenilos policlorados nesses alimentos. Diante disso, aliado com a persistência dos PCBs e seus efeitos maléficos aos seres humanos, o objetivo geral do presente trabalho foi identificar e quantificar resíduos de PCBs indicadores em amostras de arroz e feijão obtidas do estado do Rio Grande do Sul, no ano de 2010. Objetivou-se ainda calcular a ingestão diária estimada (IDE) de resíduos de PCBs, a partir da contaminação existente no arroz e feijão, e a determinação do teor de gordura para correlacionar com os níveis de PCBs. A determinação dos resíduos de PCBs foi realizada por cromatógrafo a gás acoplado a espectrometria de massas (GC-MS), no modo impacto de elétrons, após a extração dos compostos através do método QuEChERS. Nas amostras de arroz, foram encontrados valores médios de 0,05 ng g-1 para o PCB 28, 0,67 ng g-1 para o PCB 52, 0,24 ng g-1 para o PCB 101, 0,27 ng g-1 para o PCB 118, 1,28 ng g-1 para o PCB 138, 1,43 ng g-1 para o PCB 153 e 0,45 ng g-1 para o PCB 180. O PCB 52 foi o mais freqüente, sendo detectado em 72,7% das amostras de arroz, seguido dos PCBs 153 (54,5%), 138 (50,0%), 101 e 180 (13,6%), 118 (9,0%) e 28 (0,0%). Nas amostras de feijão, foram encontrados valores médios de 0,14 ng g-1 para o PCB 52, 1,63 ng g-1 para o PCB 101, 1,33 ng g-1 para o PCB 118, 0,92 ng g-1 para o PCB 138 e 0,05 ng g-1 para os PCBs 28, 153 e 180. O PCB 118 foi o mais freqüente, sendo detectado em 22,2% das amostras de feijão, seguido dos PCBs 138 (11,0%), 52 e 101 (5,5%), e 28, 153 e 180 (0,0%). Observou-se ainda que o arroz apresentou níveis médios de PCBs superiores ao feijão. Quanto a ingesta diária estimada de PCBs, esta foi de 7,82 ng Kg-1 e de 3,14 ng Kg-1 de peso corporal por dia, para o arroz e o feijão, respectivamente. Em relação ao percentual de gordura o arroz apresentou um teor de gordura de 0,32% e o feijão de 1,10%. No entanto, é de extrema impôrtancia estudos desta natureza, pois através desta pesquisa concluiu-se que ainda existem resíduos de PCBs em alimentos do Rio Grande do Sul.
43

Error Estimation for Solutions of Linear Systems in Bi-Conjugate Gradient Algorithm

Jain, Puneet January 2016 (has links) (PDF)
No description available.
44

La chimère transférentielle : proposition épistémologique, neuroscientifique et clinico-théorique du transfert psychanalytique comme système complexe / The transferential chimera : epistemological, neuroscientific and clinico-theoretical proposal of the transference as a complex system

