Synthesis and characterisation of the bis-MPA based branched materials was performed. Thymine derivative was incorporated into the polymer structure as a core moiety and an active centre for H-bonding. The formation of assemblies was investigated. / Im Rammen der Doktorarbeit wurden bis-MPA basierter dendrititsche und hochverzweigte Polymeren synthetisiert. Sie haben Thymin Derivat als Kernmolecule. Die H-Brücken zwischen Polymeren und DAPy Derivate wurden untersucht.

The diploma thesis "The position of England in the context of the regional organization of Great Britain"deals with the issue of establishing a regional level of governance in the eight regions of England in the period between 1997 and 2004. This policy was promoted by the New Labour government as an answer to demands for democratisation and responsibility of governance in the regions as well as an answer to demands for improvements in economic performance of the regions. The aim of the thesis is to respond to the question of why the public in the regions does not support plans for strengthening of the regional level of governance and for establishing elected regional assemblies in the regions and why this policy was rejected in the referendum held in 2004 in the region North East. The research was carried out using the theory of new regionalism and the concept of construction of regions. Specific criteria are set and are used as a basis for analysis of the situation in the English regions in the selected time period. The first criterion is the territorial framework of the English regions, the second criterion is the institutional framework and the last criterion is the regional identity. It clearly emerges from the analysis that the English regions are not institutionalised as distinctive units...

