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Diatom AlchemyGaddis, Christopher Stephen 03 December 2004 (has links)
This work resulted in the development of multiple distinct and novel methods of cheaply producing large numbers of biologically derived, complex, 3-dimensional microstructures in a multitude of possible compositions. The biologically derived structures employed in this work were diatoms, a type of single celled algae, which grow complex silica shells in species-specific shapes. Due to the wide diversity of naturally occurring diatom shapes (on the order of 105), and the flexibility in tailoring chemical compositions using the methods developed here, real potential exists for cheaply mass-producing industrially relevant quantities of controlled shape and size 3-d particles for the first time. The central theme of this research is the use of diatoms as a transient scaffold onto which a coating is applied. After curing the coating, and in some cases firing the coating to form ceramic, the diatom can be selectively etched away leaving a free standing replica of the original structure with the salient features of the pre-form intact, but now composed of a completely different material. Using this concept, specific methods were developed to suit various precursors. Dip coating techniques were used to create epoxy diatoms, and silicon carbide diatoms. The Sol-Gel method was used to synthesize zirconia diatoms in both the tetragonal and monoclinic phases. A multi step method was developed in which previously synthesized epoxy diatoms were used as a template for deposition of a silicon carbide precursor and then heat treated to produce a silicon carbide/carbon multi-component ceramic. A hydrothermal reaction was also developed to convert Titania diatoms to barium titanate by reaction with barium hydroxide. Finally, the device potential of diatom-derived structures was conclusively demonstrated by constructing a gas sensor from a single Titania diatom. Under suitable conditions, the sensor was found to have the fastest response and recovery time of any sensor of this type reported in the literature. Furthermore, this work has laid the groundwork for the synthesis of many other tailored compositions of diatoms, and provided several compositions for device creation.
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Surveying trends in analogy-inspired product innovationNgo, Peter 22 May 2014 (has links)
Analogies play a well-noted role in innovative design. Analogical reasoning is central to the practices of design-by-analogy and bio-inspired design. In both, analogies are used to derive abstracted principles from prior examples to generate new design solutions. While numerous laboratory and classroom studies of analogy usage have been published, relatively few studies have systematically examined real-world design-by-analogy to describe its characteristics and impacts. To better teach design-by-analogy and develop support tools for engineers, specific insights are needed regarding, for example, what types of product advantages are gained through design-by-analogy and how different design process characteristics influence its outcomes. This research comprises two empirical product studies which investigate analogical inspiration in real-world design to inform the development of new analogy methods and tools. The first, an exploratory pilot study of 57 analogy-inspired products, introduces the product study method and applies several categorical variables to classify product examples. These variables measure aspects such as the composition of the design team, the driving approach to analogical reasoning, and the achieved benefits of using the analogy-inspired concept. The full scale study of 70 analogy-inspired products uses formal collection and screening methods and a refined set of classification variables to analyze examples. It adopts a cross-sectional approach, using statistical tests of association to detect relationships among variables. Combined, these surveys of real-world analogy-inspired innovation inform the development of analogy tools and provide a general account of distant analogy usage across engineering disciplines. The cross-sectional product study method demonstrated in this work introduces a valuable tool for investigating factors and impacts of real-world analogy usage in design.