Martin-Vallas, François 21 April 2015 (has links)
Ce travail, qui s’inscrit dans le cadre de la psychologie analytique développée par Jung, propose d’introduire le concept de chimère transférentielle comme dimension du transfert qui ne peut être assignée ni à l’un ni à l’autre des deux protagonistes d’un travail analytique, bien que les concernant tous deux. Cette dénomination repose autant sur le travail de Michel de M’Uzan que sur le champ sémantique complexe associé au mot chimère. La méthodologie de ce travail est celle, théorico-clinique, développée par Widlocher sous le nom de cas singulier. Elle conduit à la recherche d’une preuve d’existence, et non à une preuve d’universalité. Une première partie propose une discussion épistémologique qui prenne en compte les changements profonds des paradigmes scientifiques résultant du développements de la physique depuis le début du XXe avec l’avènement de la relativité restreinte, rapidement suivie de la relativité générale et de la mécanique quantique puis de la théorie des systèmes complexes, aussi appelée théorie du chaos. Il est soutenu dans ce travail qu’une révision des positions épistémologiques fondées sur le travail de Popper, et une meilleure prise en compte d’approches telles que proposées par Adorno ou Morin, est nécessaire. Cette discussion conclut à l’importance de notions telle que celles d’émergence ou d’énaction, en ce qu’elles rendent compte du fait que ce qui apparaît à un moment donné de l’expérience ne préexiste pas nécessairement à sa manifestation. Enfin cette discussion épistémologique tente d’éclairer la profonde divergence entre les approches de Freud et de Jung, divergence qui apparaît ici comme résultant principalement d’une différence de point de vue épistémologique. Là aussi, le recours à la physique, précisément à la notion de section de Poincaré, permet d’éclairer cette divergence autrement que par une simple opposition. Cela permet de comprendre pourquoi, dans le champ de la psychologie clinique autant que dans celui de la psychanalyse, des théories divergentes, parfois opposées, peuvent et doivent coexister afin de pouvoir construire une représentation aussi exhaustive que possible de la réalité. Dans une seconde partie l’hypothèse de la chimère transférentielle est abordée au regard des neurosciences. Il est ainsi proposé une représentation neuroscientifique de la relation analytique. Cette représentation n’a aucunement pour objet de se prétendre vraie, mais, plus modestement, possible. Elle vise à proposer une nouvelle manière d’articuler neurosciences et théories psychanalytiques, postulant que l’expérience de la clinique psychanalytique est un niveau de complexité très supérieur à ce qui est aujourd’hui accessible aux neurosciences, ce qui permet de rendre compte de l’existence de dynamiques propres au processus analytique du fait de leur émergence entre les niveaux de complexité accessibles à la recherche neuroscientifique et celui de l’expérience psychanalytique. Enfin, dans une troisième partie, ce travail aborde différents aspects de la chimère transférentielle telle qu’elle est se manifeste dans la clinique psychanalytique. Un premier cas clinique est exposé en détail afin d’apporter une preuve d’existence de cette dimension. D’autres cas cliniques suivent, centrés sur une dimension ou un moment particulier de la cure, afin d’apporter la preuve de cette existence dans d’autres contextes, et avec des patients dont le fonctionnement et la structure psychique diffèrent autant du premier cas exposé qu’entre eux. Enfin, chacun de ces cas a été l’occasion de focaliser la discussion théorico-clinique sur un aspect particulier, saillant dans le cas considéré. / This thesis, intended as a contribution to analytical psychology as developed by CG Jung, proposes the notion of a transferential chimera as a dimension of the transference which may not be assigned to either one of the protagonists in the analytic dyad, while still attached to them both. This denomination draws as much on the work of Michel de M’Uzan as it does on the complex semantics associated with the term chimera. The methodology used here is the clinical and theoretically underscored approach to the single case. It is predicated on the search for a proof of existence, and not a proof of universality. The first part is devoted to an epistemological discussion which takes account of the fundamental changes in theoretical understanding brought about in the field of physics since the beginning of the XXth century. This encompasses restrained relativity, quickly followed by general relativity and, laiter, by the theory of complex systems and chaos theory. It is contended that Carl Popper’s position on epistemology is in need of revision and that account needs to be taken now of the developments put forward by Theodore Adorno and Edgar Morin. The present discussion concludes that ideas such as emergence and enactment are central to the proposition in that they explain how events that occur in experience at a given time do not necessarily exist prior to their manifestation. Finally, this epistemological discussion seeks to throw light on the profound divergence between the approaches of Freud and Jung that appear to stem from a difference in their particular epistemologies. Here again, reference to physics, specifically to Poincare’s map, allows this divergence to be understood as other than a simple opposition. It assists in the understanding why in clinical psychology as in the field of psycho analysis, divergent and sometimes opposing theories, can and need to co-exist in order to construct as exhaustive a representation of reality as may be possible. In part two the chimera hypothesis is examined in the light of neurosciences. An attempt is made to represent the analytic relationship in terms of neurosciences. In no sense is such a representation to be taken as real, merely as possible. The aim is to postulate a new method of articulating neuroscience and psychoanalytic theory, whereby the experience of psychoanalytic practice is at a far greater level of complexity than it is currently possible to express neuroscientifically. This enables an account to be given of the existence of dynamics inherent in the psychoanalytic process from their observed emergence between the levels of complexity that are amenable to neuroscientific research and being experienced during psychoanalysis. Finally, in part three, different aspects of the transferential chimera will be examined as it manifests in psychoanalytic practice. With the aid of a detailed clinical example an attempt is made to establish the existence of this phenomenon. Other clinical cases will centre on an aspect or a specific moment during treatment, in order to support the proof of its existence in other contexts, that is, with patients whose functioning and psychic structure contrasts as markedly from the first case as they do amongst themselves. Finally, each case gives the opportunity to focus the theoretical and clinical discussion on a salient feature of each case.Thus the working potential of this hypothesis shall have been informed by the archetypal nature of the transference according to Jungian theory, by the potential connection between it and Freudian theory, starting with primary seduction as envisaged by Laplanche, followed by the containing function of the chimera, still in the context of Jungian theory.
45

