Les systèmes multi-agents sont des systèmes dans lesquels des entités logiciellesappelées agents interagissent de façon autonome dans des environnements partagés. Ces dernièresannées, de nombreuses recherches sur les organisations multi-agents ont été menées etdivers modèles organisationnels ont été proposés. Cependant, ils n’offrent pas de solution pourune gestion effective de la problématique d’ouverture dans des organisations multi-agents normatives.Dans cette thèse, nous nous sommes intéressées à l’étude de cette problématique etdonc à la spécification des besoins relatifs à la mise en oeuvre de l’ouverture au sein d’organisationmulti-agent. Nous avons ainsi identifié trois propriétés caractéristiques de cette problématique: l’interopérabilité d’une organisation avec son environnement extérieur et interne, lagestion des entrées / sorties et la gestion du contrôle et de la régulation des agents. Pour répondreà ces propriétés, nous avons proposé un langage de modélisation d’organisation (OML)MOISE qui est une extension de Moise+. MOISE permet de spécifier de façon explicite lesprocessus d’entrée / sortie dans une organisation et notamment les exigences relatives auxmissions, buts, et rôles de l’organisation. Nous avons également proposé une infrastructure degestion d’organisation (OMI) ORA4MAS qui s’inspire du méta-modèle Agents et Artifacts(A&A). Nous avons défini le concept d’artefact organisationnel pour implémenter les fonctionnalitéscorrespondant aux spécifications du langage MOISE. Nos propositions ont été illustréesavec une spécification d’organisation de gestion de la construction d’un édifice. La miseen oeuvre des propriétés d’ouverture a été expérimentée avec la gestion des processus d’entrée/ sortie des agents, la négociation des clauses de contrat, la coordination des coopérations desagents à la réalisation des buts de construction d’un édifice, le contrôle des comportements desagents relativement aux normes de l’organisation ainsi que leur régulation. / Multi-Agent Technology concerns the development of decentralized and open systemscomposed of different agents interacting in a shared environment. In recent years, organizationhas become an important in this research field. Many models have been, and are still,proposed. While no concensual model emerges of these different works, it appears that theyall lack the ability to build open and normative organizations in the sense of management ofentry / exit of agents into organization but also decentralized control / regulation of the autonomyof the agents. In this thesis, our objective consists in the definition of a new modeladdressing these requirements. Ours reseaches allow us to extend theMOISE+ organizationalmodeling language (OML) in a new version namming MOISE. In this one we define an Entry/ Exit specification allowing to explicitly specify the ways in which the agents can enter orexit in or from an organisation by providing some requirements according to the missions, thegoals and the roles of the organisation. The organizational management infrastructure (OMI)ORA4MAS proposed take advantage of the Agents and Artifacts (A&A) approach. We definedthe Organizational Artifacts concept as the basic building block of our OMI for themanagement of organized and open MAS. To focus our study, the organizational artifacts willbe defined considering the OML specification of the MOISE model. We experimented ourproposal with the specification of an application aiming to manage the build of a house. Wethen experimented the management of the candidate agents to enter in the organisation and cooperatewith the other to build the house according to a specified social scheme, the specifiednorms and their contract clauses negociated when they will be admitted in the organisation.

Approche et outils pour la spécification du cahier des charges d'un automatisme complexe : structuration et hiérarchisation, outils de représentation des spécifications fonctionnelles, le grafcet, exemple d'application à la commande d'un procédé de distillation. Les erseaux de PETRI, et leur utilisation pour la description et l'analyse des systèmes à évolutions parallèles, grafcet et RDPI. mise en œuvre assistée par ordinateur, le systeme MAS.

