Ziel der vorliegenden Promotionsarbeit war die Entwicklung einer Methode zur Quantifizierung saurer Zentren auf Festkörperoberflächen mittels 15N-Festkörper-NMR-Spektroskopie von adsorbierten Pyridinmolekülen. Die 15N-Festkörper-NMR von adsorbiertem Pyridin ermöglicht die Unterscheidung verschiedener Arten von sauren Zentren, wie Lewis- und Brønsted-Zentren. Die Bestimmung der Art und der Konzentration auftretender saurer Zentren ist entscheidend, um die katalytische Aktivität fester Katalysatoren in einer Reaktion zu verstehen. Da 15N-NMR-Messungen zumeist zeitaufwendig sind, wurde in dieser Arbeit eine zeitoptimierte Messroutine entwickelt, die auf der Messung von 15N-Einzelpuls-Spektren mit kurzen Pulswiederholzeiten beruht. Um diese Spektren quantitativ auswerten zu können, müssen die detektierten NMR-Signale bezüglich ihrer T1-Relaxation korrigiert werden. Zudem treten in 15N-Einzelpuls-NMR-Spektren oft starke Störungen der Basislinie auf. Zur Unterdrückung dieser Störsignale wurde die EASY-Methode entwickelt, die auf der Messung von zwei schnell aufeinander folgenden Spektren basiert. Mittels dieser Methode können auftretende Störsignale in quantitativen 15N-NMR-Spektren unterdrückt werden. Die entwickelte zeitoptimierte Quantifizierungsmethode wurde an zwei Probenserien von festen Säuren getestet; zum einen an Aluminiumhydroxidfluoriden, als Vertreter von Verbindungen mit stark sauren Zentren, und zum anderen an hydroxylierten Magnesiumfluoriden, als Vertreter schwach saurer Verbindungen. Der Vergleich mit anderen quantitativen Methoden zeigte, dass die 15N-Festkörper-NMR-Spektroskopie von adsorbiertem Pyridin hervorragend für die Quantifizierung saurer Zentren geeignet ist und Einblicke in die katalytische Aktivität fester Katalysatoren ermöglicht. / The aim of the present dissertation was to develop a method for the quantification of acidic sites on solid surfaces by 15N solid-state NMR with pyridine as probe molecule. 15N NMR of adsorbed pyridine allows to distinguish different types of acidic sites like Lewis and Brønsted sites. The determination of the kind and concentrations of occurring acidic sites is crucial to understand the catalytic activity of a solid catalyst in a reaction.15N NMR measurements are often time-consuming. Hence, a time-optimized NMR quantification procedure was developed which uses 15N single pulse spectra with short pulse repetition delays. For quantitative analysis of these spectra, occurring signals were corrected according to their T1 relaxation. Furthermore, often strong baseline disturbances are observed in single pulse spectra. For the suppression of these disturbances, the EASY method was developed. The EASY method uses two successive scans to obtain quantitative NMR spectra, in which baseline disturbances are suppressed. The developed time-optimized method for the quantification of acidic sites was applied on two series of samples. One series of aluminum hydroxide fluorides as representatives of catalysts with strong acid sites and one series of hydroxylated magnesium fluorides as representatives of weak acidic catalysts. The comparison with other quantitative methods shows that 15N solid-state NMR of adsorbed pyridine is an excellent method for the quantification of acidic sites, because insights in the catalytic activity of a catalyst can be gained.

Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Three analytical methods were developed for the determination of chlorine, iodine and mercury in solid and liquid samples, directly by high resolution continuum source atomic and molecular absorption spectrometry in graphite furnace. The first method objected the determination of chlorine in solid and slurry samples of different natures and chlorine contents (CRM 81002b human hair, SRM 1568b rice flour, ERM EC681 polyethylene, CRM BCR 460 coal, SRM 2692c bituminous coal, SRM 1575 sheet Of pine, CRM 686-1 iron oxide, SRM 1549 powdered milk) through the molecular formation of CaCl. The results were compared with those already available for the SrCl molecule and were superior, especially in samples with a high calcium content. The limit of detection and quantification obtained for the two molecular absorption lines of CaCl were 2.6 and 8.7 ng (620.862 nm) and 14.2 and 61.6 ng (377.501 nm), respectively. The iodine determination was performed through the formation of the SrI molecule in two samples of medicines containing iodine. The accuracy of the method was proved by comparative analysis by inductively coupled plasma mass spectrometry. The results obtained were higher compared to the existing BaI molecule that does not provide direct determination in solids. The limit of detection and quantification obtained were 0.035 and 0.117 μg, respectively. Finally, an analytical method for the determination of mercury in blood samples (SERONORM® LEVEL III and II) and urine (SERONORM®, Clincheck Control level I and II batch 432 and level II batch 923) were developed, directly, using gold nanoparticles. The method was compared to the existing method that uses potassium permanganate as oxidizing agent. The limit of detection and quantification obtained were 0.057 and 0.190 ng, respectively. / Foram desenvolvidos três métodos analíticos para a determinação de cloro, iodo e mercúrio em amostras sólidas e líquidas, de forma direta por espectrometria de absorção atômica e molecular de alta resolução com fonte contínua em forno de grafite. O primeiro método objetivou a determinação de cloro em amostras sólidas e em suspensão de diferentes naturezas e teores de cloro (CRM 81002b cabelo humano, SRM 1568b farinha de arroz, ERM EC681 polietileno, CRM BCR 460 carvão, SRM 2692c carvão betuminoso, SRM 1575 folha de pinheiro, CRM 686-1 óxido de ferro, SEM 1549 leite em pó), através da formação molecular de CaCl. Os resultados foram comparados com os já existentes para a molécula de SrCl e mostraram-se superiores, especialmente em amostras com alto teor de cálcio. O limite de detecção e quantificação obtidos para as duas linhas de absorção molecular de CaCl foram de 2,6 e 8,7 ng (620,862 nm) e 14,2 e 61,6 ng (377,501 nm), respectivamente. Já a determinação de iodo realizou-se através da formação da molécula de SrI, em duas amostras de medicamentos contendo iodo. A exatidão do método foi comprovada através de analise comparativa por espectrometria de massas com plasma acoplado indutivamente. Os resultados obtidos se mostraram superiores em comparação com molécula já existente BaI que não proporciona a determinação direta em sólidos. O limite de detecção e quantificação obtidos foram de 0,035 e 0,117 μg, respectivamente. Por fim, foi desenvolvido um método analítico para a determinação de mercúrio em amostras de sangue (SERONORM® LEVEL III e II) e urina (SERONORM®, Clincheck Control nível I e II lote 432 e nível II lote 923) certificadas, de forma direta, utilizando nanopartículas de ouro. O método foi comparado ao método já existente que utiliza permanganato de potássio como agente oxidante. O limite de detecção e quantificação obtidos foram de 0,057 e 0,190 ng, respectivamente.

