La tesis formula un Modelo Interpretativo para el territorio rural del AMCO, en el contexto de la Región Cafetera, como aproximación para comprenderlo apostando por el estudio de las particularidades formales que en conjunto definen su identidad, con el fin de encontrar alternativas para proyectarlo desde los modelos de orden que en el mismo territorio subyacen. El Estado de la Cuestión se estructura en cuatro grupos: aproximación disciplinar, estructuras agrarias, ocupación rural en Colombia y la región e información local, permitiendo la contextualización conceptual y metodológica. Los análisis generales del AMCO (Capítulo 1) incluyen la génesis, la estructuración histórica y las variables socioeconómicas, biofísicas y de la construcción territorial. Ésta se inscribe en el periodo denominado Formación Espacial Agraria (1850-1950) donde desaparecen los vestigios de asentamientos indígenas prehispánicos y del periodo colonial, se roturan los suelos y se desarrollan los asentamientos compactos y dispersos de lógica rural. El periodo de Urbanización (posterior a 1950) evidencia la expansión de las ciudades y procesos de superposición al espacio rural de asentamientos suburbanos, instalaciones industriales y de equipamientos periféricos. El análisis morfológico y espacial en detalle de seis muestras del territorio del AMCO (Capítulo 2) evalúa los diferentes patrones de ocupación y los elementos que trascienden o se extienden en la escala más amplia, incluyendo: los elementos naturales y antrópicos, o de construcción territorial, las singularidades y una imagen modélica, para aproximarse de manera sintética y múltiple al Modelo Interpretativo. En el Capítulo 3, se interpretan y sintetizan las categorías de elementos y estructuras, teniendo en cuenta los valores formales reproducibles por repetición o continuidad y las situaciones o estructuras singulares, mediante cinco categorías formales: estructuras de soporte, mosaicos, núcleos compactos, agrupaciones lineales y objetos de la dispersión. El Modelo resultante demuestra el poder de réplica que tienen las imágenes halladas en las muestras en condiciones geográficas y espaciales similares, haciendo de su expresión formal lógicas reconocibles de construcción territorial, demostrando la matriz de ordenación principal que imponen las aristas y concavidades naturales. Los elementos singulares en cuanto a función, densidad y forma (núcleos compactos, agrupaciones suburbanas y corredores regionales) se explican por su localización en lugares geográficos particulares y la posición estratégica en la red de vías y caminos. El espacio rural más transformado se abre paso hacia el occidente, como contrapeso espacial al lugar de la ciudad compacta, con formas y crecimientos suburbanos dispersos. La síntesis de Usos y Costumbres (Capítulo 4) se centró en tres categorías de elementos de repetición que podrían ser reglamentadas a partir de las lógicas de construcción rural en el AMCO. Las REDES, definidas por los sistemas de acceso y la matriz vegetal, se sintetizan como conjuntos dispuestos de forma articulada para la estructuración formal y funcional del espacio rural; los RITMOS, determinados por el orden encontrado en la edificación agrupada o dispersa, en términos de frecuencia, disposición geográfica o funcional en relación con los cultivos; y los MOSAICOS, entendidos como conjuntos de divisiones o compartimentaciones que se relacionan con la propiedad, la disposición de los cultivos y su alternancia con las Redes. La investigación permitió trascender la validación de los elementos hallados en otra área geográfica de la Región Cafetera colombiana, sistematizando los elementos territoriales encontrados en el Modelo Interpretativo para delimitar unidades homogéneas del Paisaje Cultural Cafetero en el Departamento de Caldas, demostrando el valor de la tesis como aproximación válida para territorios con características geográficas y productivas de similar condición a la estudiada (Anexo I). / The thesis formulates an interpretative model for the AMCO rural area, in the Colombian coffee region, as an approach to understand the formal particularities which together define their identity, with a goal of finding alternative ways to plan it from the order models that in the same territory underlie it. The Current Status and Issues is structured in four groups: disciplinary approach, farm structures, rural occupation in Colombia and the region and local information, allowing conceptual and methodological contextualization. The AMCO general analysis (Chapter 1) includes the origin, the historic structure and the socioeconomic, biophysical and territorial construction. This one is written in the period known as Agrarian Space Training (1850-1950) where the vestiges of pre-Hispanic indigenous settlements and the colonial period disappear, the soil is tilled and buildings and streets are developed. The Urbanization period (after 1950) shows the expansion of cities and space overlapping processes into rural like suburban settlements, industrial and peripheral equipments. The morphological and spatial analysis detail of six samples of the AMCO territory (Chapter 2) evaluates different occupancy patterns and elements that transcend or spread on a wider scale, including: natural and anthropic elements, or territorial construction, singularities and an exemplary image, in order to approach in a synthetically and multiple way and to the Interpretative Model. In Chapter 3, categories of elements and structures are interpreted and summarized, keeping in mind formal reproducible values by repeated or continuity and situations or unique structures, throughout five formal categories: support structures, mosaics, compact cores, linear arrays and dispersion objects. The resulting model shows the replica power that the images found in the samples and similar spatial geographic conditions, making logical formal expression recognizable territorial construction, showing the primary matrix of sort imposed by the edges and natural cavities. The unique elements in function, density and shape (compact cores, suburban corridors and regional groupings) are explained by its particular geographic locations and strategic position in the network of roads and paths. The more transformed rural area opens its way westward, as a counter space to the compact city location, shaped and scattered in a suburban growth. The synthesis of Manners and Customs (Chapter 4) focused on three categories of repeating elements that could be regulated from the logic of rural construction in the AMCO. The NETWORKS, defined by access systems and the vegetable matrix, are synthesized as articulated assemblies arranged for formal and functional structure of rural; the RHYTHMS, determined by the order found in the building clustered or dispersed, in terms of frequency, geographical or functional arrangement in relation with crops; and the MOSAICS, understood as division or partitioning sets that relate to the property, disposition of crops and their alternation with the Networks. The investigation allowed the validation of the elements found in a different area of the Colombian Coffee Region, systematizing the territorial elements found in the Interpretive Model to define homogeneous units of the Coffee Cultural Landscape in the Department (State) of Caldas, demonstrating the value of the argument as valid approach for areas with geographical and productive of a similar condition to the study (Appendix I).