Aplicação de cromatografia gasosa acoplada à espectrometria de massas na identificação de substâncias obtidas de algas marinhas de dois estados do Nordeste brasileiro / Application of gas chromatrography-mass spectrometry to identify substances obtained from seaweed of two states in Northeastern Brazil

Silva, Daniel Lira da 26 August 2014 (has links)
Seaweeds are organisms which live in oceans and seas. They have ability to perform photosynthesis and feed many species of aquatic organisms. Macroalgae, which can be divided by characteristic colors in: Red algae (Phylum Rhodopyta), Green algae (Phylum Chlorophyta) and Brown algae (Class Phaeophyceae). Seaweeds are used for centuries by Asians as an important part of their diet, and also as source of compounds to Pharmaceutical and Cosmetic industries. The Brazilian Northeastern has a large coastal area; it possesses several forms of marine organisms especially for being in a Tropical hot water zone. Based on the importance of macroalgae, a chemical study was conducted using five species of algae (Bryothamnion seaforthii; Colpomenia sinuosa; Dictyosphaeria versluysii, Digenea simplex and Galaxaura rugosa) to prepare methanolic extracts and sequential fractions. 72 substances were identified using the GC-MS technique under the following operation conditions: helium as the carrier gas; 1.52 mL/min flow rate; oven temperature 60 º (25 ºC/min 300 ºC, heating rate); Splitless; injected volume 1 μL; solvent cutting 3 minutes. The mass spectra were obtained in the same equipment by electron impact ionization (EI) at 70 eV; and the ion source was maintained at 300 ° C. Hexadecanoic acid, in all fractions; 1-isopropyl-1,3,4-trimethyl-cyclohexane, 1,4-diisopropyl-cyclohexane and isopentyl decanoate, first identified in seaweeds; several esters, hydrocarbons and fatty acids can be mentioned as identified substances. / Conselho Nacional de Desenvolvimento Científico e Tecnológico / Alga é uma forma de vida que vive em oceanos e mares e possui a capacidade de realizar fotossíntese e servir de alimento e/ou abrigo para muitas espécies de organismos aquáticos. As macroalgas, que podem ser divididas pela cor característica que possuem, em algas vermelhas (Filo Rhodophyta), verdes (Filo Chlorophyta) e pardas (Classe Phaeophyceae), são utilizadas pelos orientais como parte importante de sua alimentação há vários séculos, além de utilizá-las como fonte de produtos farmacêuticos e da indústria de cosméticos. O nordeste brasileiro possui uma vasta área litorânea e costeira sendo rico em diversas formas de vida marinha, principalmente por estar em uma zona tropical de águas quentes. Com base na importância destas macroalgas, foi realizado um estudo químico de cinco espécies de algas, Bryothamnion seaforthii, Colpomenia sinuosa, Dictyospharia versluysii, Digenea simplex e Galaxaura rugosa, através de extratos metanólicos e frações. A técnica de cromatografia gasosa acoplada à espectroscopia de massas foi utilizada com as seguintes condições de operação: hélio como gás de arraste; velocidade do fluxo, 1,52 mL/min; a temperatura inicial do forno foi 60 ºC, com uma taxa de aquecimento de 25 ºC/min até 300 ºC; “Splitless”, como modo de injeção; 1 μL de volume injetado; e corte do solvente em 3 minutos. O tempo total de corrida foi 25 minutos. Os espectros de massas foram obtidos no mesmo equipamento, através de ionização por impacto de elétrons (EI) de 70 eV; e a fonte de íons foi mantida a 300 ºC. Desse modo foram identificadas 72 substâncias, dentre as quais podem ser citadas: ácido hexadecanoico, presente em todas as frações; os hidrocarbonetos 1-isopropil-1,3,4-trimetilcicloexano, 1,4-di-isopropilcicloexano e decanoato de isopentila, identificados pela primeira vez em algas; além de diversos ésteres, hidrocarbonetos e ácidos graxos.
46