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Moléculas orgânicas sobre superfícies metálicas : uma investigação teórica / Organic molecules on metalic surfaces : a thoretical investigationBrunetto, Gustavo, 1983- 07 August 2009 (has links)
Orientador: Douglas Soares Galvão / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica "Gleb Wataghin" / Made available in DSpace on 2018-08-14T05:39:30Z (GMT). No. of bitstreams: 1
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Previous issue date: 2009 / Resumo: Recentemente, a primeira nanoroda molecular foi caracterizada a partir de experimentos com o microscópio de tunelamento eletrônico (STM). Foi demonstrado que a molécula de hidrocarboneto (C44H24) especificamente desenhada poderia rolar sobre a superfície de cobre ao longo da direção [110] da superfície. A molécula consiste em duas rodas baseadas no grupo triptycene as quais são conectadas por um eixo. Nós reportamos um estudo teórico da simulação desse processo. Usamos métodos ab initio (DMol 3) e de dinâmica molecular clássica (UFF). Consideramos diferentes orientações cristalográficas ([111], [110], e [100]) para a superfície de cobre, a fim de determinar como estas diferentes orientações afetam o processo de rolamento molecular. Nossos resultados estão em boa acordância com os dados experimentais disponíveis. As simulações mostraram que o mecanismo de rolamento só é possível para a direção [110]. Para as outras direções ([111] e [100]) a superfície é muito suave e não pode prover o torque necessário para o processo de rolamento. Para estes casos a molécula somente desliza (movimento de translação), sem rolar quando interage com a ponta do microscópio. Para a direção [110] a separação espacial entre as colunas de cobre é suficiente para travar a molécula e criar um torque. Além da superfície correta, a posição relativa da molécula sobre a superfície é muito importante. A molécula deve estar com seu eixo principal paralelo à direção [110]. Este efeito de comensurabilidade, entre a molécula e a superfície, é similar a difusão seletiva na superfície recentemente observada para outras classes de moléculas orgânicas. Os perfis experimentais observados para o empuramento, puxamento e rolamento também podem ser explicados em termos destas características geométricas entre a molécula e as diferentes direções cristalográficas do cobre / Abstract: Recently, the first molecular nanowheel was characterized with scanning tunneling micro-scope experiments. It was demonstrated that a specifically designed hydrocarbon molecule (C44H24) could roll over a copper substrate along the [110] direction of a surface. The molecule consists in two wheels based on two triptycene groups which are connected by an axle. We report a theoretical study of the simulations of this process. We used ab initio (DMol 3) and classical molecular dynamics methods (UFF). We have considered different crystallographic orientations ([111], [110], and [100]) for the copper surface, in order to determine how these different orientations affect the molecular rolling processes. Our results are in good agreement with the available experimentally data. The simulations showed that the rolling mechanism is only possible for the [110] direction. For the others directions ([111] and [100]) the surfaces are too smooth and cannot provide the necessary torque to the rolling process. For these cases the molecule just slides (translational movement), without rolling when interact with the STM tip. For the [110] direction the spatial separation among rows of copper atoms is enough to trap the molecule and to create a torque. Besides the correct surface the relative position of the molecule on the surface is very important. The molecule should be with its main axis in the parallel direction to [110]. This commensurability effect, between the molecule and the surface, is similar to the surface selective diffusion recently observed for other classes of organic molecules. The experimental observed pushing, pulling, and rolling profiles can also be explained in terms of these geometrical features between the molecule and the different Cu crystallographic directions / Mestrado / Mestre em Física
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Uma proposta imuno-inspirada para segmentação de imagens com texturas usando transformada wavelet packet / An immune-inspired proposal for textured image segmentation using wavelet packet transformSilva, Karinne Saraiva da 15 August 2018 (has links)
Orientador: Yuzo Iano / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Eletrica e de Computação / Made available in DSpace on 2018-08-15T16:56:14Z (GMT). No. of bitstreams: 1