A set of intentioned readings over Cordoba's ancient landscape, reveal the occupation logics developed over centuries of territorial construction. These logics result from the combination of cultural ways of domination and exploitation of the space, the technical resources available and the natural landscape conditions imposed. Models of order emerge from such processes, constituting the synthesis of human work accumulated in time and expressing ways of space organization and a specific way of rurality. The keys for future planning reside in these models. The study area is North of Traslasierra, Córdoba, Argentina, a large territory of more than eleven thousand square kilometers, with an estimate of one hundred small villages and settlements, and a population that is just over thirty thousand people. lt's an area of ancient colonial settlements and important economic weight between the seventeenth and nineleenth centuries when it entered a gradual socioeconomic decline. As a result, today it is a regional space in crisis with a significant delay in terms of territorial policies. Its "traserrana" position and the natural settlement of its valleys and mountains have also been an impediment for its development and have helped to set up a territorial invisibility box. The general hypothesis of this research is the presumption that the North ofTraslasierra is an undervaluated region -in terms of its cultural attributes - and unknown as representative of the local history. The area counts with numerous highly explanatory evidences of the regional identity and of Cordoba's native culture, offering some keys for the comprehension of the rural highland territories . Other secondary hypotheses hover around the presumption that both the scale of the Latin-American territory and the omnipresence of nature, "minimize" the traces of human work, discussing the notion of "will to project". However, it emerges the suspicion that in non-agrarian rurality (on the European way) it is also possible to discover spatial models of order appropriate to the scale and the vastness , in a way of organization that can be named "rural constellations". Therefore, the study of the production activities on the area (mules, goods, blankets and minerals) and their spatial expression, could allow the comprehension of the conformation of a way of rurality and also offer clues to rethink the future of the region. lt is also maintained that the scale of the area, the vast distances and the low density of material traces, demand the construction of a regional story to study and visualize this postponed highland space. It is intended to create new readings over this landscape of Córdoba in order to define a body of knowledge about it. In that process, the aim is to value its cultural and landscape resources, as a way to recover the regional history and to construct a narrative of the territory. Finally, new inputs of territorial order with a focus set to the material reality of the local spaces are expected to be generated in order to guide the definition of future projects and intentions at the region. The methodology is divided into two procedures: first, selective and intentioned readings of the territorial processes, applying scales which express the actions of spatial definition and using drawing as the main instrument of reading and recording, in order to get a closer proximity to a tangible reality, secondly, a description and interpretation in the sense that to understand is to interpret, and to interpret is to evidence.

The thesis describes infrared spectra recorded during the adsorption of water, acetone, acetic acid and hexifluaroacetone onto oxidized and reduced rutile, and the development of a technique for recording the infrared spectrum of a solid immersed in a liquid. Bands observed on the hydroxylated rutile surface have been assigned to hydroxyl groups on the (110) plane and water IrDlecules adsorbed onto strong and weak Lewis sites on all exposed planes. The hydroxyl groups exist as isolated or hydrogen bonded groups on surface titanium ions or as hydrogen ions on bridging oxygen ions. Reduction of the rutile surface considerably decreased the amount of rmlecular water adsorbed on the hydroxylated surface. The adsorption of acetone onto the hydroxylated surface took place in three consecutive stages, the first involved acetone molecules Lewis bonding to weak sites, the second resulted in the formation of mesityl oxide on strong surface sites and occurred with stage one in the absence of surface water molecules. In the third stage acetate molecules were formed as a result of the decomposition of mesityl oxide. Adsorption of acetic acid onto rutile resulted in the formation of water and arpeaxeme of bands due to acetate groups and Lewis-bonded co lexes on the weak sites. Hexafluoroacetone reacted with surface hydroxyls to produce a salt of the gem-diol hexifluoropropane-2,2-dio1, which decomposed on the removal of water to form trifluoroacetate species. An infrared cell has been developed enabling solid discs to be treated and inmiersed in a solution under inert conditions. The cell, of path length 0.7cm, has been used to study the adsorption of ether, from a solution in carbon tetrachloride, onto silica. Designs of variable path length cells for use Hexafluoroacetone reacted with surface hydroxyls to produce a salt of the gem-diol hexifluoropropane-2,2-dio1, which decomposed on the removal of water to form trifluoroacetate species. An infrared cell has been developed enabling solid discs to be treated and inmiersed in a solution under inert conditions. The cell, of path length 0.7cm, has been used to study the adsorption of ether, from a solution in carbon tetrachloride, onto silica. Designs of variable path length cells for use unier vacuum are included.