Estudo químico e avaliação da atividade antiprotozoária in vitro do óleo volátil de Lavandula angustifolia Miller (Lamiaceae) / Chemical composition and in vitro antiprotozoal activity of the vola-tile oil from Lavandula angustifolia Miller (Lamiaceae)

Erika Yamamichi 04 November 2014 (has links)
O número de pessoas infectadas por protozoários dos gêneros Leishmania e Trypanosoma cruzi, no mundo, permanece preocupante, havendo cerca de 12 milhões de casos de leishmaniose e 7 a 8 milhões referentes à doença de Chagas. Face ao grave quadro destas doenças e às limitações da terapêutica atual, a busca de novos fármacos é urgente. Considerada uma das principais estratégias disponíveis, a pesquisa a partir de espécies vegetais contendo constituintes bioativos é promissora fonte de moléculas potencialmente ativas. Neste contexto, espécies do gênero Lavandula mostraram atividade anti-Leishmania in vitro, tendo motivado a seleção de L. angustifolia (Lamiaceae). Embora tenham sido comprovadas diversas atividades farmacológicas desta espécie, a atividade antiprotozoária frente aos agentes avaliados ainda não havia sido estudada. Além disto, a produção em larga escala e o seu uso bastante difundido no mundo, sobretudo nas indústrias cosméticas, de perfumes e de domissanitários, despertou interesse. O presente trabalho visou à análise da composição do óleo volátil de uma variedade de L. angustifolia aclimatada ao Brasil e à avaliação de sua atividade antiprotozoária in vitro, frente a cepas de Leishmania infantum, L. amazonensis e de Trypanosoma cruzi. A análise do óleo volátil das inflorescências e das folhas, por CG-EM, indicou a predominância de monoterpenos, tendo-se estabelecido análise comparativa entre estes órgãos. De forma geral, o óleo foi inativo frente às espécies de Leishmania, tendo apresentado promissora atividade anti-Trypanosoma. / The number of people infected by Leishmania and Trypanosoma cruzi protozoa around the world has increased and raised concerns that approximately 12 million cases of leishmaniasis and 7 to 8 million cases of Chagas disease have been reported. The alarming statistics involving these diseases and limitations of therapeutics currently in use point to an urgent need for new drugs. Considered one of the main strategies available, research on plants containing bioactive constituents is a promising source of potentially active molecules. Species of Lavandula genus have shown in vitro anti-Leishmania activity and this encouraged the present study on L. angustifolia (Lamiaceae) species. Although several pharmacological activities have been identified, the antiprotozoal activity against these specific agents has not yet been approached. Moreover, the possibility of a large-scale production and its quite comprehensive use worldwide, especially for the manufacturing of cosmetics, perfumes and household sanitizing products have attracted our interest. This study aimed at the analysis of the volatile oil compounds of the L. angustifolia species acclimatized in Brazil as well as the evaluation of the in vitro antiprotozoal activity against the strains of Leishmania (L.) infantum, L. (L.) amazonensis and Trypanosoma cruzi. The CG-EM analysis of the volatile oil from the inflorescences and leaves has shown monoterpenes as majority constituents also allowing a comparative analysis between these organs. Overall, the oil was not active against the Leishmania species but presented promising anti-Trypanosoma activity.
47

The use of Digital Visual Effects in contemporary TV-series : An analysis of the use of digital visual effects as a narrative device in the television series Doctor Who, Defiance and Terra Nova

Eklund, Thorbjörn January 2014 (has links)
In this thesis the argument of a new visual language as a narrative device will be discussed and looked at, by analyzing four different TV-series in the science-fiction genre: Terra Nova 2011, Defiance 2013-, Doctor Who 1963 – 1989 and Doctor Who 2005-. It will be possible to see the use of digital visual effects as a narrator in the image. To do this one main question has been asked and to be able to answer that question a framework model has been created, consisting of seven different questions: How are DVFx used as a visual language in the TV-series? What key elements drive the TV-series forward? What influence did DVFx have on the TV-series? How is DVFx used in the series as a narrator? What does DVFx represent in the image? Could the series have been created without DVFx? Techno-enhancement, visual language or hybrid?
48