La combinaison du traitement sémantique des connaissances (Semantic Processing of Knowledge) et de la modélisation des étapes de raisonnement (Modeling Steps of Reasoning), utilisés dans le domaine clinique, offrent des possibilités intéressantes, nécessaires aussi, pour l’élaboration des ontologies médicales, utiles à l'exercice de cette profession. Dans ce cadre, l'interrogation de banques de données médicales multiples, comme MEDLINE, PubMed… constitue un outil précieux mais insuffisant car elle ne permet pas d'acquérir des connaissances facilement utilisables lors d’une démarche clinique. En effet, l'abondance de citations inappropriées constitue du bruit et requiert un tri fastidieux, incompatible avec une pratique efficace de la médecine.Dans un processus itératif, l'objectif est de construire, de façon aussi automatisée possible, des bases de connaissances médicales réutilisables, fondées sur des ontologies et, dans cette thèse, nous développons une série d'outils d'acquisition de connaissances qui combinent des opérateurs d'analyse linguistique et de modélisation de la clinique, fondés sur une typologie des connaissances mises en œuvre, et sur une implémentation des différents modes de raisonnement employés. La connaissance ne se résume pas à des informations issues de bases de données ; elle s’organise grâce à des opérateurs cognitifs de raisonnement qui permettent de la rendre opérationnelle dans le contexte intéressant le praticien.Un système multi-agents d’aide à la décision clinique (SMAAD) permettra la coopération et l'intégration des différents modules entrant dans l'élaboration d'une ontologie médicale et les sources de données sont les banques médicales, comme MEDLINE, et des citations extraites par PubMed ; les concepts et le vocabulaire proviennent de l'Unified Medical Language System (UMLS).Concernant le champ des bases de connaissances produites, la recherche concerne l'ensemble de la démarche clinique : le diagnostic, le pronostic, le traitement, le suivi thérapeutique de différentes pathologies, dans un domaine médical donné.Différentes approches et travaux sont recensés, dans l’état de question, et divers paradigmes sont explorés : 1) l'Evidence Base Medicine (une médecine fondée sur des indices). Un indice peut se définir comme un signe lié à son mode de mise en œuvre ; 2) Le raisonnement à partir de cas (RàPC) se fonde sur l'analogie de situations cliniques déjà rencontrées ; 3) Différentes approches sémantiques permettent d'implémenter les ontologies.Sur l’ensemble, nous avons travaillé les aspects logiques liés aux opérateurs cognitifs de raisonnement utilisés et nous avons organisé la coopération et l'intégration des connaissances exploitées durant les différentes étapes du processus clinique (diagnostic, pronostic, traitement, suivi thérapeutique). Cette intégration s’appuie sur un SMAAD : système multi-agent d'aide à la décision. / The combination of semantic processing of knowledge and modelling steps of reasoning employed in the clinical field offers exciting and necessary opportunities to develop ontologies relevant to the practice of medicine. In this context, multiple medical databases such as MEDLINE, PubMed are valuable tools but not sufficient because they cannot acquire the usable knowledge easily in a clinical approach. Indeed, abundance of inappropriate quotations constitutes the noise and requires a tedious sort incompatible with the practice of medicine.In an iterative process, the objective is to build an approach as automated as possible, the reusable medical knowledge bases is founded on an ontology of the concerned fields. In this thesis, the author will develop a series of tools for knowledge acquisition combining the linguistic analysis operators and clinical modelling based on the implemented knowledge typology and an implementation of different forms of employed reasoning. Knowledge is not limited to the information from data, but also and especially on the cognitive operators of reasoning for making them operational in the context relevant to the practitioner.A multi-agent system enables the integration and cooperation of the various modules used in the development of a medical ontology.The data sources are from medical databases such as MEDLINE, the citations retrieved by PubMed, and the concepts and vocabulary from the Unified Medical Language System (UMLS).Regarding the scope of produced knowledge bases, the research concerns the entire clinical process: diagnosis, prognosis, treatment, and therapeutic monitoring of various diseases in a given medical field.It is essential to identify the different approaches and the works already done.Different paradigms will be explored: 1) Evidence Based Medicine. An index can be defined as a sign related to its mode of implementation; 2) Case-based reasoning, which based on the analogy of clinical situations already encountered; 3) The different semantic approaches which are used to implement ontologies.On the whole, we worked on logical aspects related to cognitive operators of used reasoning, and we organized the cooperation and integration of exploited knowledge during the various stages of the clinical process (diagnosis, prognosis, treatment, therapeutic monitoring). This integration is based on a SMAAD: multi-agent system for decision support.

