In recent years, the ‘right to the city’ has emerged as a key concept and practice amongst both academics and social movements around which to organise a response to the crisis of Fordist production and political representation. In Spain this response has taken to the streets, with millions of people coming together and shouting ‘They don’t represent us!’. As a key site of both neoliberal urban governance and political insurgency, Barcelona provides a powerful site through which to examine the relationships between urban social movements, urban governance and struggles around the right to the city. In this thesis I build a (partial and provisional) genealogy of the right to the city, examining the relevance of those struggles that have emerged inside and against neoliberal governmentality since the early 1980s in an effort to assemble the right to the city through the material combination of struggles around urban production and citizenship rights. To do this, I return to the relation between genesis and management as an uneven dialectic in the production of rights; drawing on and building new connections between post-colonial studies, autonomous marxist debates, critical studies of citizenship and urban studies to investigate how strangers, outsiders and the governed challenge European capitalism from inside and assert a different imagination of contemporary urban life. I also explore my own role in these dynamics. In contrast to an understanding of academic knowledge as analytical and objective representation, my position as both a militant and a researcher provides the ground upon which I analyse social movements as a factory of concepts and practices capable of assembling an instituent politics against neoliberal governmentality.

This thesis analyses how and why the Westminster Assembly (1643-1653), the Long Parliament’s advisory committee for religious matters, attempted to suppress antinomianism, one of the fastest-growing radical religious movements of the early seventeenth century. The Assembly addressed antinomianism in its dual capacity as an arm of Parliament and, in its own self-understanding, as a body of theologians tasked with religious reformation. In the eyes of the Assembly, antinomianism presented a two-fold threat. Socially, antinomianism had the potential to bring anarchy and disorder: the Assembly responded to this threat by examining antinomian ministers, forming its own antinomian committee, and liaising with Parliament to determine whether antinomians should be branded as heretics with concomitant civil punishment. Theologically, for the Assembly, antinomianism encompassed more than simply the belief that obligation to the Ten Commandments had passed away; it contained a complex structure of soteriology that was fundamentally at odds with the Reformed tradition. Working in the overarching backdrop of the rise of English Arminianism, the divines debated soteriological questions raised by antinomianism, issues at the heart of the Reformation such as: the relationship between the Old and New Testaments, the continued effectiveness of the moral law, the nature of Christ’s propitiatory work of redemption, the role and timing of justifying faith, and the relationship between sanctification and justification. The Assembly’s 1643 debates over antinomian theology, conducted as it revised the Thirty-nine Articles, produced revised Articles, which formed the foundation for the Assembly’s 1646 Confession of Faith. The Assembly then used the Confession of Faith to present a concise but comprehensive refutation of antinomian theology. The study uncovers the significance of antinomianism for contextualising the Assembly’s debates, and thus advances and nuances current perception of both the Westminster Assembly and English antinomianism. Analysis of debates carried out on the floor of the Assembly provoked by antinomian theology reveals that, while the divines as a whole disagreed with antinomian tenets, they were far from united in their understanding of basic soteriological definitions and were also divided over the best way to thwart antinomianism. A detailed investigation of this state of affairs enhances interpretation of the Assembly’s documents, such as the Confession of Faith and Larger and Shorter Catechisms, which in and of themselves do not reveal the theological uncertainties and tensions present in the Assembly. The study also offers a new example of the Assembly functioning as a regulatory body. This thesis draws on a substantial new pool of primary material: The Minutes and Papers of the Westminster Assembly (edited by Chad van Dixhoorn, OUP 2012, 3200 pages), the first full critical edition of the Assembly’s debates; also, the first volume of Assembly member John Lightfoot’s journal, recently transcribed, which supplies the only record of crucial exchanges between the Assembly and antinomian theologians. A major contribution of this thesis, working with these new resources, is to demonstrate how the Assembly interacted far more with antinomianism than previous scholars have thought. The thesis breaks new ground by using both theological and historical methods to provide a fine-grained contextual account of the Assembly’s debates and actions against antinomianism.