A snapshot of the unity and diversity of biological systems at the level of chemistry : structural and mechanistic studies of Cg10062, a homologue of cis-3-chloroacrylic acid dehalogenase, FG41 malonate semialdehyde decarboxylase and the catalytic domain of pyruvate dehydrogenase phosphatase 1

Guo, Youzhong, 1974- 15 September 2010 (has links)
The tautomerase superfamily is composed of a group of proteins characterized by two key features: the N-terminal proline and a beta-alpha-beta-motif. This superfamily has been divided into five families represented by 4-oxalocrotonate tautomerase (4-OT), 5-(carboxymethyl)-2-hydroxymuconate isomerase (CHMI), cis-3-chloroacrylic acid dehalogenase (cis-CaaD), malonate semialdehyde decarboxylase (MSAD), and macrophage migration inhibitory factor (MIF). Cg10062 is a homologue of cis-CaaD, but has several distinct biochemical properties from cis-CaaD. For example, Cg10062 can be irreversibly inhibited by (R)- or (S)-oxirane-2-carboxylate, whereas cis-CaaD can only be irreversibly inhibited by (R)-oxirane-2-carboxylate. FG41MSAD is a homologue of MSAD, with comparable decarboxylase activity but missing Arg-73 known to be crucial for the MSAD activity. In order to understand the unique biochemical characteristics of Cg10062 and FG41MSAD, we have solved five crystal structures. These crystal structures have established a solid structural basis for understanding the mechanisms of their activities. The eukaryotic protein phosphatases are composed of a group of proteins that are responsible for reversible phosphorylation. The eukaryotic protein phosphatases have been divided into three families, the phosphoprotein phosphatase (PPP) family, the protein phosphatase Mg2+- or Mn2+-dependent (PPM) family and the protein Tyr phosphatase (PTP) family. PDP1 is a member of PPM family. PDP1 is also an important component of the large pyruvate dehydrogenase complex (PDC) which catalyzes the decarboxylation of pyruvate to yield acetyl-CoA with the accompanying reduction of NAD+. In order to understand the mechanism in which it dephosphorylates its target protein we have solved the structure of the catalytic domain of PDP1. Analysis of these structures in the light of their evolutionary contexts enables us to appreciate the unity and diversity of the biological systems at the chemical level and help us solve interesting problems, such as the possible physiological functions for some members within the tautomerase superfamily. / text
49

Biodegradação dos pesticidas clorpirifós, metil paration e profenofós por fungos de origem marinha / Biodegradation of pesticides chlorpyrifos, methyl parathion and profenofos by marine fungi