Ce travail s'inscrit dans le cadre d'une étude systématique des propriétés physico-chimiques de polyphosphates à l'argent permettant d'avancer sur de nouvelles voies pour les dispositifs tels que l'éclairage, les lasers accordables dans le visible, la radiophotoluminescence. L'objectif de ce travail vise la compréhension des mécanismes de luminescence de l'ion Ag+ dans les composés Na_1-xAg_xLn(PO₃)₄ (Ln = La et Y) dont la structure a été parfaitement déterminée. La luminescence des monocristaux provient des ions Ag⁺, dans des sites isolés et proches de lacunes positives (Ag²⁺) résultant de la photosensibilité aux UV pour les cristaux au lanthane. La luminescence des verres Na_1-xAg_xLa(PO₃)₄ (seuls vitrifiables) a été élucidée grâce à une étude après irradiation et à celle des verres Na_2-xAg_xZnP₂O₇. Elle est due aussi aux ions Ag⁺ dans des sites isolés.

Les cobaltites lamellaires d'alcalins font l'objet d'une intense compétition à l'échelle internationale en raison des applications potentielles et de leurs propriétés électroniques associées à des corrélations fortes. Ces matériaux, bien connus pour leurs propriétés électrochimiques lorsqu'ils sont intercalés avec le lithium, sont aussi des candidats prometteurs pour la conversion thermoélectrique.<br />Cette étude porte sur l'élaboration et la caractérisation physico chimique des composés AxCoO₂ (x ~ 0.5-0.6 et A = Li, Na et K). L'influence des degrés de liberté cristallochimiques (nature, site et distribution des alcalins) sur les propriétés électroniques (spin, charge et orbitale) est discutée.

<p><b>Background and aims:</b> Type 2 diabetes mellitus is connected with elevated glucose levels, which cause impaired glucose-stimulated insulin secretion (GSIS) and degeneration of β-cells. Mechanisms for such glucotoxic effects were explored in the present study.</p><p><b>Materials and methods:</b> INS-1E cells were cultured for 5 days in 5.5, 11, 20 or 27 mM glucose in the presence or absence of AMPK-agonist AICAR. GSIS was determined from INS-1E cells and islets obtained from type 2 diabetes and control donors. Human islets and INS-1E cells were functionally characterized (GSIS) and protein profiled (SELDI-TOF MS). Glucose-induced <i>de novo</i> synthesis of fatty acyls (HR-MAS NMR spectroscopy), fatty acid composition (GC-MS), triglyceride content and specific proteins (Western blotting) were determined in INS-1E cells.</p><p><b>Results:</b> Impaired GSIS was observed from INS-1E cells exposed to chronic hyperglycaemia and islets isolated from type 2 diabetics compared to INS-1E cells cultured at normal glucose levels and control islets, respectively. Several glucose-regulated proteins were found when type 2 diabetes and control islets or mitochondria from INS-1E cells cultured at different glucose concentrations were protein profiled. Glucose induced lipid <i>de novo</i> synthesis of both saturated and unsaturated fatty acids in specific proportions. Glucose-induced impairment of function and mass was reverted by inclusion of AICAR, which lowered levels of pro-apoptotic protein CHOP but left triglyceride content unaffected.</p><p><b>Conclusions:</b> Impaired GSIS and increased apoptosis observed in β-cells after prolonged exposure to elevated glucose concentrations involved accumulation of lipid species in specific proportions, AMPK-inactivation, ER-stress activation and complex, coordinated changes in expression patterns of mitochondrial and human islet proteins.</p>

<b>Background and aims:</b> Type 2 diabetes mellitus is connected with elevated glucose levels, which cause impaired glucose-stimulated insulin secretion (GSIS) and degeneration of β-cells. Mechanisms for such glucotoxic effects were explored in the present study. <b>Materials and methods:</b> INS-1E cells were cultured for 5 days in 5.5, 11, 20 or 27 mM glucose in the presence or absence of AMPK-agonist AICAR. GSIS was determined from INS-1E cells and islets obtained from type 2 diabetes and control donors. Human islets and INS-1E cells were functionally characterized (GSIS) and protein profiled (SELDI-TOF MS). Glucose-induced de novo synthesis of fatty acyls (HR-MAS NMR spectroscopy), fatty acid composition (GC-MS), triglyceride content and specific proteins (Western blotting) were determined in INS-1E cells. <b>Results:</b> Impaired GSIS was observed from INS-1E cells exposed to chronic hyperglycaemia and islets isolated from type 2 diabetics compared to INS-1E cells cultured at normal glucose levels and control islets, respectively. Several glucose-regulated proteins were found when type 2 diabetes and control islets or mitochondria from INS-1E cells cultured at different glucose concentrations were protein profiled. Glucose induced lipid de novo synthesis of both saturated and unsaturated fatty acids in specific proportions. Glucose-induced impairment of function and mass was reverted by inclusion of AICAR, which lowered levels of pro-apoptotic protein CHOP but left triglyceride content unaffected. <b>Conclusions:</b> Impaired GSIS and increased apoptosis observed in β-cells after prolonged exposure to elevated glucose concentrations involved accumulation of lipid species in specific proportions, AMPK-inactivation, ER-stress activation and complex, coordinated changes in expression patterns of mitochondrial and human islet proteins.