Space is the expression of society, and contemporary society is built around flows; hence the existence of a characteristic spatial form. However, most people still live in places and perceive their space by virtue of them. The coexistence of these two conflicting spatial logics results in a structural schizophrenia that threatens to break the channels of communication in society. The challenge of building bridges between the two entails dealing with processes that involve, in addition to material practices, other dimensions of social space. That is why both that multidimensionality and the procedures that enable the reconstruction of places in the context that it determines have assumed great relevance. With regard to the multidimensionality, the thesis acknowledges the fact that history -which underpins local identities- can be integrated into the physical environment to facilitate its experience simultaneously to that of other strictly spatial facets of what may be called 'interpreted places', where material heritage can play a significant role. With regard to the procedures, it highlights the importance of community processes in the reconstruction both of inclusive narratives and the places that they represent and in which they are represented. However, it is also argued that in the current context, which involves the disintegration of civil society, these processes may not be implemented in the absence of citizen mobilizations that demand the revision of institutional approaches that tend to generate 'altered places'. In Barcelona the gestation of this state of things had a decisive moment in 1986, when the city was nominated as an Olympic venue. That event can be understood as the beginning of a stage in which a quantum leap in the cultural-identitarian claims of the local urban movement took place, both from a quantitative and a qualitative perspective: quantitative, as much as it involved a change of scale in relation to the demands that had addressed the importance of heritage in previous stages, from the architectural element or complex to the urban area; qualitative because, on that scale, non-monumental heritage sites -especially the industrial- became appreciated per se rather than as mere releasers or containers of public space. This phenomenon began to manifest through the renewal of the Port Vell, starting from 1988. After the 1993-1997 period, which was marked both by the ebb of the Olympics and the municipal debt, the period that has been characterized by the urbanization of the so-called New Projects has become a prime setting for its development. This is suggested by the rise of citizen mobilizations in opposition to redevelopment plans that has been registered between 1998 and 2006. Among them, the ones that have affected Trinitat Nova neighbourhood, Lesseps Square, and Parc Central del Poblenou area have had a particular social and spatial impact. From a cultural viewpoint, this reality suggests the possibility of preserving 'spaces of hope' in the construction of an alternative globalization, provided that they acquire and consolidate a structural meaning through the combination of multiple local processes. From a political point of view, it reveals the role of participatory planning as a locus of encounter for actors and strategies that otherwise may be irreconcilable. Finally, a material stance highlights the complex impact of the above on the physical environment, in a time when the social emphasis on images and discourses can result either in a lively coherence between the perception, conception and experience of space, or an extraordinary lack of correlation between them. / El espacio es la expresión de la sociedad, y la sociedad contemporánea está construida en torno a flujos. De ambas constataciones se deriva la existencia de una forma espacial característica. Sin embargo, la mayor parte de las personas sigue viviendo en lugares y percibe su espacio en virtud de ellos. La coexistencia de estas dos lógicas espaciales opuestas tiene como consecuencia una 'esquizofrenia estructural' que amenaza con romper los canales de comunicación de la sociedad. El reto de tender puentes entre ambas obliga a hacer frente a procesos que involucran, además de las prácticas materiales, otras dimensiones del espacio social. De ahí que tanto la multidimensionalidad de este último como los procedimientos que posibilitan la reconstrucción de los lugares en el marco que determina hayan cobrado gran relevancia. En relación con el primer aspecto, se pone de relieve que la historia, vertebradora de las identidades locales, puede integrarse en el medio físico para facilitar su experiencia simultánea a la de otras facetas estrictamente espaciales de lo que cabe denominar 'lugares interpretados', en los que el patrimonio material puede asumir un papel significativo. En relación con el segundo aspecto, se hace patente la importancia de los procesos comunitarios en la reconstrucción de narraciones inclusivas, así como de los lugares que representan y que las representan. Pero también que en el contexto actual, caracterizado por la desintegración de la sociedad civil, dichos procesos pueden no implementarse si no es como resultado de movilizaciones ciudadanas en demanda de la revisión de planteamientos impulsados por las instituciones y destinados a generar 'lugares alterados'. En Barcelona la gestación de este estado de cosas tuvo un momento determinante en 1986, con la nominación olímpica de la ciudad. En el periodo que se inició con ella se produjo un salto cuantitativo y cualitativo en las reivindicaciones culturales-identitarias del movimiento vecinal. Cuantitativo porque implicó un cambio de escala en relación con las demandas de componente patrimonial de etapas anteriores: desde la pieza o conjunto arquitectónico al área urbana. Cualitativo porque, a tal escala, el patrimonio no monumental -en especial el industrial- pasó a valorarse per se en vez de como mero liberador o contenedor de espacio público. Tal fenómeno empezó a evidenciarse con el proceso de reordenación del Port Vell, a partir de 1988. Una vez superada la etapa 1993-1997, marcada por el reflujo de los JJOO y la deuda municipal, el periodo caracterizado por el urbanismo de los New Projects ha devenido un escenario privilegiado para su desarrollo. Así lo sugiere el repunte registrado entre 1998 y 2006 en las movilizaciones ciudadanas en oposición a planes de remodelación, entre las cuales han tenido un particular impacto social y espacial las que han afectado al barrio de Trinitat Nova, a la plaza Lesseps y al sector Parc Central del Poblenou. Desde una vertiente fundamentalmente cultural, la realidad analizada apunta a la posibilidad de mantener abiertos 'espacios de esperanza' en la construcción de una globalización alternativa. Desde un punto de vista eminentemente político, revela la condición del planeamiento urbanístico participado de punto de encuentro de actores y estrategias diversas. Desde una perspectiva material, pone de relieve la compleja incidencia de lo anterior sobre el medio físico, en un momento en el que el acento puesto en las imágenes y los discursos puede traducirse tanto en una vivaz coherencia entre la percepción, la concepción y la vivencia del espacio, como en una extraordinaria falta de correspondencia entre las mismas.