L’étude de l’interaction entre des protéines et leurs ligands est essentielle pour la compréhension de leur rôle physiologique ainsi que de leur rôle dans la mise en place de pathologies. En particulier, dans le cas de maladies neurodégénératives, comme les maladies d’Alzheimer ou de Creutzfeld-Jacob, ou d’autres pathologies liées au mépliement de protéines, la compréhension des interactions entre protéines, qui peuvent modifier de façon considérable le paysage conformationnel des partenaires, est une des clés pour décrypter les étapes moléculaires élémentaires induisant une cascade d’événements qui mènent à la formation d’assemblages protéiques de grande taille. Dans le cadre de cette thèse, nous avons étudié la dynamique de taille de trois types d’assemblages protéines/ peptides.Interactions faibles impliquées dans la structuration d’assemblages de PrPSc et dans l’équilibre entre les formes PrPSc et suPrP : Dans un premier temps, l’étude des étapes précoces de la réplication du prion nous a permis de mettre en évidence une voie de diversification structurale qui implique une voie de templating secondaire. En utilisant une méthode de solubilisation en conditions natives et une approche reposant sur une série de souches différentes, nous avons démontré que, pour toutes les souches testées, les assemblages de prion ont la propriété de se dépolymériser en deux ensembles discrets d’assemblages oligomériques, dont la taille varie entre des dimères et tétramères. Des approches d’amplification de prion in vitro et in vivo ont démontré que ces assemblages oligomériques comportent toute l’information nécessaire à la réplication ainsi que les déterminants structuraux de la souche. Le motif de glycosylation, la cartographie par épitopes ainsi que l’empreinte PK ont mis en évidence des différences structurales entre les espèces oligomériques, soulignant la coexistence d’ensembles d’assemblages structuralement distincts au sein d’une souche donnée. Des expériences de dépliement partiel ont montré la présence d’une dynamique constitutionnelle entre les assemblages reposant sur un échange de matière et un réarrangement structurel à l’échelle de l’unité élémentaire (suPrP) ainsi qu’une diversité structurale au sein des assemblages de prion.Partenaires et oxydation de la PrPc: Bien que des travaux préalables aient mis en évidence l’existence d’interactions entre PrP et Aβ, Aβ1-40 ne forme que des complexes très instables avec la PrP monomérique. La spectrométrie de masse n’a pas permis de mettre en évidence cette interaction, même après optimisation des paramètres en conditions natives ou via des mesures indirectes reposant sur des échanges hydrogène - deutérium d’amide. L’oxydation radioloytique de la PrPC a été étudiée par SEC couplée à la mobilité ionique et la spectrométrie de masse, montrant la formation d’assemblages de haut poids moléculaires associée à des changements de structure.Fortes interactions peptide/peptide : Le système Synapt G2Si (Waters), qui combine de la mobilité ionique avec de la spectrométrie de masse, a été utilisé pour l’analyse d’une série de peptides issus de la capside externe du birnavirus de l’IBDV. Ces peptides peuvent former des complexes avec des énergies de liaison intermoléculaires proches de l’énergie de la liaison peptidique. En plus de la mise en évidence des changements structuraux au sein de ces complexes liés à l’introduction de mutations dans la séquence peptidique, des déviations par rapport aux attentes expérimentales ont été observées au cours de ce travail lors de mesures en conditions de mobilité ionique. Ces écarts ont pu être reliés à la conception de la cellule Tri-Wave de l’instrument, qui conduit à un mélange des différents gaz tampon qui ne peut être évité. De ce fait, les biais introduits par ce mélange influencent les paramètres de modélisation et la comparaison entre instruments pour tous les utilisateurs de ce modèle d’instrument. / Interactions between proteins and their ligands play a crucial in the understanding of their physiological function as well as their role in disease mechanisms. Especially in all forms of neurodegenerative diseases like Alzheimer, Creutzfeld-Jacob disease and others pathologies due to protein misfolding, the understanding of protein interaction, which can cause a dramatic change in the conformational landscape of the binding partners, is key in the deciphering of elementary molecular steps leading to cascade of events finally resulting in the formation of large protein assemblies. In the scope of this thesis we studied the size dynamic of three types of protein/peptides assemblies.Weak interactions involved in the structuration of PrPSc assemblies and in the detailed balanced between PrPSc and suPrP: The earliest steps in prion protein conversion were studied using both in vitro bona fide prion amplification method. We showed that the early step of the replication leads to a deterministic diversification process involving a secondary templating pathway. Furthermore, by using a native solubilization method and through a multi-strain approach. We demonstrated a generic property of prion assemblies to depolymerize into two discreet sets of oligomeric assemblies with a size ranging between dimers and tetramers for all tested strains. Both in vitro and in vivo prion amplification approaches showed that the oligomeric assemblies harbour all the replicative information as well as the strain structural determinant. Glycopattern, epitope-mapping and PK fingerprint revealed structural differences between the oligomeric species highlighting the coexistence of structurally distinct set of assemblies within a given strain. Partial unfolding experiments demonstrated the existence of a constitutional dynamic between the assemblies based on material exchange and structural rearrangement at the level of the elementary subunits (suPrP).PrPc partners and oxidative modifications: Although previous work had shown the existence of interactions between PrP and Aβ, monomeric Aβ1-40 forms only very weak complexes with monomeric PrP and mass spectrometry, even after optimization of the native instrument settings or by indirect measurements based on amide hydrogen deuterium exchange was not able to detect this interaction. Oxidation of PrPc was also suggested as a pathway towards pathology: the appearance and structural changes induced by gamma-radiolysis of water on PrPc were studied by mass spectrometry and ion mobility.Strong peptide/peptide interactions: The Waters Synapt G2Si instrumental set-up which couples ion mobility with mass spectrometry was used for the analysis of a collection of peptides derived from the shell of the IBDV binavirus. These peptides can form complexes with binding energies close or similar to the binding energy of the peptide bond. In addition to a better description of the changes in structure of these complexes varying with the mutations introduced in peptide sequence, we observed deviation from expected instrument characteristics when performing ion mobility measurements. Due to the design of the Tri-wave module in the Waters Synapt G2Si mass spectrometer, a mixture of the different buffer gases intrinsically cannot be avoided. Consequently, these biased measurements influence the outcome of modelling approaches and the inter-instrument comparison for all users of this instrument type.