Due to the nature of globalization, new strategies have been designed to break into new markets. Joint Venture is a common strategy to enter new markets and by using a Joint Venture, companies share risks and establish new contacts with local knowledge. Brazil is a market where foreign investors gain more and more interest. Brazil's economy is growing fast and made well during the global financial crisis. The middle class in Brazil is constantly growing and for the first time, poverty is not a majority in Brazil.In an International Joint Venture (IJV), it is usually a foreign company establishing a partnership with a local company. Often, IJVs fail because companies have problems collaborating, depending on different variables. In this thesis, we chose to analyze the cultural barriers in a Brazilian-Swedish IJV on the Brazilian market. The purpose of this thesis is to gain an understanding and describe cultural barriers in an IJV partnership, and high-light those to increase the chances for successful IJVs between Brazilian and Swedish companies in the future.This thesis is qualitative, with an abductive approach, in order to gain a deeper and better understanding of experienced barriers. We have chosen to see culture from both a national and an organizational perspective as earlier research has showed that national culture affects the organizational culture within an IJV. Using Hofstede's (1991) four dimensions of national culture as a supplement to Wilson’s (2001) four factors influencing the organizational culture, we have conducted four interviews in two Swedish-Brazilian IJV companies located in São Paulo, Brazil. The companies we have chosen to interview have been small or medium-sized manufacturing. Interviews were conducted face-to-face in a comfortable environment for all respondents. In our analysis, we used matrices to make it easier to see what differences and/or similarities there are between the case-companies.Results of this study, demonstrate that the experiences from the two case-studies are well in line with each other. The organizational structure in Brazil has been perceived as more hierarchical than the Swedish vertical and more open structure. This in turn, has strengthened the differences in communication between managers and employees, which been perceived as more top-down in Brazil than in Sweden. Our conclusion is that cultural barriers have been perceived, in the perception of the leaders’ expected behavior, language barriers, differences in planning and management of uncertain situations, Brazil's more family-oriented society and close relationship between private life and work in the Brazilian market.Several of these barriers have been experienced during the early start-up of an IJV, something we believe increases the importance of being well prepared for cultural barriers that may arise. The importance of an agreement upon the structure and policies at the company at an early stage is crucial, to reduce future possible conflicts. Show mutual respect and understanding for one's partners’ culture and experienced cultural barriers, use these to avoid any negative effects, and instead create a positive impact for the IJV. / Minor Field Study

In recent years many people have built Personal Assistant Agents, Information Agents and the like, and have simply added them to the operating system as auxiliary applications, without regard to architecture. This thesis argues that an agent architecture, one designed as a sophisticated representation of an individual user, should be embedded deep in the device system software, with at least equal status to the GUI – the graphical user interface. A sophisticated model of the user is then built, drawing upon contemporary Analytical Psychology – the Psychology of Subselves. The Shadowboard Agent architecture is then built upon that user model, drawing both structural and computational implications from the underlying psychology. An XML DTD file named Shadowboard.dtd is declared as a practical manifestation of the semantics of Shadowboard. An implementation of the Shadowboard system is mapped out, via a planned conversion of two existing integrated systems: SlimWinX, an event-driven GUI system; and XSpaces, an object-oriented tuplespace system with Blackboard-like features. The decision making mechanism passes logic terms and contraints between the various sub-agent components (some of which take on the role of Constraint Solvers), giving this agent system some characteristics of a Generalised Constraint Solver. A Shadowboard agent (built using the system) consists of a central controlling autonomous agent named the Aware Ego Agent, and any number of sub-agents, which collectively form an integrated but singular whole agent modelled on the user called the Digital Self. One such whole-agent is defined in a file named DigitalSelf.xml – which conforms to the schema in Shadowboard.dtd - which offers a comprehensive and generic representation of a user’s stance in a 24x7 network, in particular - the Internet. Numerous types of Shadowboard sub-agents are declared.