In this work we have explored the possibility of using surfactant/polyelectrolyte complexes as templates to synthesize inorganic mesostructured materials mainly with a film morphology. Inorganic species deposit in those regions of the films which are filled with a polymer hydrogel, surrounding the arrays of ordered surfactant micelles. This method produced thick robust films where the inorganic regions are reinforced and functionalized by the polymer, thus these materials are expected to have potential applications in separation, absorption, catalysis and chemical sensing. Initial work involved mixing silicate precursors directly into CTAB/PEI solutions to form highly ordered 2D hexagonal silica films at the air/water interface. Time resolved synchrotron SAXS allowed investigation of processes occurring in solution during the reaction, from which a film growth mechanism was proposed. Films had good thermal properties and after post-synthesis TMOS vapour treatment, retained structure upon template removal. Silica gel monoliths with various mesostructures were also rapidly fabricated in one minute with surfactant/LPEI complexes. Cat-ionic surfactant mixtures with polymers were also employed to template silica films with different cubic mesostructures at the air/water interface. The mesophases of the interfacial films were enriched due to more complicated interactions between the polymers and two surfactants. Polymer molecular weight, total composite concentration, chemical nature of the polymer as well as the cationic-anionic surfactant molar ratio was used to systematically control the silica film mesophase. Robust titania films were also prepared with cat-anionic surfactant mixtures and polymers at the air/water interface. Although the film mesostructure was lost after calcination, the in-situ and dry free-standing films display ordered cubic mesostructures and the films are stable to calcination after post-synthesis treatment. Ordered lamellar iron oxide films templated by SDS/LPEI complexes were also prepared at the air/water interface.

"The design and development of chemically modified surfaces for bioanalytical applications is presented. Chemical surface modification is demonstrated to be a method to control surface properties on the molecular level by selecting the appropriate substrate, linking chemistry, and terminal group functionality. These systems utilize spontaneous interactions between individual molecules that allow them to self-assemble into larger, supramolecular constructs with a predictable structure and a high degree of order. Applications investigated in this thesis include: surface patterning, switchable surface wettability, and biological sensor devices that combine surface based molecular recognition, electrochemical detection methods, and microfluidics. A multilayered approach to complex surface patterning is described that combines self-assembly, photolabile protecting groups, and multilayered films. A photolabile protecting group has been incorporated into molecular level films that when cleaved leaves a reactive surface site that can be further functionalized. Surface patterns are created by using a photomask and then further functionalizing the irradiated area through covalent coupling. Fluorophores were attached to the deprotected regions, providing visual evidence of surface patterning. This approach is universal to bind moieties containing free amine groups at defined regions across a surface, allowing for the development of films with complex chemical and physico-chemical properties. Systems with photoswitchable wettability were developed by fabricating multilayered films that include a photoisomerizable moiety, cis-/trans- dicarboxystilbene. When this functionality was incorporated into a multilayered film using non-covalent interactions, irradiation with light of the appropriate wavelength resulted in a conformational change that consequently changed the hydrophobicity of the substrate. Methods were investigated to increase the reversibility of the photoswitching process by creating surface space between the stilbene ligands. Utilizing mixed monolayers for spacing resulted in complete isomerization for one cycle, while the use of SAMs with photolabile groups produced surfaces that underwent isomerization for three complete cycles. A microfluidic device platform for ion sensing applications has been developed. The platform contains components to deliver small volumes of analyte to a surface based microelectrode array and measure changes in analyte concentration electrochemically in an analogous method to that used in conventional electrochemical cells. Crown ether derivatives that bind alkali metal ions have been synthesized and tested as ionophores for a multi-analyte device of this type, and the sensing platform was demonstrated to measure physiological relevant concentrations of potassium ions. Advantages of this design include: high sensitivity (uM to mM), small sample volumes (less than 0.1 mL), multi-analyte capabilities (multiple working electrodes), continuous monitoring (a flow through system), and the ability to be calibrated (the system is reusable). The self-assembled systems described here are platform technologies that can be combined and used in molecular level devices. Current and future work includes: photopatterning of gold and glass substrates for directed cell adhesion and growth, the design and synthesis of selective ion sensors for biological samples, multi-analyte detection in microfluidic devices, and incorporating optical as well as electrochemical transduction methods into sensor devices to allow for greater sensitivity and self-calibration."