Traces in the landscape. Permanencies and absences as guidelines for the interpretation of the coastal territory. La Guardia - San Javier section. For the Province of Santa Fe, the occupation of floodable areas is a fact in appearance as usual as inevitable, as the its geography is determined by the presence of the strong River Paraná, which defines its East limit with the provinces of Entre Ríos and Corrientes. A series of smaller streams integrate its fluvial system, and in the coast of this river and its tributary there are located important cities, urban centers of medium and minor hierarchy that have also contributed to the particular definition of the territory and coastal landscape. Historically the river is the axis of the communications and the economy of these urban centers and the territories that support them, but also is a potential threat dueto its periodic level rise and the floods it causes. This is the reason why different disciplines and practices involved in the conformation of these areas of high hydric vulnerability are frequently compelled to problematize their knowledge and traditions, matter that this research focuses operating from the field of urbanism and territorial history on a concrete fragment of this territory, between La Guardia and San Javier. In this context, the research intends to identify and comprehend which are the spatial particularities that the coast has acquired in the processes that have determined its construction, that differentiate it and provide its identity. In other words, to explain which are the features that manifest a specific construction culture (fluvial) and distinguish it from the interior (mediterranean) of the Province. In order to accomplish this, the research carefully observes the contemporary landscape, intending to find material and immaterial vestiges, signals or marks of permanencies and hints of ancient occupations that enrich a first, general and inattentive glance, giving special relevance to the physical object orto the vestiges of its presence, understanding that its existence allows to confirm the hypothetical statements of this research, specially the development of its strategies of construction and of its persistence. For the theoretical trame the contributions from the field of urbanism have been relevant, but also of geography, hydric sciences and other disciplines. Also, the notions of territory, landscape, cultural landscape and resilience have been very important. For the methodology, the use of territorial history, multi-scalar analysis and indicia! analysis have been central. The strategies of interpretation and design presented in the research are potentially replicable not only the north and south of the area under analysis, but also to other coastal situations and of interaction with bodies of water. Among the conclusions of major importance that this research arrives it is relevant to highlight the persistence of sorne territorial elements set up by the Hispanic colonization, the recognition of the area landscape as a particular and unique construction in the Province of Santa Fe, strongly determined by t he incomplete modernization of the nineteenth century coastal colonies, the identification of the elements that conform the landscape -natural and manmade- and the development of strategies of resilience or adaptation to the hydric demands, the landscape inter-scalar relationships, and the revision of the concept of corridor to interpret and intervene on the area and its replacement by the idea of rhizome. / La ocupación de áreas inundables es para la provincia de Santa Fe un hecho en apariencia tan habitual como inevitable, ya que la propia geografia provincial se encuentra ideterminada por la presencia del caudaloso río Paraná que conforma su límite Este con las provincias de Entre Ríos y Corrientes. Una serie de cursos menores integran su sistema fluvial y en la ribera de este río y de sus afluentes se han emplazado ciudades importantes, núcleos urbanos de jerarquía intermedia y menor que han contribuido también a modelar particularmente el territorio yel paisaje ribereño. Históricamente el río es el eje de las comunicaciones y la economía de estas localidades y los territorios que las sustentan, pero también una latente amenaza dado que son periódicas sus crecidas y las inundaciones que provoca. Es por ello que las distintas disciplinas y prácticas involucradas en la conformación de estas áreas de alta vulnerabilidad hídrica se ven frecuentemente compelidas a problematizar sus saberes y tradiciones, cuestión que esta investigación aborda operando desde el campo del urbanismo y la historia territorial en un fragmento concreto de este territorio comprendido entre las localidades de La Guardia y San Javier. En este contexto se trata de identificar y comprender cuáles son las particularidades espaciales que ha adquirido la ribera en los procesos que determinaron su construcción, que la diferencian y le otorgan identidad. En otras palabras, explicar cuáles son los rasgos que manifiestan una cultura de construcción específica (fluvial) y que la distinguen del interior (mediterráneo) de la provincia. Para lograrlo observa cuidadosamente el paisaje contemporáneo, tratando de encontrar vestigios materiales e inmateriales, señales o marcas de permanencias e indicios de antiguas ocupaciones que enriquecen una primera mirada general y algo desatenta, dando especial relevancia al objeto fisico o a los vestigios de su presencia, entendiendo que su existencia permite confirmar los enunciados hipotéticos de este trabajo, especialmente el desarrollo de sus estrategias de construcción yde su persistencia. Para el marco teórico han sido muy relevantes los aportes provenientes del campo del urbanismo pero también de la geografia, de las ciencias hídricas y de otras disciplinas, y muy importantes las nociones de territorio, paisaje, paisaje cultural, resiliencia. Para la metodología ha sido central la utilización de la historia territorial, del análisis multi-escalar y el análisis indicia!. Las estrategias de interpretación y proyecto presentada en la investigación son potencialmente replicables no sólo hacia el norte y sur del área analizada, sino también en otras situaciones de ribera, costa e interacción con cuerpos de agua. Entre las conclusiones de mayor importancia a las que llega la investigación interesa destacar, la persistencia de algunos elementos territoriales instalados por la colonización hispana, la ponderación del paisaje del área como una construcción particular y única de la provincia de Santa Fe fuertemente signada por la modernización incompleta de las colonias decimónicas ribereñas, la identificación de los elementos conformadores del paisaje -naturales y antrópicos- y el desarrollo de estrategias de resiliencia o adapatación ante las demandas hídricas, las relaciones inter-escaleres del paisaje, la revisión del concepto de corredor para interpretar y actuar sobre el área y su reemplazo por la idea de rizoma.