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Previous issue date: 2010 / Resumo: Segmentação de texturas é um ponto crucial em muitas aplicações da área de visão computacional e processamento digital de imagens. Muitas são as aplicações que utilizam imagens com texturas, como: sensoriamento remoto, análise de imagens médicas, inspeção industrial, etc. Para análise de texturas, é essencial o uso de um extrator de características capaz de representar bem cada textura presente na imagem. A transformada wavelet packet fornece a caracterização necessária para discriminação de texturas, oferecendo também uma representação multi-escala, ferramenta muito importante na análise de texturas. Outro ponto importante neste trabalho, é o fato da metodologia aqui proposta ser não supervisionada. Para tal, é utilizado o algoritmo de clusterização ARIA, que determina automaticamente o número de clusters presentes no conjunto de dados. A eficiência do método desenvolvido é comprovada aplicando-o em diversas imagens, como: mosaicos de Brodatz, imagens naturais, imagens médicas e outras aplicações. / Abstract:Texture segmentation is a crucial aspect in many computer vision and digital image processing applications. Several of these applications use texture images, such as remote sensing, medical image analysis, industrial inspection, etc. For texture analysis, it is essential to use a feature-extractor that can represent precisely each of the textures present in the picture. The wavelet packet transform provides the characteristics required for discrimination of the textures, as well as offering a multi-scale representation, which is a very important tool in texture analysis. Another important aspect in this work is that the proposed methodology is unsupervised. To achieve that, the clustering algorithm ARIA is used, which automatically determines the number of clusters present in the data set. The efficiency of the developed method is clear in the application of the method on several types of images, such as mosaics of Brodatz, natural images, medical images and other applications. / Mestrado / Telecomunicações e Telemática / Mestre em Engenharia Elétrica
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Alocação de geração distribuída em sistemas de distribuição de energia elétrica via otimização bioinspirada na ecolocalização de morcegosCoelho, Francisco Carlos Rodrigues 16 August 2013 (has links)
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Previous issue date: 2013-08-16 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A alocação de geração distribuída em sistemas de distribuição de energia elétrica
consiste em definir a localização ótima para instalação de centrais geradoras distribuídas no
sistema e a quantidade de potência que deverá ser injetada por estas centrais, de modo a
minimizar as perdas técnicas inerentes aos sistemas de distribuição. Este é um problema de
otimização de difícil solução e que apresenta implicações ambientais e econômicas.
A técnica de otimização empregada nesta pesquisa para determinar a alocação dos
geradores distribuídos é recente, sendo a mesma bioinspirada. Ela se baseia na ecolocalização
de morcegos e foi desenvolvida em 2010 pelo pesquisador Xin-She Yang. Esta técnica de
otimização agrega em sua constituição conhecimento prévio adquirido por outras técnicas de
otimização, como enxame de partículas e busca harmônica, utilizando assim, as vantagens
inerentes a cada uma destas ferramentas. Esta característica confere à otimização via
ecolocalização uma expectativa de sucesso em problemas de difícil solução, com
características combinatórias, que é o caso do problema em estudo.
Com o intuito de melhorar o desempenho da técnica de otimização em questão, foi
proposta uma etapa adicional em sua constituição. Esta alteração no algoritmo original se
mostrou eficiente nas simulações realizadas, pois o mecanismo de busca modificado alcançou
resultados de melhor qualidade com maior frequência, tanto em sua validação, onde foram
utilizadas funções matemáticas não convexas, como na aplicação do método ao problema
referente à alocação de geração distribuída em sistemas de distribuição de energia elétrica.
Utilizando-se três sistemas teste, de trinta e três, de cinquenta e de sessenta e nove
barras, foram realizados testes com alocação exclusiva de potência ativa e reativa, e também
alocação simultânea destes dois tipos de potência, sendo que os resultados obtidos foram
comparados com resultados presentes na literatura especializada. Além das perdas, fatores
como perfil de tensão resultante nas barras e trajetória de convergência do algoritmo inspirado
na ecolocalização de morcegos foram analisados para a avaliação da metodologia de
otimização empregada nesta pesquisa. / The optimal distributed generation placement in electrical power systems is a complex
problem involving environmental and economical issues. The solution to this problem
consists of choosing the optimum location of distributed power plants, and to define the
amount of power that must be injected by these plants in order to minimize technical losses in
electrical distribution systems.
The optimization technique utilized in this work to determine the placement of
distributed generators is recent. It was developed in 2010 by Xin-She Yang. The optimization
procedure is inspired by the echolocation of bats phenomenon, and uses some previous
knowledge from others techniques, like Particle Swarm Optimization and Harmony Search,
combining their advantages. This feature gives the Bat-Inspired Algorithm an expectation of
success on difficult problems, such as the combinatorial problem under study.