With 500,000 coronary artery bypass procedures performed each year in the United States, and only one-third of patients possessing suitable autologous grafts, there is a clinical need for tissue engineered blood vessels (TEBVs). The overall goal of this project was to develop a one- step approach to rapidly produce entirely cell- derived tubular tissue constructs without scaffold materials. To achieve this goal, we developed "centritubing"-- a system based on applying centrifugal force to suspended cells to create a tube-shaped cellular aggregate. Briefly, rat aortic smooth muscle cells were injected into cylindrical polycarbonate spinning chambers and then spun to apply centrifugal force, which pelletted the cells on the inner wall of the chamber. After three days in culture with growth medium, the cells remodeled to form tissue tubes. In previous work we have shown, in principle, that centritubing produces tubular constructs, however tissue tube production was not consistently achieved. The first objective of this study was to develop modifications to the centritubing device that would lead to consistent lumen diameter, rapid cellular aggregation into a tube construct, and an improved success rate of tube formation. The second objective was to investigate cellular parameters that contribute to tubular tissue construct formation using centritubing. Prior to changes in manufacturing of the centritubing device and culture system, the success rate of centritubing was inconsistent. After these changes, the success rate of tubular construct formation improved to 85% (11/13). Noteworthy modifications to the centritubing device included the addition of a central mandrel as a substrate for tissue contraction, development of a smoother seeding surface, and manufacture of a reusable culture chamber. The results of this study support the proof of concept for centritubing as a device for rapid production of tubular tissue constructs and provide insight for future progress using the centritubing methodology.

One-dimensional nanostructures have offered unique advantages in many fields. Protein based nanotubes, in particular, are desirable for biomedical applications due to their ease of functionlization and intrinsic biocompatibility. Template-assisted methods are widely used to fabricate cylindrical nanostructures like carbon nanotubes, metal nanowires, polymer nanorods, etc. In the fabrication of protein nanostructures, the layer by layer (LbL) technique has long been applied to deposit protein multilayers on planar and spherical substrates. The success in each area led to the conclusion that the combination of these two techniques will potentially bring us the capability of fabricating protein nanotubes in a more controllable fashion. In this work, protein nanotubes have been successfully deposited inside nanoscopic pores by sequential filtration of bovine serum albumin (BSA) solution at pH 3.8 and pH 7.0 through the channels in the anodic aluminum oxide (AAO) template. The morphologies of the obtained nanostructures have been examined using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Also, a simple analysis from UV/Vis spectroscopy has shown that the solutions used in our experiment will not significantly damage the bioactivity of BSA. Our future work will focus on strengthening the mechanical stability of the protein nanotubes and controlling their morphology more precisely.

Orientador: Edison Barbieri / Resumo: As praias arenosas e os estuários são ambientes importantes para as aves por serem utilizados como locais de repouso e alimentação, porém ainda há poucas informações sobre a interação das aves com estes ecossistemas. As informações sobre abundância, distribuição e biologia das populações animais são importantes para a preservação dos ambientes estuarinos e das espécies ali presentes. Portanto, este trabalho estudou a assembleia e a dinâmica de populações das aves no Baixio do Arrozal, localizado na Baía de Trapandé, seguindo o pressuposto de que as variações de abundância, dominância e diversidade apresentariam diferenças em relação aos meses e estações do ano. Os dados utilizados foram coletados em censos quinzenais durante o período de abril de 2013 a dezembro de 2016, pelo método do ponto fixo. A partir das amostras obtidas, foram calculadas a frequência de ocorrência, constância abundância, dominância e diversidade. Para o estudo da assembleia foi feito análise de similaridade e teste de correlação com as estações e com os anos de coleta de dados, juntamente com gráfico de barras com erro padrão da abundância total em função da mensalidade e gráfico boxplot deste mesmo índice em função das estações do ano, quanto ao estudo das populações, as variações das abundâncias de cada espécie registrada foram avaliadas através de gráfico boxplot e gráfico de barras com erro padrão em função das estações e da mensalidade. Através da análise de similaridade foram identificados três g... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The sandy beaches and estuaries are important environments to the birds, because they use these places as resting and foraging areas, but there is not a lot of information about the interaction of birds with these ecosystems. Information about abundance, distribution and biology of animal populations are important for preservation of the estuaries and species. Thus, this work studied the assembly and the dynamic population of birds at the Baixio do Arrozal, in Trapandé Bay, supposing the variations of abundance, dominance and diversity would exhibit differences regarding the months and seasons. The data were collected in fortnightly censuses between April 2013 and December 2016, by the point count method. From the collected samples, we calculated the abundance, constance, dominance and diversity index. For the assembly study were made the similarity analysis and correlation test of dominance, abundance and diversity with seasonality and monthly, together with bar chart with standard error to total abundance in function of monthly and a boxplot chart of abundance in function of seasons. For the population study the variations of abundance were evaluated by boxplot chart and bar chart with standard error in function of months and seasons for each registered specie. The similarity analysis resulted in three different groups, which were determined according to abundance and constance, the group I constituted by Thalasseus acuflavidus, Nannopterum brasilianus e Rynchops niger, the... (Complete abstract click electronic access below) / Mestre