European Historic Urban Districts are highly appreciated by their inhabitants and visitors and they can be considered as one of the most valuable collective achievements of the European culture. The preservation of our urban heritage requires the protection of the social context as well as the preservation of the authenticity and integrity of its physical materiality. That means to improve the quality of life of their inhabitants as well as the sustainability of the historic districts. This dissertation analysed the Historic Urban Districts as complex energy and informational systems in order to address the challenge to improve their sustainability and liveability while protecting their cultural values. First, a methodological framework for energy retrofitting in all its phases has been defined based on a strategic information management and from a multiscale perspective. Secondly, a decision making methodology that allows the modelling of the historic city and the selection of the best strategies has been developed. In order to support the whole system a multiscale data model has been designed. Finally, the historic city of Santiago de Compostela has been selected for the implementation. / Los distritos urbanos históricos europeos, además de ser muy valorados por sus habitantes y visitantes, pueden ser considerados como uno de los logros colectivos más valiosos de la cultura europea. La conservación de nuestro patrimonio urbano requiere de la protección de su contexto social, tanto como de la preservación de la integridad y la autenticidad de las su materialidad física. Esto significa mejorar la calidad de vida de sus habitantes así como la sostenibilidad de los barrios históricos. Esta tesis aborda los distritos urbanos históricos (HUD) como sistemas energéticos e informacionales complejos con el fin de abordar el reto de mejorar su sostenibilidad y habitabilidad al tiempo que se protegen sus valores culturales. Dentro de esta tesis se han desarrollado principalmente tres temas: el marco metodológico integral, dónde la rehabilitación energética de los HUD se articula a partir de un enfoque multiescala, la metodología de toma de decisiones que permite la selección de las estrategias y la gestión de la información basada en un modelo multiescala que apoya todo el sistema. La ciudad histórica de Santiago de Compostela ha sido seleccionada para la implementación. Las principales contribuciones de esta tesis son los siguientes: - Un marco metodológico para la rehabilitación energética de los HUD, aplicable en la mayoría de los barrios históricos europeos. El marco se basa en la gestión estratégica de la información desde una perspectiva multiescala con el fin de garantizar la viabilidad, la eficiencia, la continuidad y la coherencia de todo el proceso. -Una estrategia de modelado de las HUDs, basada en la categorización del parque edificado y la selección de edificios representativos, que tiene en cuenta los valores históricos, así como sus características energéticas. Para ello, se han propuesto parámetros que son fáciles de adquirir, así como un método para llevar a cabo la categorización de una manera flexible. Se han propuesto, también, unos coeficientes de ajuste del impacto dependiendo de la selección de los edificios representativos con el fin de corregir el impacto final con un factor de aplicabilidad. - Con el objetivo de dar cabida en la metodología a los diferentes escenarios posibles de disponibilidad de información se han propuesto diferentes niveles de toma de decisiones (LoDM). - Se han propuesto, también, cuatro categorías de criterios y dos de restricciones con el fin de considerar todos los factores importantes para la toma de decisiones para la rehabilitación energética en entornos históricos. Para la evaluación de las restricciones (significado histórico y compatibilidad) se ha adaptado el método desarrollado en el proyecto EFFESUS. - Se han desarrollado cuatro extensiones para un modelo de datos multiescala, basado en el estándar CityGML, para el apoyo a la gestión estratégica de la inform ación y la toma de decisiones. Dos de las extensiones tienen como objetivo utilizar la extensibilidad del modelo de datos para estructurar toda la información temática necesaria (energía y características culturales de los edificios). La tercera extensión estructura la información acerca de los indicadores con elfin de permitir la monitorización y la cuarta se refiere a los datos dinámicos.