In order to improve the performance of the optimization technique an additional step
was proposed in its search engine. Endowed with this change, the algorithm has achieved
better results more frequently. Nonconvex benchmark mathematical functions were used, as
well as in its application on distributed generation placement.
Using three different bus systems (33, 50 and 69 busses), simulations were performed
placing real and reactive Power separately, and those two kind of Power together. The
produced results were compared to specialized literature. Real power losses, bus voltage and
convergence trajectory indicates the level of success reached by the optimization technique
utilized in this research work.
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Algoritmos bio-inspirados para minimização do makespan do problema de escalonamento de produção / Bio-inspired algorithms for minimizing the makespan of the production scheduling problemCarvalho, Marcia Braga de 19 August 2018 (has links)
Orientadores: Akebo Yamakami, Tatiane Regina Bonfim / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação / Made available in DSpace on 2018-08-19T06:06:35Z (GMT). No. of bitstreams: 1
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Previous issue date: 2011 / Resumo: Este trabalho propõe novas abordagens híbridas baseadas em técnicas da computação bio-inspirada para o problema de escalonamento do tipo Job Shop. Como o problema do tipo job shop pertence a classe NP-difícil e não existe algoritmo exato capaz de solucionar todos os tipos deste problema. Normalmente é necessária a elaboração de métodos de resolução mais sofisticados para contornar essa alta complexidade. Desta forma, nesta tese propomos abordagens híbridas baseadas em algoritmo memético e algoritmo de otimização por colônia de formigas a fim de contornar essa complexidade e ser capaz de explorar eficientemente o espaço de busca obtendo resultados de alta qualidade. Os algoritmos híbridos propostos são aplicados tanto no problema de job shop com tempo de processamento preciso, como nos problemas de job shop com tempo de processamento incerto. No caso de problema com tempo de processamento incerto, os algoritmos visam encontrar um conjunto diversificado de escalonamentos com alto grau de possibilidade de serem ótimos / Abstract: This work proposes new hybrid approaches based on techniques of bio-inspired computing for the Job Shop scheduling problem. As the job shop scheduling problem is NP-hard and there is no exact algorithm capable of solving all kinds of this problem. Usually it is necessary to elaborate more sophisticated methods of resolution to overcome this high complexity. Thus, in this work we propose hybrid approaches based on memetic algorithm and ant colony optimization algorithm in order to explore the search space in an efficient manner and obtain high quality results. The proposed hybrid algorithms are applied in both the job shop scheduling problem with precise processing time, as in job shop scheduling problems with uncertain processing time. In the case of problem with uncertain processing time, the algorithms obtain a diversified set of schedules with high possibility of being optimal / Doutorado / Automação / Doutor em Engenharia Elétrica
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Conception des catalyseurs hétérogènes bio-inspirés à base de métaux divalents greffés dans des silices mésoporeuses pour l'activation de CO2 / Design of heterogeneous bio-inspired catalysts using divalent metals anchored into mesoporous silica for CO2 activationDoghri, Hanène Kaouther 29 June 2017 (has links)
Des complexes bio-inspirés de zinc(II) ont été ancrés à la surface des nanopores d’une silice mésoporeuse de type MCM-41 adopté la technique du pochoir moléculaire à motifs périodiques pour assurer l’isolation des sites en utilisant des ions TMA+ comme espaceur pour contrôler le greffage des fonctions triméthylsilyle. L’objectif étant de mimer le doigt de zinc de l’anhydrase carbonique, une enzyme qui catalyse la réaction réversible d’hydratation du dioxyde de carbone en bicarbonate. Des complexes aminés de métaux de transition ont été aussi ancrés par analogie au site métallique de l’anhydrase carbonique avec un contrôle du voisinage moléculaire comparable à celui des matériaux contenant les complexes à base de zinc. L’interaction du CO2 adsorbé avec les sites actifs de ces matériaux a été aussi étudiée. Les matériaux intermédiaires sont caractérisés à chaque étape par un panel de techniques, dont DRX, analyses élémentaires, adsorption-désorption d’N2, FT-IR, 29Si RMN, XPS et RPE qui confirment l’intégrité de la structure poreuse et la formation des complexes. / Bio-inspired diethylenetriamine zinc(II) complexes were anchored into the nanopores of hexagonal mesoporous MCM41-like silicas. A step-by-step approach called “Molecular Stencil Patterning” was adopted to perform an in situ synthesis in order to mimic the zinc finger of the carbonic anhydrase. In the presence of a surface-masking pattern of TMA+ ions, some silanol groups were capped using grafted trimethylsilyl functions. Transition metal complexes have also been anchored in analogy to the metallic site of carbonic anhydrase with a molecular vicinity control comparable to that of materials containing zinc complexes. The interaction of adsorbed CO2 with the active sites of these materials has also been studied. The materials were characterized with a panel of techniques including XRD, elemental analysis, N2-adsorption-desorption, FT-IR, 29Si NMR, XPS and EPR that confirm the integrity of the porous structure and the complexes formation.