Although the basic structure of biological membranes is provided by the lipid bilayer, most of the specific functions are carried out by membrane proteins (MPs) such as channels, ion-pumps and receptors. Additionally, it is known, that mutations in MPs are directly or indirectly involved in many diseases. Thus, structure determination of MPs is of major interest not only in structural biology but also in pharmacology, especially for drug development. Advances in structural biology of membrane proteins (MPs) have been strongly supported by the success of three leading techniques: X-ray crystallography, electron microscopy and solution NMR spectroscopy. However, X-ray crystallography and electron microscopy, require highly diffracting 3D or 2D crystals, respectively. Today, structure determination of non-crystalline solid protein preparations has been made possible through rapid progress of solid-state MAS NMR methodology for biological systems. Castellani et. al. solved and refined the first structure of a microcrystalline protein using only solid-state MAS NMR spectroscopy. These successful application open up perspectives to access systems that are difficult to crystallise or that form large heterogeneous complexes and insoluble aggregates, for example ligands bound to a MP-receptor, protein fibrils and heterogeneous proteins aggregates. Solid-state MAS NMR spectroscopy is in principle well suited to study MP at atomic resolution. In this thesis, different types of MP preparations were tested for their suitability to be studied by solid-state MAS NMR. Proteoliposomes, poorly diffracting 2D crystals and a PEG precipitate of the outer membrane protein G (OmpG) were prepared as a model system for large MPs. Results from this work, combined with data found in the literature, show that highly diffracting crystalline material is not a prerequirement for structural analysis of MPs by solid-state MAS NMR. Instead, it is possible to use non-diffracting 3D crystals, MP precipitates, poorly diffracting 2D crystals and proteoliposomes. For the latter two types of preparations, the MP is reconstituted into a lipid bilayer, which thus allows the structural investigation in a quasi-native environment. In addition, to prepare a MP sample for solid-state MAS NMR it is possible to use screening methods, that are well established for 3D and 2D crystallisation of MPs. Hopefully, these findings will open a fourth method for structural investigation of MP. The prerequisite for structural studies by NMR in general, and the most time consuming step, is always the assignment of resonances to specific nuclei within the protein. Since the last few years an ever-increasing number of assignments from solid-state MAS NMR of uniformly carbon and nitrogen labelled samples is being reported, mostly for small proteins of up to around 150 amino acids in length. However, the complexity of the spectra increases with increasing molecular weight of the protein. Thus the conventional assignment strategies developed for small proteins do not yield a sufficiently high degree of assignment for the large MP OmpG (281 amino acids). Therefore, a new assignment strategy to find starting points for large MPs was devised. The assignment procedure is based on a sample with [2,3-13C, 15N]-labelled Tyr and Phe and uniformly labelled alanine and glycine. This labelling pattern reduces the spectral overlap as well as the number of assignment possibilities. In order to extend the assignment, four other specifically labelled OmpG samples were used. The assignment procedure starts with the identification of the spin systems of each labelled amino acid using 2D 13C-13C and 3D NCACX correlation experiments. In a second step, 2D and 3D NCOCX type experiments are used for the sequential assignment of the observed resonances to specific nuclei in the OmpG amino acid sequence. Additionally, it was shown in this work, that biosynthetically site directed labelled samples, which are normally used to observe long-range correlations, were helpful to confirm the assignment. Another approach to find assignment starting points in large protein systems, is the use of spectroscopic filtering techniques. A filtering block that selects methyl resonances was used to find further assignment starting points for OmpG. Combining all these techniques, it was possible to assign nearly 50 % of the observed signals to the OmpG sequence. Using this information, a prediction of the secondary structure elements of OmpG was possible. Most of the calculated motifs were in good aggreement with the crystal structures of OmpG. The approaches presented here should be applicable to a wide variety of MPs and MP-complexes and should thus open a new avenue for the structural biology of MPs. / Biologische Membranen bestehen hauptsächlich aus Lipiden, ihre Funktion wird jedoch vor allem durch die eingebetteten Membranproteine (z.B. Kanäle, Ionenpumpen und Rezeptoren) bestimmt. Mutationen in dieser Proteinklasse können zum Auftreten verschiedener Krankheitsbilder führen, weshalb die Untersuchung der dreidimensionalen Struktur von Membranproteinen nicht nur von strukturbiologischem, sondern auch von pharmakologischem Interesse ist. In den letzten Jahren wurde eine Methode, die Festkörper NMR Spektroskopie, für Strukturuntersuchungen an Proteinproben im festen Aggregatzustand entwickelt. Diese Arbeit beschäftigt sich mit drei verschiedenen Präparationsarten von Membranproteinen, die eine Aufnahme von hochaufgelösten Festkörper NMR Spektren erlauben. Als Modelsystem wurde das Protein G der äußeren Membrane (outer membrane protein G, OmpG) von Escherichia coli gewählt. Eine wichtige Vorraussetzung zur Berechnung der Proteinstruktur aus den NMR-Spektren, ist die Zuordnung der einzelnen Signale zur jeweiligen Aminosäure in der Proteinsequenz. In dieser Arbeit wurde eine Methode entwickelt, die das Auffinden von Startpunkten für die sequentielle Zuordnung in großen Membranproteinen, wie zum Bsp. OmpG (281 Aminosäuren), erlaubt. Multidimensionale NMR Experimente mit verschieden spezifisch markierten Proben wurden durchgeführt und ermöglichten die Zuordnung von 50 % der NMR Signale der OmpG Proteinsequenz. Zur Überprüfung der gewonnenen Daten wurden diese zur Vorhersage von Sekundärstrukturelementen genutzt. Es konnte gezeigt werden, dass die berechneten Strukturmotive in guter Übereinstimmung zu den bisher veröffentlichten OmpG Strukturen liegen. Die in dieser Arbeit angewendeten Methoden sollten auf eine Vielzahl anderer Membranprotein anwendbar und somit einen neuen Weg zur Strukturbiologischen Untersuchung von Membranproteinen eröffnen.