Thesis. 1979. Sc.D.--Massachusetts Institute of Technology. Dept. of Mechanical Engineering. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Includes bibliographical references. / by Sergio N. Simunović S. / Sc.D.

Ce travail de thèse propose une nouvelle approche pour la préparation de membranes à matrice mixte basée sur l’utilisation de copolymères à blocs et de nanoparticules inorganiques disposant de propriétés magnétiques. Des aggrégats de copolymères ont été préparés avec une morphologie variée (sphères, cylindres et vésicules) à partir du copolymère poly(acide méthacrylique)-b-poly(méthacrylate de méthyle). Ce dernier a été synthétisé par polymérisation radicalaire contrôlée par transfert de chaîne réversible par addition-fragmentation (RAFT) dans l’éthanol à 70°C. Des particules d’oxyde de fer ont, quant à elles, été préparées en présence de différents stabilisants à température variée pour permettre d’atteindre la charge de surface et les propriétés magnétiques recherchées. La structure des copolymères à bloc a permis d’obtenir à la fois des membranes hydrophobes via le procédé de séparation de phase induite par un non-solvant, ainsi que des membranes hydrophiles lorsque que la technique de spin-coating était appliquée aux aggrégats formés par auto-assemblage induit lors de la polymérisation. Grâce à l’étude détaillée des propriétés de filtration des membranes obtenues, la relation structure-propriété a été discutée sous l’action d’un champ magnétique externe. Enfin, la sensibilité au colmatage a été vérifiée via la filtration de solutions de protéines. Il a ainsi été démontré une diminution notable du colmatage sous champ magnétique, ouvrant de belles perspectives pour ces nouvelles membranes. / This thesis presents a new approach to produce mix matrix membranes using block copolymers and inorganic nanoparticles having magnetic properties. The polymeric nanoparticle with different morphologies (linear, Spheres, worms, and vesicles), from poly (methacrylic acid)-b-(methyl methacrylate) diblock copolymer, were synthesized using Reversible addition−fragmentation chain transfer polymerization (RAFT) in ethanol at 70 ֠C. The inorganic counterpart, iron oxide nanoparticles were prepared using different stabilizers at various temperatures to acquire the necessary surface charge and magnetic properties. The chemistry of the particles leads to form both hydrophobic membranes using non-solvent induced phase separation as well as a hydrophilic membrane by using the simple spin coating technique with the particles from polymerization induced self-assembly. By a detailed experimental study of the membrane filtration, the influence of different parameters on the process performance has been investigated with and without magnetic field. Finally, membrane fouling has been studied using protein solution. Also, the membrane performance was examined under magnetic field revealing the successful reduction in the fouling phenomenon making them new performant membranes in the area of membrane technology.