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Division of labour in groups of robotsLabella, Thomas Halva 09 February 2007 (has links)
In this thesis, we examine algorithms for the division of labour in a group of robot. The algorithms make no use of direct communication. Instead, they are based only on the interactions among the robots and between the group and the environment.<p><p>Division of labour is the mechanism that decides how many robots shall be used to perform a task. The efficiency of the group of robots depends in fact on the number of robots involved in a task. If too few robots are used to achieve a task, they might not be successful or might perform poorly. If too many robots are used, it might be a waste of resources. The number of robots to use might be decided a priori by the system designer. More interestingly, the group of robots might autonomously select how many and which robots to use. In this thesis, we study algorithms of the latter type.<p><p>The robotic literature offers already some solutions, but most of them use a form of direct communication between agents. Direct, or explicit, communication between the robots is usually considered a necessary condition for co-ordination. Recent studies have questioned this assumption. The claim is based on observations of animal colonies, e.g. ants and termites. They can effectively co-operate without directly communicating, but using indirect forms of communication like stigmergy. Because they do not rely on communication, such colonies show robust behaviours at group level, a condition that one wishes also for groups of robots. Algorithms for robot co-ordination without direct communication have been proposed in the last few years. They are interesting not only because they are a stimulating intellectual challenge, but also because they address a situation that might likely occur when using robots for real-world out-door applications. Unfortunately, they are still poorly studied.<p><p>This thesis helps the understanding and the development of such algorithms. We start from a specific case to learn its characteristics. Then we improve our understandings through comparisons with other solutions, and finally we port everything into another domain.<p><p>We first study an algorithm for division of labour that was inspired by ants' foraging. We test the algorithm in an application similar to ants' foraging: prey retrieval. We prove that the model used for ants' foraging can be effective also in real conditions. Our analysis allows us to understand the underlying mechanisms of the division of labour and to define some way of measuring it.<p><p>Using this knowledge, we continue by comparing the ant-inspired algorithm with similar solutions that can be found in the literature and by assessing their differences. In performing these comparisons, we take care of using a formal methodology that allows us to spare resources. Namely, we use concepts of experiment design to reduce the number of experiments with real robots, without losing significance in the results.<p><p>Finally, we apply and port what we previously learnt into another application: Sensor/Actor Networks (SANETs). We develop an architecture for division of labour that is based on the same mechanisms as the ants' foraging model. Although the individuals in the SANET can communicate, the communication channel might be overloaded. Therefore, the agents of a SANET shall be able to co-ordinate without accessing the communication channel. / Doctorat en sciences appliquées / info:eu-repo/semantics/nonPublished
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Perfectionnement des algorithmes de contrôle-commande des robots manipulateur électriques en interaction physique avec leur environnement par une approche bio-inspirée / Improvement of control algorithms of electrical robot arms in physical interaction with their environment with bio-inspired approachMelnyk, Artem 18 December 2014 (has links)