Un système de solides peut être classé suivant trois états de mobilité: l’état non assemblé, l’état assemblé rigide et l’état assemblé mobile. L’étude se focalise sur les systèmes de solides sur-contraints en boucle fermée. Lors de l’étape de conception ou reconception, les dimensions d’un système de solides sur-contraints sont amenées à être modifiées, ce qui peut avoir pour conséquence la perte de son état de mobilité.L’approche présentée dans cette thèse a pour but de proposer une assistance au concepteur lors du redimensionnement, lui permettant de modifier ou conserver l’état de mobilité d’un système de solides. Le redimensionnement de systèmes de solides sur-contraints nécessite la connaissance de relations dépendant de leurs dimensions: les équations d’assemblage et les conditions de mobilité. Ces relations sont obtenues à l’aide d’un outil de résolution algébrique: les bases de Gröbner. La résolution algébrique est parfois coûteuse, voire impossible en un temps raisonnable, c’est ce qui justifie les méthodes décrites dans cette thèse.La solution proposée est composée de deux étapes principales. Tout d’abord, les représentations algébriques d’un système de solides fermé et mobile sont décrites. Les équations de fermeture d’un système de solides composé de plusieurs boucles sont obtenues en utilisant un paramétrage en coordonnées relatives. Les équations de mobilité sont elles générées à partir des équations de fermeture, à l’aide de méthodes directes ou incrémentales. Ensuite, afin de faciliter la génération des équations d’assemblage et de mobilité, une analyse algébrique reposant sur des outils d’analyse numérique est définie. L’état de mobilité du système de solides à redimensionner est déterminé à partir d’un ensemble de valeurs des paramètres le décrivant. Si le concepteur souhaite modifier l’état de mobilité du système de solides, de nouvelles valeurs sont alors générées. Lorsque l’état de mobilité souhaité est obtenu, il est possible de varier les dimensions tout en conservant cet état. Pour cela, certaines dimensions sont spécialisées afin de faciliter la génération des équations d’assemblage et des conditions de mobilité. Si les paramètres choisis sont liés ou trop nombreux, l’analyse mène inéluctablement à une absence de solutions. Des stratégies de partitionnement pour pallier ces problèmes sont aussi proposées. Enfin, les outils développés dans le logiciel Maple® afin d’illustrer les différents concepts proposés sont présentés, et un outil interactif permettant au concepteur de naviguer sur les équations de fermeture, équations d’assemblage et les conditions de mobilité obtenues après spécialisation, est proposé. / An assembly can be partitioned into three mobility states: the impossible state, the rigid state and the mobile state. The study focuses in over-constrained closed-loop assemblies. During the process of design or re-design, the dimensions of the assembly can vary and this can lead to the loss of its mobility state.The method presented in this thesis aims at helping the designer to resize an assembly. There exist relationships between the dimension of the assembly that ensure the closure and the mobility of over-constrained. These relationships called assembly equations and mobility conditions are hence necessary to resize an over-constrained solid assembly. Assembly equations and mobility conditions are computed by a computer algebra tool: Gröbner bases. However, the algebraic solving using Gröbner bases can be costly and may fail because of unreasonable computing time, this is the main reason of the strategies described in this thesis.The approach proposed in this thesis is composed of two main steps. First of all, an algebraic representation of a closed assembly and a mobile assembly is descibed. The closed-loop equations are written by using a coordinate free method and the mobility equations are generated from the closed-loop equations using direct and incremental methods. To simplify the computation of assembly equations and mobility conditions an algebraic analysis that rely on numerical analysis tools is proposed. Starting from a set of values of the parameters that describe the assembly to resize, the mobility state of the assembly is determined. Then, if the designer want to change the mobility state, a new set of values that have the mobility state chosen by the designer is generated. Once the initial set of values has the right mobility state, some dimensions are specialized to ease the computation of assembly equations and mobility conditions. However, if the parameters chosen are linked or its number is to high, there is a high chance that the study lead to no solution. Strategies to avoid these problems are also proposed. Finally, the tools developped in Maple® software that illustrate the methods proposed are described and an interactive tool that permits the designer to visualize the solutions of the closed-loop equations, assembly equations and mobility conditions computed after specialisation is proposed.

Le dimensionnement des liaisons boulonnées représente une part non négligeable du travail des bureaux d’études des industries aéronautiques. En effet leur nombre peut varier de plusieurs milliers à plusieurs millions selon le type d’avion. À l’heure actuelle la mise au point de ce type d’attache se fait grâce à des éléments finis en trois dimensions. La complexité des phénomènes mis en jeux par ce type de connexion tels que le contact le frottement et les jeux entraînent des calculs non linéaires très chronophages.L’objectif des travaux de thèse a été de proposer un connecteur élément fini remplaçant l’ensemble de la discrétisation 3D d’un boulon pour les calculs numériques de dimensionnement en étant basé sur des paramètres liés au comportement mécanique.La mise au point d’un algorithme prenant en compte le contact afin de modéliser le comportement global des parties assemblées fut le point de départ de la réflexion.Cet algorithme a été implémenté au sein du logiciel Samcef à travers une routine codée en Fortran 77.Des tests de qualifications du comportement normal et tangentiel ont été effectués afin de valider l’algorithme mis au point.Une méthode d’identification des paramètres du connecteur est ici proposée : certains peuvent être déterminés de manière analytique et d’autres de manière numérique.Enfin des cas tests de validation sur des assemblages industriels ont été effectués afin de mettre en évidence un gain en temps de calcul conséquent tout en maintenant une qualité suffisante pour le dimensionnement. / The design of bolted connections represents a significant part of the work of research department of aeronautical industries. Indeed, their number can vary from several thousands to several millions depending on the aircraft type. At the present time, the development of this type of attachment is done with finite elements in three dimensions. The complexity of concerned phenomena by this type of connection as the contact friction and gaps requires nonlinear computations which are very time consuming.The aim of the thesis was to propose a finite element connector for replacing the whole 3D discretisation of a bolt during the design computations while being based on parameters related to mechanical behaviour.The development of an algorithm taking into account contacts to model the overall behaviour of the parts was the starting point of the reflexion.Then this algorithm was implemented in the SAMCEF software through a routine coded in Fortran 77.Normal and tangential behaviour qualification tests were performed to validate the algorithm developed.A method for identifying connector parameters is proposed here, some of these parameters can be determined using an analytical approach, others need a numerical one.Finally, validations on industrial test cases were carried out to prove a substantial cpu time savings while maintaining a good level of quality.