Ce travail est relatif à la synthèse et la caractérisation structurale des oxydes Ce1-xCaxO2-x et des nouveaux oxyfluorures Ce1-xCaxO2-x-y/2Fy. Les oxydes Ce1-xCaxO2-x ayant déjà fait l'objet de nombreuses études dans le cadre de l'absorption des rayonnements UV, l'originalité de ce travail consiste à introduire des ions Ca2+ et F- au sein de la cérine CeO2 pour mener à des propriétés optiques intéressantes. La présence du fluor, du fait de son caractère fortement électronégatif, contribue en effet à réduire la polarisabilité électronique du réseau et donc à abaisser l'indice de réfraction dans le domaine du visible par rapport aux oxydes à base de calcium et de cérium. L'environnement local des ions fluorures a été identifié grâce à la RMN du fluor. L'influence de cations tétravalents (Zr4+, Sn4+) sur l'environnement local du cérium, sur le taux final de fluor et sur les propriétés physico-chimiques, est également présentée ainsi que la fluoration de l'oxyde de cérium IV.<br />Les propriétés d'absorption UV de ces composés sont évaluées et corrélées à la composition chimique et aux paramètres structuraux.

In der vorliegenden Arbeit wird die Synthese chromophorer Xerogele des Typs II auf Grundlage nucleophiler aromatischer Substitutionsreaktionen von Fluorarenen mit aminofunktionalisierten Trialkoxysilanen in Tetraethoxysilan als Lösungsmittel beschrieben. Die Herstellung von anorganisch-organischen Sol-Gel-Hybridmaterialien gelingt dabei in einer Eintopfreaktion. Neben kommerziell erhältlichen Fluoraromaten, wie z.B. 4-Fluornitrobenzen, wurden fluorfunktionalisierte Azomethine, Diazoverbindungen und Diphenylaminderivate eingesetzt. Die Synthese und Charakterisierung literaturunbekannter Fluoraromaten wird beschrieben. Besonderes Augenmerk lag auf der Reproduzierbarkeit der Xerogelsynthesen und der Charakterisierung der Xerogele durch Methoden der Festkörper-NMR- und UV/Vis-Spektroskopie sowie der Elektronenmikroskopie.

No description available.

Glass materials surround us, impacting our lives on a daily basis, whether geologically deposited by volcanic activity or synthesized in large volume by industry. These amorphous oxide materials are vastly important due to their variety of applications including solid electrolytes, cookware, and storage of high-level nuclear waste. Although they are used for different applications, one common characteristic of these materials is the absence of long-range periodic order. This makes it difficult to use traditional solid-state characterization methods such as x-ray and neutron diffraction to study glass structure. Nuclear magnetic resonance (NMR), is ideally suited to study materials that exhibit short-range non-periodic order as it probes directly at a nucleus of interest and is sensitive to its local structural environment. This ability of solid-state NMR is illustrated by revealing local structural features in various oxide materials presented in this thesis. Within is a compilation of studies looking at basic borates, followed by borovanadates and complex borosilicate glasses. A multinuclear application of using quantum chemical calculations, single and double resonance methods and charge-balance models are discussed to deconvolute the complex structures of these disordered materials. This is followed by a study of a difficult low-gamma nucleus, 73Ge, (once considered “impossible” for solid-state NMR) which is explored for future material studies by looking at 73Ge NMR of crystalline and glassy germanates. 73Ge chemical shifts were related to coordination environments and quadrupolar coupling constants were related to bond length distortions.