Les robots intégrés aux chaînes de production sont généralement isolés des ouvriers et ne prévoient pas d'interaction physique avec les humains. Dans le futur, le robot humanoïde deviendra un partenaire pour vivre ou travailler avec les êtres humains. Cette coexistence prévoit l'interaction physique et sociale entre le robot et l'être humain. En robotique humanoïde les futurs progrès dépendront donc des connaissances dans les mécanismes cognitifs présents dans les interactions interpersonnelles afin que les robots interagissent avec les humains physiquement et socialement. Un bon exemple d'interaction interpersonnelle est l'acte de la poignée de la main qui possède un rôle social très important. La particularité de cette interaction est aussi qu'elle est basée sur un couplage physique et social qui induit une synchronisation des mouvements et des efforts. L'intérêt d'étudier la poignée de main pour les robots consiste donc à élargir leurs propriétés comportementales pour qu'ils interagissent avec les humains de manière plus habituelle.Cette thèse présente dans un premier chapitre un état de l'art sur les travaux dans les domaines des sciences humaines, de la médecine et de la robotique humanoïde qui sont liés au phénomène de la poignée de main. Le second chapitre, est consacré à la nature physique du phénomène de poignée de main chez l'être humain par des mesures quantitatives des mouvements. Pour cela un système de mesures a été construit à l'Université Nationale Technique de Donetsk (Ukraine). Il est composé d'un gant instrumenté par un réseau de capteurs portés qui permet l'enregistrement des vitesses et accélérations du poignet et les forces aux points de contact des paumes, lors de l'interaction. Des campagnes de mesures ont permis de montrer la présence d'un phénomène de synchronie mutuelle précédé d'une phase de contact physique qui initie cette synchronie. En tenant compte de cette nature rythmique, un contrôleur à base de neurones rythmiques de Rowat-Selverston, intégrant un mécanisme d'apprentissage de la fréquence d'interaction, est proposé et etudié dans le troisième chapitre pour commander un bras robotique. Le chapitre quatre est consacré aux expériences d'interaction physique homme/robot. Des expériences avec un bras robotique Katana montrent qu'il est possible d'apprendre à synchroniser la rythmicité du robot avec celle imposée par une per-sonne lors d'une poignée de main grâce à ce modèle de contrôleur bio-inspiré. Une conclusion générale dresse le bilan des travaux menés et propose des perspectives. / Automated production lines integrate robots which are isolated from workers, so there is no physical interaction between a human and robot. In the near future, a humanoid robot will become a part of the human environment as a companion to help or work with humans. The aspects of coexistence always presuppose physical and social interaction between a robot and a human. In humanoid robotics, further progress depends on knowledge of cognitive mechanisms of interpersonal interaction as robots physically and socially interact with humans. An illustrative example of interpersonal interaction is an act of a handshake that plays a substantial social role. The particularity of this form of interpersonal interaction is that it is based on physical and social couplings which lead to synchronization of motion and efforts. Studying a handshake for robots is interesting as it can expand their behavioral properties for interaction with a human being in more natural way. The first chapter of this thesis presents the state of the art in the fields of social sciences, medicine and humanoid robotics that study the phenomenon of a handshake. The second chapter is dedicated to the physical nature of the phenomenon between humans via quantitative measurements. A new wearable system to measure a handshake was built in Donetsk National Technical University (Ukraine). It consists of a set of several sensors attached to the glove for recording angular velocities and gravitational acceleration of the hand and forces in certain points of hand contact during interaction. The measurement campaigns have shown that there is a phenomenon of mutual synchrony that is preceded by the phase of physical contact which initiates this synchrony. Considering the rhythmic nature of this phenomenon, the controller based on the models of rhythmic neuron of Rowat-Selverston, with learning the frequency during interaction was proposed and studied in the third chapter. Chapter four deals with the experiences of physical human-robot interaction. The experimentations with robot arm Katana show that it is possible for a robot to learn to synchronize its rhythm with rhythms imposed by a human during handshake with the proposed model of a bio-inspired controller. A general conclusion and perspectives summarize and finish this work.