Dans la recherche de performance de chaînes logistiques, la modélisation et la simulation de ces chaînes prenant en compte des aspects organisationnels s‘avèrent nécessaire. Dans cette perspective, nous proposons tout d‘abord un nouveau cadre méthodologique de modélisation et simulation orienté agents de chaînes logistiques, prenant en compte explicitement les aspects organisationnels, tant structurels que dynamiques, ainsi que des observables et indicateurs dans la modélisation de ces chaînes. Ce cadre méthodologique est structuré selon deux niveaux d'abstraction principale qui sont : un niveau conceptuel et un niveau opérationnel. Pour chacun de ces niveaux nous avons différents modèles qui sont proposés et décrit en détail. Ensuite, afin de simuler les modèles de simulation de ces chaines logistiques obtenus par ce cadre méthodologique, nous proposons une architecture logicielle multi-paradigmes spécifique. Cette architecture qui supporte l‘intégration de différentes plates-formes de simulation, est basée sur un médiateur, constituant un système multi-agents, et assurant l‘interaction entre les simulateurs. Les agents de ce médiateur sont chargés de collecter les informations permettant de produire les observables, maintenir la structure organisationnelle lorsque des entités organisationnelles (groupes) sont distribués sur différents simulateurs, l‘interopérabilité entre ces simulateurs, et enfin garantir la validité de la simulation d‘un point de vue temporel. Enfin, la mise en œuvre du cadre méthodologique et de l‘architecture logicielle proposés sont illustrées sur un cas industriel réaliste de chaîne logistique. La présentation des phases de conception est détaillée ainsi que la spécification et l‘implémentation du cas industriel au sein de l‘environnement de modélisation et de simulation proposé. / In the search for performance of supply chains, modeling and simulation of these chains, taking into account the organizational aspects are needed. In this perspective, firstly we propose a new methodology for modeling and simulation of supply chains oriented agents, taking into account explicitly the organizational aspects, both structural and dynamic as well as observable indicators in the modeling of these chains. This methodological framework is structured along two main levels of abstraction, conceptual and operational levels. For each level we have models that are proposed and described in details. Then, to simulate the simulation models of supply chains obtained by this methodological framework, we propose a multi-paradigm software architecture specific. This architecture supports the integration of different platforms simulation is based on a mediator, providing a multi-agent system, and ensuring the interaction between the simulators. The agents of this mediator is responsible for collecting required information to produce observables and maintaining the organizational structure while the organizational entities (groups) are distributed over different simulators and interoperability between these simulators, and finally ensuring the validity of the simulation for a temporal point of view. Finally, the implementation of the methodological framework and the proposed software architecture are shown in a realistic industrial case supply chain. The presentation of the design phase is detailed and the specification and implementation of industrial case in environmental modeling and simulation proposed.