Les diaryléthènes et leurs dérivés terrylènes sont prometteurs pour la prochaine génération de dispositifs optoélectroniques en raison de leurs excellentes propriétés photochimiques. Pour les rendre viables pour les appareils électroniques miniaturisés, il est nécessaire d'étudier cette classe de molécules au niveau unimoléculaire avec le microscope à tunnel sous vide ultra-élevé (UHV STM). Cette thèse comporte trois parties: 1) développement de terarylènes hautement sensibles à la commutation; (2) leur modification pour les études STM; et 3) les résultats de ces études STM. Pour être étudié à l'échelle de la molécule unique par STM, des terarylènes ayant une sensibilité de commutation élevée ont été sélectionnés. Ces composés présentent des rendements quantiques élevés allant jusqu'à 100%. Cependant, la réaction de cycloréversion reste faible, de sorte qu'une voie alternative, grâce à un mécanisme oxydatif à réaction en chaîne, a été recherchée. Dans une première partie, nous montrons que l'efficacité et la vitesse de cette réaction peuvent être contrôlées par la fixation de groupes aromatiques sur les carbones réactifs. Dans la deuxième partie, nous avons fonctionnalisé ces molécules afin de les étudier par STM en introduisant des groupes tert-butyle et chlorure. Tout en préservant leurs excellentes propriétés photochimiques, les groupes tert-butyle présentent un excellent contraste lumineux dans les images STM, ils minimisent aussi l'agrégation de ces molécules sur la surface et découplent légèrement les molécules de la surface. Les atomes de chlore permettent de contrôler les assemblages moléculaires sur des substrats isolants de type bicouche de NaCl cristalline précédemment déposés sur un substrat métallique. Dans la troisième partie, les résultats de STM sont présentés. Nous avons développé une nouvelle approche ascendante pour la formation reproductible de nano-assemblages du terarylène non modifié à 77 K. Quant au terarylène modifié par les groupes tert-butyle, il présente à 5 K sur une surface d'Ag (111) différentes formes qui, grâce à la position des groupes tert­butyles à contraste élevé et à l'aide de calculs DFT, ont pu être assignées comme étant différentes conformations de surface de la molécule. Sur NaCl / Ag (111), il a été possible de visualiser les états occupés et inoccupés de la molécule. Cela illustre que, pour ces applications, des molécules avec des propriétés appropriées peuvent être des candidates intéressantes pour des études STM afin d'obtenir des informations sur leurs propriétés à l'échelle de la molécule unique. De telles molécules peuvent être optimisées pour tenir compte de la surface, car sa simple présence peut induire un comportement bien différent de celui obtenu en solution. Cette thèse ouvre les terarylènes à des applications futures nécessitant une surface solide. / Photoswitching diarylethenes, and their terarylene derivatives, are promising for the next generation optoelectronic devices because of their excellent photochemical properties. To make them viable for miniaturized electronic devices, it is necessary to study this class of molecules at the single molecular level by scanning tunneling microscopy under ultra-high vacuum (UHV STM). This thesis has three parts: 1) development of terarylenes highly sensitive to switching; (2) their modification for STM studies; and 3) results of STM investigations. To be studied at the single molecular level by STM, terarylenes with high switching sensitivity have been selected. These compounds display high quantum yields of up to 100 %. However, the cycloreversion reaction remains low so an alternative route, through a chain-reaction oxidative mechanism, has been sought. In the first part, we show that the efficiency and speed of this reaction may be controlled by attachment of aromatic groups on the reactive carbons. In the second part, we functionalized these molecules for STM studies by attaching tert-butyl and chloride groups. These substituents preserve their excellent photochemical and switching properties while tert-butyl groups show bright contrast in STM images, minimize aggregation of these molecules on the surface, and slightly decouple the molecule from the surface. The chlorine group has been introduced to direct their surface assembly on insulating substrates composed of crystalline NaCl bilayer previously grown over a metallic substrate. In the third part, results of STM are presented. We developed a new bottom-up approach for forming reproducible nanoassemblies of the unmodified terarylene at 77 K. Meanwhile, at 5 K, the terarylene functionalized with tert-butyl groups present different forms on the Ag(111) surface. From the positioning of the high-contrast tert-butyl groups and with the aid of DFT calculations, we assign different conformations of the molecule on the surface. On NaCl/Ag(111), direct visualization of the occupied and unoccupied states could be achieved. This illustrates that for these applications, molecules with appropriate properties can be interesting candidates for STM studies to obtain information at the single molecular level. Such molecules may be redesigned with a consideration of the surface as its mere presence may induce behavior previously unobserved or neglected if they were studied in solution. This thesis opens terarylenes to future applications which require a solid surface.