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Etude de la relation structure-activité de complexes bio-inspirés de la réductase de l'oxyde nitreux / Structure-activity relationships in copper complexes bio-inspired from nitrous oxide reductaseEsmieu, Charlène 13 November 2014 (has links)
Etude de la relation structure-activité de complexes bio-inspirés de la réductase de l'oxyde nitreux N2O est un puissant gaz à effet de serre et est impliqué dans la destruction de la couche d'ozone, ce qui rend sa dégradation très intéressante. Il s'agit d'un intermédiaire du cycle catalytique de la nitrification bactérienne. En effet, en biologie une métalloenzyme est capable de réduire N2O à deux électrons en N2 et H2O. Le site actif de la réductase de l'oxyde nitreux, le centre CuZ, renferme l'unique association de quatre ions cuivre pontés par un ion sulfure. Afin d'obtenir des complexes capables d'activer N2O et d'approfondir la compréhension du mécanisme catalytique de l'enzyme nous avons élaboré des modèles inspirés du centre CuZ. Il s'agit de complexes dinucléaires de cuivres possédant le motif {Cu2(µ-S)} supposé indispensable à l'activation de N2O. Les complexes à valence mixtes décrits dans ces travaux ont été complétements caractérisés et leur activité vis-à-vis de la réduction de N2O a été évaluée. Ces complexes constituent le premier modèle de ce type capable de réduire N2O. Des études spectroscopiques, électrochimiques et théoriques nous ont également permises de proposer un mécanisme réactionnel, passant par la formation d'un adduit complexe-N2O. Nous avons également pu mettre en évidence le rôle crucial de la molécule d'eau, ligand exogène des complexes, dans ce mécanisme. En parallèle, la stabilité en solution de différentes liaisons disulfures présentes au sein de ligands tétranucléants, en présence de CuII, a été évaluée. La réactivité de la liaison disulfure est dépendante de la fixation des ions cuivre à proximité des atomes de soufres. Trois ligands possédants des substituants aminés différents ont été testés, chacun présentant une réactivité particulière. Nous avons montré pour l'un de ces ligands que l'oxydation de la liaison disulfure pouvait être réalisée en absence d'oxydant fort, l'eau jouant le rôle de nucléophile. / Structure-activity relationships in copper complexes bio-inspired from nitrous oxide reductase N2O is a powerful greenhouse gas and is involved in the ozone layer destruction, which makes it degradation very interesting. N2O is an intermediate of the catalytic cycle of bacterial nitrification. Indeed, in biology a metalloenzyme can reduce N2O with two electrons to N2 and H2O. The active site of nitrous oxide reductase, the CuZ center, contains a unique combination of four copper ions bridged by a sulfide ion. In order to obtain complexes able to activate N2O and deepen the understanding of the catalytic mechanism of the enzyme we have developed models based on the CuZ center. Binuclear copper containing the {Cu2(μ-S)} pattern that is supposed essential to N2O activation have been synthetized. Mixed valent complexes described in this work were fully characterized and their activity toward N2O was evaluated. These complexes are the first model like this capable of N2O reduction. Spectroscopic, electrochemical and theoretical studies have also allowed us to propose a reaction mechanism, which passes through the formation of an adduct complex-N2O. We were also able to highlight the crucial role of the exogenous water molecule in this mechanism. In parallel, the solution stability of different disulfide bonds present in tetranucleating ligands in the presence of CuII was evaluated. The reactivity of the disulfide bond is dependent upon the binding of copper ions near sulfur atoms. Three ligands with different amino groups were tested, each having a specific reactivity. We have shown for one of them that the oxidation of the disulfide bond could be carried out in the absence of strong oxidizer, water acting as the nucleophil
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