The topic of this thesis is Barcelona's pre-democratic metropolitan plans, protagonists and their theoretical references. The metropolitan planning of the Franco period is usually interpreted as an attempt at technical modernization in a politically conservative context. However, the ambiguity between the technical and the political contribution shifted throughout time, as a result of the regime's differences in technical and political visions, the imposition of a changing reality, the relative autonomy of the technicians' role and the epistemological changes in the planning discipline. The first section of the thesis focuses on the Regional Plan of 1953 from autarky time, a precedent of metropolitan planning, which was co-authored by the architects Pedro Bidagor, Director of Urban Planning in Madrid, and Josep Soteras, a former member of GATCPAC at the Republican era. This section problematizes the dialectic between the internalization of some foreign references, such as the Anglo-Saxon Regional Planning, and the moral rhetoric of the Falange's ideology. The Regional Plan introduced innovations that would be expressed in the Land Act of 1956. The second section of the thesis discusses the conceptual renewal of urban planning that sought its epistemological legitimacy in science during the sixties, expressed in the Barcelona's Metropolitan Master Plan of 1966. Architects Manuel Ribas Piera, Xavier Subias and engineer Albert Serratosa led the multidisciplinary team in charge of 1966 plan. The sixties were years of profound urban changes arising from the developmentalist state policy, which consolidated the metropolitan phenomenon In Barcelona in which the mayor Porcioles set the stage of his "Great Barcelona" plan. The third and final section of the thesis problematizes the urban planning at the late Franco era and the transition to democracy, taking as its focus the Metropolitan General Plan - MGP, outcome of the accumulation of experiences over twenty years of metropolitan planning and the two Barcelona's previous metropolitan plans. The MGP was the result of the work of a technocracy ideologically progressive and the political pressure from the Left parties and neighborhood associations. Subsequently, the aim of social emancipation through the urban planning would often be reduced by possibilism in democracy. This thesis is concerned with the different elements involved in the Barcelona's metropolitan planning at the Franco era, the changes of urban paradigm, and the success of some pretty extraordinary characters, open to the world and knowledge that acted brilliantly in a bleak reality. / L'objecte d'aquesta tesi són els plans, protagonistes i referents teòrics del planejament metropolità de la Barcelona predemocràtica. El planejament del període franquista s'acostuma a interpretar com a un intent de modernització tecnica en un marc polític reaccionari, pero la realitat política del regim va anar canviant al llarg del temps i també anaren canviant el paper deis tècnics, els paradigmes urbanístics i les actituds vers l'actuació sobre la ciutat . La primera part de la tesi té com a centre el Pla Comarcal de 1953 durant l'autarquia, un antecedent del planejament de l'àmbit metropolità, que tingué com a coautors els arquitectes Pedro Bidagor i Josep Soteras. Aquesta primera part problematitza la dialèctica entre la interiorització d'uns referents estrangers, com el Regional Planning anglo-saxó o l'organicisme de Bardet i l'ideari de ciutat subjacent a la ideologia conservadora de la Falange que, amb la seva retòrica moralitzant, legitimava el planejament d'aleshores, però que introduí innovacions tècniques que serien expressades en la Llei del Sòl de 1956. La segona part de la tesi parla de la renovació conceptual de l'urbanisme, que buscà la seva legitimació epistemològica en la ciencia i que a Barcelona tingué com a expressió la redacció del Pla Director de l'Àrea Metropolitana de 1966, realitzat per un equip multidisciplinar liderat per Manuel Ribas, Xavier Subías i Albert Serratosa. Els anys seixanta foren anys de profundes transformacions econòmiques i polítiques, amb l'arribada dels tecnòcrates de l'Opus Dei, i urbanes derivades del desarrollismo, en que es consolidà el fenomen metropolità a Barcelona i en els quals l'alcalde Porcioles posà les bases de la seva "Gran Barcelona". La tercera i última part problematitza l'urbanisme del tardofranquisme i de la transició democràtica, tenint com a centre el Pla General Metropolità, resultat de la sedimentació d'experiències de més de vint anys de planejament metropolità i dels dos plans anteriors realitzats a Barcelona. El PGM, orfe de direcció política, fou el producte d'una tecnocràcia ideològicament progressista i de les pressions dels partits d'esquerres i de les Associacions de Veïns. Posteriorment, l'anhel d'emancipació social a través de l'urbanisme quedaria sovint rebaixada pel possibilisme en democràcia. Aquesta tesi s'interessa pels diferents elements que intervingueren en el planejament metropolità del període franquista a Barcelona, els canvis de paradigma urbanístic i en l'encert d'alguns personatges bastant extraordinaris que, oberts al món i al coneixement, van fer possible actuar amb certa brillantor en una realitat grisa i tancada.