Glass materials surround us, impacting our lives on a daily basis, whether geologically deposited by volcanic activity or synthesized in large volume by industry. These amorphous oxide materials are vastly important due to their variety of applications including solid electrolytes, cookware, and storage of high-level nuclear waste. Although they are used for different applications, one common characteristic of these materials is the absence of long-range periodic order. This makes it difficult to use traditional solid-state characterization methods such as x-ray and neutron diffraction to study glass structure. Nuclear magnetic resonance (NMR), is ideally suited to study materials that exhibit short-range non-periodic order as it probes directly at a nucleus of interest and is sensitive to its local structural environment. This ability of solid-state NMR is illustrated by revealing local structural features in various oxide materials presented in this thesis. Within is a compilation of studies looking at basic borates, followed by borovanadates and complex borosilicate glasses. A multinuclear application of using quantum chemical calculations, single and double resonance methods and charge-balance models are discussed to deconvolute the complex structures of these disordered materials. This is followed by a study of a difficult low-gamma nucleus, 73Ge, (once considered “impossible” for solid-state NMR) which is explored for future material studies by looking at 73Ge NMR of crystalline and glassy germanates. 73Ge chemical shifts were related to coordination environments and quadrupolar coupling constants were related to bond length distortions.

This thesis is concerned with applications of modern solid-state NMR spectroscopy. Investigations of three quite different types are undertaken, each of which attempt to advance knowledge in the fields of chemistry and NMR. The goal of each project is to obtain insight into the effects of chemical environment, in particular bonding, on the NMR observables. Carbon-13 and nitrogen-15 solid-state nuclear magnetic resonance has been used to study solid samples containing the dicyanoaurate(I) anion, [Au(CN)2]-, with n-butylammonium, potassium, and thallium counterions. Differences in Au-Tl metallophilic bonding are shown to cause a difference in the isotropic cyanide carbon-13 chemical shift of up to 15.7 ppm, while differences in Au-Au aurophilic bonding are found to be responsible for a change of up to 5.9 ppm. Disordered polymeric gold(I) monocyanide was also investigated, and a range of 7+-2% to 25+-5% of the AuCN chains are found to be "slipped" instead of aligned with the neighbouring chains at the metal position. An investigation of the chemical shift tensors of the 13C-labelled carbons in solid samples of Ph13C≡13CPh and (η2-Ph13C≡13CPh)Pt(PPh3)2·(C6H6) has also been carried out. Coordination of diphenylacetylene to platinum causes a change in the 13C chemical shift tensor orientation and a net increase in the isotropic chemical shift. The carbon chemical shift tensors in the platinum complex bear a striking similarity to those of the alkenyl-carbons in trans-Ph(H)C=C(H)Ph, and a theoretical discussion of these observations is presented. Each of the fundamental NMR interaction tensors (σ, J, D and V) may be decomposed into isotropic, symmetric, and antisymmetric components. Observations of all theoretically allowed components other than the antisymmetric portion of J (Janti) have previously been published. Andrew and Farnell's theory (Mol. Phys. 15, 157 (1968)) for the effects of Janti on NMR spectra has been extended to powdered samples, and methods for analyzing the resultant line shapes have been determined. Finally, the first reported experimental attempts to measure Janti are presented, and experimental proof that no elements of Janti(119Sn,119Sn) in hexa(p-tolyl)ditin are larger than 2900 Hz is given.

Recent developments in embedded systems give robots access to the Internet and make them more flexible and capable of performing more complex applications. However, these robots are still limited in terms of size, CPU power, storage resources and memory. Consequently, these robots have only been manufactured for certain specific applications and cannot be re-used for other applications. This presents us with a challenge to design a software framework - Robot Colony. The Robot Colony enables robots to be suitable for a wide range of applications, not originally received from manufacturers, to achieve greater functionality, flexibility and utility. This research outlines the architecture and functionality of the Robot Colony to support the collaboration between devices in the P2P community and also analyse the JXTA platform, which was the framework originally proposed. Lastly we present a customized P2P architecture that specifically addresses the interaction betweensoftware components across the network. We further discuss the following technologies applied in theframework: * XML-based Directory Service Provider * HTTP-based publish/describe control commands * Remote Process Invoke To fully complete the project, a thorough evaluation of the framework based on either the JXTAplatform or the customized P2P channel has been conducted. This evaluation provides basic statistics data for the proposed framework design and implementation. Further more, we have presented a realtime Demo at the Smart Device lab of the Queensland University of Technology.