No description available.

While variation analysis methods for compliant assemblies are not new, little has been done to include the effects of multi-step, fixtured assembly processes. This thesis introduces a new method to statistically analyze compliant part assembly processes using fixtures. This method, consistent with the FASTA method developed at BYU, yields both a mean and a variant solution. The method, called Piecewise-Linear Elastic Analysis, or PLEA, is developed for predicting the residual stress, deformation and springback variation in compliant assemblies. A comprehensive, step-by-step analysis map is provided. PLEA is validated on a simple, laboratory assembly and a more complex, production assembly. Significant modeling findings are reported as well as the comparison of the analytical to physical results.

[pt] Nas últimas décadas o Brasil tem apresentado características de uma modificação na estrutura da religiosidade, com as religiões tradicionais perdendo adeptos para religiões ascendentes. Atualmente, este movimento de transição se mostra mais evidente com a perda de fies do catolicismo e o ganho de fies pela Assembleia de Deus. O fenômeno, todavia, se destaca em âmbitos além do religioso, se espraiando por vias da política institucional, através do processo eleitoral. Esta atuação na via política é tida pela mídia e por parte da sociedade como um risco à democracia e à diversidade social. Portanto, através da análise da do processo eleitoral, da territorialidade da ação política, e das ações parlamentares esta pesquisa se propôs a identificar os fundamentos do temor. A análise consistiu em verificar a atuação de dois vereadores, na décima legislatura da cidade do Rio de Janeiro, ligados à duas fragmentações da Assembleia de Deus tradicional. São eles, Eliseu Kessler, ligado à Assembleia de Deus Ministério Madureira e Alexandre Isquierdo, ligado à Assembleia de Deus Vitória em Cristo. Para investigamos os fundamentos e potencialidades da questão foram analisados os locais de votação e confluências entre a espacialidade das igrejas afim de verificar se a eleição dos representantes foi ou não um investimento institucional; além de leis e projetos de leis de autoria dos parlamentares, afim de verificar possíveis perdas aos valores democráticos a partir destas gestões. / [en] In recent decades, Brazil has shown characteristics of a change in the structure of religiosity, with traditional religions losing adherents to ascendant religions. Currently, this transitional movement is more evident with the loss of faith in Catholicism and the gain of faith in the Assembly of God. The phenomenon, however, stands out in areas beyond the religious, spreading through institutional politics, through the electoral process. This action in the political way is seen by the media and by society as a risk to democracy and social diversity. Therefore, through the analysis of the electoral process, through the territoriality of political action, and parliamentary actions, this research aimed to identify the foundations of fear. The analysis consisted of verifying the performance of two councilors, in the 10th legislature of the city of Rio de Janeiro, linked to two fragmentations of the traditional Assembly of God. They are Eliseu Kessler, linked to the Assembly of God Ministry Madureira and Alexandre Isquierdo, linked to the Vitória em Cristo Assembly of God. To investigate the fundamentals and potential of the issue, the polling places and confluences between the spatiality of the churches were analyzed in order to verify whether the election of representatives was an institutional investment or not; in addition to laws and bills authored by parliamentarians, in order to verify possible losses to democratic values from these administrations.