The use of the subsoil in our cities was limited until more or less a century ago. The technological advances of the twentieth century and the increased need for greater urban comfort has led to intensive building in all European capitals both above and below ground-level. This constitutes a radical change in the way we understand cities today and its consequences affect urban aspects, and open a knowledge and reflection on the contemporary city field. The construction of the metropolis is now a reality thanks in large part to the underground work. Therefore, it is considered today that the urban underground deserves special attention. Unlike other cities with extraordinary and little comparable phenomena, Barcelona, which is the case study of this research, stands out as similar to other European cities because since its founding it has been developed in the same geographical location and has been expanding and regenerating at a similar pace, responding to socio-economic changes. For this reason, the study of urban underground allows general contributions on the relevance of the subsoil in a large contemporary city, and uncovers facets of Barcelona. While the visible part of Barcelona has been extensively studied, the invisible and below ground has not had the same attention. The research approach starts with the process of formation of the Barcelona underground. lts evolution is studied both in terms of network and in terms of the spaces occupied. This approach allows four broad categories to be made within the synthesis of services which occupy the urban subsoil. The reduction of the current plans of the urban underground in this city is cause and effect while the schematic vision that so often occurs in the simplicity and the failings of urban interventions below ground. In fact, im proving the description is, somehow, to propose. One of the main goals is drawing, as a means of analysis and reflection, at three different levels, the reality of the hidden Barcelona. Firstly, the small scale detects that there are ways in which volumes and pipes that are repeated can be understood as types. They have a distinct character to the types of buildings on the surface Classification pinpoints a number of categories for understanding what the ingredients of this underground city are. Secondly, the study reveals peculiar fragments of the urban subsoil. On one hand, it is observed that each element largely responds to their condition and functional requirements, with little regard to the surrounding environment, as opposed to the surface. Moreover, depending whether the underground elements are service networks, transport networks or underground spaces-volumes , development occurs in limited spatial directions. Finally, the comparative study of different areas places in relation fragments that do not have much in common on the surface, and highlights the main aspects which determine the morphological characteristics in unique places. Thirdly, the study of the entire hidden Barcelona allows reflections of different kinds. lt is discovered that there is a range of the underground city, with a structure, organization, individual identity and logic, which is the first step to having the opportunities underground in a large contemporary city. / L'ús del subsòl a les ciutats era, fins fa tot just un segle, molt limitat. Durant el segle XX, els avenços tècnics, l'augment de les necessitats i el confort urbà han conduit a incrementar-lo fins al punt que avui en dia qualsevol capital europea construeix tant sota com sobre rasan!. El canvi que això representa en la constitució de la ciutat actual és radical, i les seves conseqüències afecten a aspectes urbanístics que ofereixen un camp obert al coneixement i a la reflexió sobre la ciutat contemporània. L'observació de les grans ciutats contemporànies permet afirmar que la construcció de la metròpolis actual és una realitat gràcies, en gran part, a la tasca subterrània. Per tant, es considera que a dia d'avui el subsòl mereix una especial atenció urbanística. A diferència d'altres ciutats amb fenòmens extraordinaris i poc comparables, el cas d'estudi de la present investigació, Barcelona, destaca per ser similar a d'altres ciutats europees en tant en quant des de la seva fundació ha estat desenvolupada al mateix indret geogràfic i s'ha anat ampliant i regeneran! amb un ritme similar, donant resposta als canvis socioeconòmics. Per aquest motiu, l'estudi del sota rasant urbà d'aquesta ciutat permet fer aportacions de caràcter general sobre la rellevància del subsòl en una gran ciutat contemporània, així com desvetllar facetes d'aquesta. Si bé la part visible de Barcelona ha estat àmpliament estudiada, l'invisible i sota rasant no ha tingut la mateixa atenció. La investigació parteix d'una aproximació al procès de formació de la Barcelona subterrània. S'estudia l'evolució en la seva ocupació tant pel que fa a xarxes com pel que fa a espais. Gràcies a aquest atansament, es fa una síntesi de les motivacions que han portat a ocupar el subsòl urbà en quatre grans categories: les raons primàries, les possibilitats de la técnica, les motivacions funcionals i les qüestions compositives. La reducció temàtica deis plànols actuals del subsòl a aquesta ciutat és causa i efecte a la vegada de l'esquematisme de visió que tantes vegades es produeix en el simplisme i el desencert de les intervencions urbanes en sota rasant. En realitat, millorar la descripció ja és , d'alguna manera, proposar. S' utilitza el dibuix com a recurs d'anàlisi i reflexió, i a tres escales diferents, es descriu la realitat de la Barcelona oculta. En primer lloc, l'escala menuda detecta que en sota rasant hi ha formes, bàsicament volums i conductes , que es repeteixen i que es poden entendre com a tipus. Aquests tenen un caràcter diferenciat als tipus de construccions en superficie. La seva classificació desgrana una sèrie de categories que permeten entendre quins són els ingredients d'aquesta ciutat soterrada. En segon lloc, l'estudi de fragments de ciutat desvetlla particularitats del subsòl urbà. D'una banda, es detecta que cada peça respon en gran mesura a la seva condició i necessitat, sense tenir massa relació amb el que succeeix en el seu entorn, a diferència de la superficie. D'altra banda, segons si els elements soterrats són xarxes de servei, xarxes de transport o soterranis, el seu desenvolupament es produeix amb direccions espacials limitades en els eixos X, Y i Z. Finalment, l'estudi comparatiu de diferents àmbits posa en relació fragments que no tenen massa en comú en superficie, i posa de manifest quins són els aspectes principals que condicionen les característiques morfològiques en indrets singulars. En tercer lloc, l'estudi del conjunt de la ciutat soterrada permet fer reflexions de diferent índole. Es descobreix que existeix una autonomia de la ciutat soterrada, amb una estructura, entitat, identitat i lògiques particulars , que suposen un primer pas per comptar amb les oportunitats que brinda el subsòl a una gran ciutat contemporània.