Silva, Natália Alvarenga da 26 April 2013 (has links)
Neste trabalho, foi realizada uma triagem com os fungos marinhos Aspergillus sydowii CBMAI 934, Aspergillus sydowii CBMAI 935, Aspergillus sydowii 1241, Penicillium decaturense CBMAI 1234, Penicillium raistrickii CBMAI 931, Penicillium raistrickii CBMAI 1235 e Trichoderma sp. CBMAI 932 com o objetivo de avaliar o potencial enzimático destes micro-organismos frente à biodegradação dos pesticidas organofosforados clorpirifós, metil paration e profenofós. Os fungos selecionados para as reações em meio líquido de malte 2%, que melhor adaptaram-se na presença do pesticida clorpirifós, foram as cepas de A. sydowii CBMAI 935 e Trichoderma sp. CBMAI 932, na presença de metil paration foram A. sydowii CBMAI 935 e P. decaturense CBMAI 1234 e na presença de profenofós foram os fungos A. sydowii CBMAI 935 e P. raistrickii CBMAI 931. Foram realizadas curvas analíticas com o objetivo de estimar a extensão da biodegradação dos pesticidas clorpirifós, metil paration, profenofós, e seus respectivos produtos de hidrólise, os derivados fenólicos 3,5,6-tricloro-2-piridinol, 4-nitrofenol e 4-bromo-2-clorofenol, respectivamente. As reações de biodegradação em meio líquido de malte 2% foram avaliadas com 10, 20 e 30 dias de reação com concentração inicial dos pesticidas organofosforados de 50 ppm. O pesticida, profenofós, apresentou uma biodegradação completa com o fungo P.raistrickii CBMAI 931 com 30 dias de reação, e 70% com o fungo A. sydowii CBMAI 935, para o mesmo período. Os fungos também apresentaram potencial para a degradação (ou conjugação) do metabólito, 4-bromo-2-clorofenol. Na presença dos fungos A. sydowii CBMAI 935 e Trichoderma sp. CBMAI 932, clorpirifós apresentou a menor degradação entre os pesticidas avaliados, com uma taxa de degradação de 63 e 72%, respectivamente, em 30 dias de reação. Os fungos selecionados não foram capazes de promover uma degradação apreciável do 3,5,6-tricloro-2-piridinol. Na presença dos fungos A. sydowii CBMAI 935 e P. decaturense CBMAI 1234, o metil paration apresentou uma degradação de 100% em 20 dias de reação. O 4-nitrofenol apresentou degradação (ou conjugação) de aproximadamente 50 e 40% na presença dos fungos A. sydowii CBMAI 935 e P. decaturense CBMAI 1234, respectivamente. Finalmente, os estudos apresentados comprovam a eficiência dos fungos de ambiente marinhos na biodegradação de pesticidas organofosforados. / In this work was performed a screening with the marine fungi Aspergillus sydowii CBMAI 934, Aspergillus sydowii CBMAI 935, Aspergillus sydowii 1241, Penicillium decaturense CBMAI 1234, Penicillium raistrickii CBMAI 931, Penicillium raistrickii CBMAI 1235 e Trichoderma sp. CBMAI 932 to evaluate the enzymatic potential of these microorganisms in the presence of organophosphate pesticides chlorpyrifos, methyl parathion and profenofos. The selected fungi for the reactions in liquid medium of malt 2%, which demonstrated better adaptation in presence of the pesticide chlorpyrifos, were the strains of A.sydowii CBMAI 935 and Trichoderma sp. CBMAI 932, in the presence of methyl parathion were A.sydowii CBMAI 935 and P. decaturense CBMAI 1234 and, in presence of profenofos were the fungi A. sydowii CBMAI 935 and P. raistrickii CBMAI 931. Analytical curves were performed in order to estimate the extent of biodegradation of the pesticide chlorpyrifos, methyl parathion, profenofos, and their hydrolysis products, 3,5,6-trichloro-2-pyridinol, 4-nitrophenol, 4-bromo 2-chlorophenol, respectively. Biodegradation reactions in liquid medium of malt 2% were evaluated with 10, 20 and 30 days with an initial concentration of 50 ppm of organophosphate pesticides. Profenofos, presented a complete biodegradation (100%) with the fungus P.raistrickii CBMAI 931, in 30 days of reaction, and 70% of biodegradation in the presence of the fungus A. sydowii CBMAI 935, at the same period. The fungi also showed a potential for degradation (or conjugation) of 4-bromo-2-chlorophenol. In the presence of the fungus A. sydowii CBMAI 935 and Trichoderma sp. CBMAI 932, chlorpyrifos exhibited the lowest degradation among the evaluated pesticides, presenting a degradation rate of 63 and 72%, respectively, at 30 days of reaction. The selected fungi were not capable of promoting an appreciable degradation of 3,5,6-trichloro-2-pyridinol. In the presence of A. sydowii CBMAI 935 and P. decaturense CBMAI 1234, methyl parathion showed a degradation of 100%, at 20 days of reaction. The 4-nitrophenol showed a degradation (or conjugation) of approximately 50 and 40% in the presence of the fungus A. sydowii CBMAI 935 and P. decaturense CBMAI 1234, respectively. Finally, the presented studies demonstrated the efficiency of the marine fungi in biodegradation of organophosphate pesticides.
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Desenvolvimento e validação de método para análise de nicotina e cotinina em amostras de mecônio utilizando a cromatografia em fase gasosa acoplada à espectrometria de massas / Development and validation of a methodology for analysis of nicotine and cotinine in meconium samples using gas chromatography-mass spectrometry.