Even though there is a strong public support for more ambitious policies to mitigate climate change, the politics do not yet follow. Climate assemblies (CA) have been suggested to improve climate change governance by bringing the citizens into the policymaking. However, in systems of representative democracy, the effect of CAs is largely decided by whether the politicians choose to follow the CA’s recommendations. Therefore, the politicians’ attitudes to CAs are of importance. This study is based on interviews with politicians in four Swedish municipalities who are about to conduct their first CA. The politicians’ attitudes to CAs are explored regarding how they view the democratic qualities of the CA and what their expectations are. The results show that CAs are mainly valued as a tool to create innovative policy proposals that are unlikely to stem out of the regular processes. Furthermore, the politicians see it as advantageous compared to regular citizen participation processes that the participants are well-informed and many social groups are represented. Regarding the role of the CA, the politicians frequently contrast the CA’s narrow focus on climate with their responsibility for the whole municipality. The argument is that the CA is not knowledgeable enough to make prioritisations concerning the whole municipality. Thus, the CA produces recommendations that the politicians will consider, but not necessarily follow. The study also highlights implications of the results for the design of CAs, for example in terms of recruitment and scope. There is no one size fits all approach, instead there are trade-offs that need to be acknowledged in the design to increase the chances of the CA to reach its set purpose.

Various technologies depend on interfacial events that are influenced by various molecular interactions at a solid-liquid interface. The functionality of a surface plays an important role in many applications such as catalysis, sensing, and bio-compatibility, which can benefit from distinctive chemical and physical surface properties. To create tailor-made functional surfaces, surface host-guest assemblies based on Langmuir-Blodgett and self-assembly technique have been employed as a model system as they may offer the potential ability to regenerate surface properties via intercalation of various functional guest molecules. This thesis ranges over the development and characterization of host-guest assemblies and their feasibilities for the regeneration of surface properties via intercalation of functional guests. In our work, 3-dimensional host structures with cavities are constructed on a targeted solid substrate using Langmuir-Blodgett and self-assembly techniques. In particular, by adopting the fundamental concept of host-guest interaction in supramolecular chemistry, we expect that structurally homologous guest molecules where functional groups are anchored can be intercalated into the cavities between hydrophobe arrays at the liquid-solid interface from solution under well-controlled conditions. This approach offers the potential of separating the functional of the monolayer from the inherent structure of the host. The first part of this thesis details two-dimensional host-guest assemblies consisting of guanidinium (G), octadecylsulfonate (S) and various functional alkane guests at the air-aqueous interface and following deposition onto solid substrates via the Langmuir-Blodgett technique. In particular, we evaluated the stability of the host-guest assemblies and the feasibility of exchanging molecular guests under exposure to various organic solvent environments. Analysis of X-ray reflectivity measurements of the thin films showed that good stability of the host-guest assembly could not be achieved due to weak interactions between the host monoalyer and the solid surface. In addition, no evidence of intercalation of guest molecules into guest-free host-cavities was observed. The second part of this thesis discusses the effective methodologies to prepare low-density self-assembled monolayers (LDSAMs) with cavities on silicon substrates. We employed a step-wise reaction based on hydrolytic or silane chemistry: integral spacer molecules such as anthracene-derivatives were anchored to the Si substrate and then long alkane chains were appended to the spacer molecules. The results showed that LDSAMs using an anthryl spacer are attached at the SAM/Si interface via a Si-O-C linkage, and the films do not exhibit a densely packed monolayer quality as would be expected for a non-sterically hindered alkyltrichlorosilane on Si. Thus, the resulting LDSAMs (with cavities) may be capable of accommodating other guest molecules with hydrocarbon chains through intercalation in order to form host-guest assemblies. The third part of this thesis demonstrates the ability of LDSAMs to produce functional surfaces via the intercalation of various functional guest molecules. Self-assembled monolayers of (10-octadecyl)-9-anthracenethiol (host-SAMs) on Au substrates were prepared. Quartz crystal microbalance with dissipation (QCM-D) measurements was used to demonstrate the capacity of LDSAMs to confine guest molecules in the cavities and to probe the structural changes of the host-guest assembly during guest intercalation from ethanol solution. X-ray photoelectron spectroscopy (XPS) measurements were then used to probe host-guest monolayers formed by immersing the host monolayer in solutions in a variety of other solvents. A combined study of QCM-D and XPS showed that guest molecules were intercalated into host-cavities. The reversibility of the intercalation process allows a guest already situated in a host-cavity to be replaced with second guest under well-regulated solvent conditions. / Ph. D.