Barros, Luiza Saldanha Ribeiro 18 April 2011 (has links)
O mecônio é uma matéria fecal que começa a acumular no intestino do feto por volta do terceiro mês de gestação e normalmente é eliminado nos primeiros dias de vida do recém nascido. No mecônio ocorre o acúmulo de substâncias com as quais a mãe entrou em contato durante o período de gestação e, portanto, sendo possível avaliar a exposição fetal. Nos casos de mães fumantes, compostos presentes no tabaco tais como nicotina e substâncias que são formadas após a metabolização da nicotina como por exemplo a cotinina, podem ser também detectadas nas amostras de mecônio, já que ocorre o acúmulo de nicotina e seus metabólitos no mesmo. O uso do cigarro durante o período gestacional acarreta em uma série de problemas ao feto como baixo peso ao nascer, parto pré-maturo, doenças no trato respiratório, dentre outros. Nos dias atuais é possível fazer a pesquisa de drogas lícitas e ilícitas em várias amostras biológicas tais como, sangue, urina, cabelo, fluido oral, mecônio, entre outras. O mecônio é uma boa opção, por vários motivos: amostragem fácil e não invasiva (a coleta pode ser feita na fralda), indica o histórico do uso de substâncias pela mãe durante a gestação por ser cumulativo, etc. O objetivo foi desenvolver e validar um método analítico empregando cromatografia em fase gasosa acoplada a espectrometria de massas para a determinação de nicotina e, seu metabólito, cotinina em amostras de mecônio coletadas de recém nascidos. Para o desenvolvimento do método foi utilizado 0,5g de mecônio e os analitos foram extraídos com metanol e em seguida a amostra foi submetida a purificação através da extração em fase sólida utilizando cartuchos Bond Elut Certify I. O método foi validado de acordo com os parâmetros estabelecidos pela ANVISA e demonstrou linearidade de 160 1600 ng/g para nicotina e de 160 1000 ng/g para cotinina. Os limites de detecção estabelecidos foram de 10 ng/g para nicotina e 60 ng/g para cotinina, enquanto os limites de quantificação foram de 60 ng/g para nicotina e 100 ng/g para cotinina. A exatidão apresentou valores de 91,73% a 103,73%, a precisão intra-ensaio variou entre 3,21% a 10,86%, e a precisão inter-ensaio obteve valores entre 4,91% a 9,88%. O método validado foi aplicado em amostras de mecônio coletadas no Hospital das Clínicas da Faculdade de Medicina de Ribeirão Preto (HCFMRP-USP). / Meconium is a fecal matter passed by the newborn after birth. It begins to form around the 3th month of gestation and accumulates in the fetus until birth. Substances which the mothers had contact during the gestation period may accumulate in meconium and, therefore, its possible to assess fetal exposure. Substances from the tobacco smoke, like nicotine and its metabolite cotinine, also accumulates in the meconium and can be detected .Maternal smoking during pregnancy is hazardous to the fetus and it is associated with low birth weight, prematurity, respiratory tract infections and others. Nowadays it is possible to assess licit and illicit drugs in several biological samples like blood, urine, hair, oral fluid, meconium and others. Meconium is the best choice because its easy to collect and its noninvasive, indicates a history of substances use by the mother in the latter half of pregnancy, etc. The purpose of this study was to develop and validate a methodology using gas chromatography-mass spectrometry to assess nicotine and cotinine in meconium samples collected from newborns. To the development of the methodology 0,5g of meconium was used per assay and the analytes were extracted from the matrix using methanol. Then, a solid phase extraction was applied using Bond Elut Certify I cartridges. The methodology was validated in the range of 160 1600 ng/g for nicotine and 160 - 1000 ng/g for cotinine. The limit of detection established was 10 ng/g for nicotine and 60 ng/g for cotinine, while the limit of quantification was 60 ng/g for nicotine and 100 ng/g for cotinine. The accuracy showed values between 91,73% and 103,73%, the intra-assay precision between 3,21% and 10,86% and the inter-assay precision between 4,91% and 9,88%. The validated methodology was applied to analysis of meconium samples collected from newborns in the Hospital das Clínicas da Faculdade de Medicina de Ribeirão Preto (HCFMRP-USP).

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