In order to develop safe and effective topical and transdermal formulations to treat either local skin disorders or for systemic drug delivery, it is first imperative to assess skin permeation using a reliable and comprehensive analysis method. The assessment of drug permeation into/across the skin is traditionally accomplished using Franz diffusion cells with subsequent analysis by conventional chromatographic methods such as HPLC and more recently using advanced imaging techniques. In this context, time of flight-secondary ion mass spectrometry (ToF-SIMS) offers distinctive advantages in mapping drugs within skin with high sensitivity and chemical specificity without the need for fluorescent tags or radiolabels. The work in this thesis uses the combination of conventional and advanced methods to evaluate drug permeation into the skin. This approach provides complementary and detailed information regarding the permeated mass, the permeation depth and the spatial distribution and localisation of drugs within skin. As ToF-SIMS does not produce quantitative results, due to the matrix effects, a novel high throughput method was successfully developed to quantify ToF-SIMS data. This method involved the homogenisation of skin tissue followed by microarray printing of this skin homogenate with known concentrations of active pharmaceutical ingredients, specifically imiquimod and chlorhexidine. The subsequent analysis by ToF-SIMS of the resulting array allowed the generation of a calibration curve that can be used in the quantification of the unknown drug concentration in the tape strips. This work has demonstrated the potential of a method to quantify ToF-SIMS data of drugs within skin. Imiquimod is an immune modulator drug approved by the FDA for the treatment of superficial basal cell carcinoma (BCC) but not the nodular lesions. An assessment of imiquimod permeation from commercially available Aldara™ cream into ex vivo porcine skin was carried out using the complementary approach of HPLC and ToF-SIMS analysis. This work represents the most detailed assessment to date of the true extent of permeation of imiquimod from Aldara™ cream as previous studies analysed the permeation of Aldara™ cream showed a limitation in the analytical methodology employed (i.e. analysis by HPLC only). The results showed that imiquimod does permeate into the stratum corneum but is very limited in the deeper skin cell layers. In addition, the ToF-SIMS ion images of Aldara™ cream tape strips illustrated a non-uniform distribution of imiquimod within skin which may result in a decreased efficacy of the cream to uniformly treat whole BCC lesions giving rise to the likelihood of tumour recurrence. This offers previously unobserved insights about the spatial distribution of imiquimod delivered from Aldara™ cream. As other studies have reported that Aldara™ cream has some limitations in the treatment of nodular BCC lesions due to the cream’s inability to deliver imiquimod into the deeper more invasive nodular lesions, an enhancement of imiquimod permeation is thought to be useful to overcome these limitations. Therefore, an attempt to improve delivery of imiquimod into the deeper skin layers using microemulsions and microneedles was investigated. Imiquimod microemulsions were formulated, characterised and then tested for skin permeation enhancement. However, the assessment of imiquimod permeation from the formulated microemulsions alone and with microneedle pre-treatment using HPLC and ToF-SIMS demonstrated a limited ability of the microemulsions to improve delivery of imiquimod over Aldara™ cream. In contrast, Aldara™ cream with microneedle pre-treatment using a derma stamp electric pen showed improved delivery of imiquimod into the skin. This work is believed to be the first attempt to enhance imiquimod delivery using microemulsions and microneedles. Utilising the high sensitivity offered by the ToF-SIMS instrument in the analysis of individual tape strips, an in vivo and ex vivo comparison of chlorhexidine permeation into the stratum corneum was performed using commercial products currently used in hospitals within the UK for skin antisepsis. A comparison was carried out using the tape stripping technique with subsequent analysis of an individual tape strip by ToF-SIMS. The results showed that HiBiSCRUB® 4% produces a higher concentration of chlorhexidine in the upper stratum corneum layers than other products. This work demonstrated the first known application of ToF-SIMS to compare the in vivo skin permeation of commercially available chlorhexidine products and provides the foundation for the potential application of ToF-SIMS in assessing bioequivalence of topical products.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) has proven its ability to characterise (in)organic surfaces, and is increasingly used for the characterisation of biological samples such as single cells. By combining ion imaging and molecular depth profiling it is possible to render 3D chemical images, which provides a novel, label-free way to investigate biological systems. Major challenges lie, however, in the development of data analysis tools and protocols that preserve the cell morphology. Here, we develop and employ such tools and protocols for the investigation of neuronal networks. One of the reasons 3D ToF-SIMS imaging of cells is underused is the lack of powerful data analysis tools as 3D ToF-SIMS measurements generate very large data sets. To address this issue, we developed a method that allows the application of principal component analysis (PCA) to be expanded to large 3D images making 3D ToF-SIMS image processing of whole, intact cells and cellular networks with multivariate analysis now accessible on a routine basis. Using this method, we are able to separate cellular material from the substrate and can then correct z-offsets due to the cells' topography resulting in a more accurate surface heightmap. The method also facilitates differentiation between cellular components such as lipids and amino acids allowing the cell membrane, the cytoplasm and the extracellular matrix (ECM) to be easily distinguished from one another. These developments permit us to investigate the intracellular localisation of specific native and non-native compounds label-free, not just in single cells but also in larger cellular networks. The visualisation of the cellular uptake of non-native compounds, namely fluorescent dyes, in primary rat cortical neurons and the chemical differentiation between cell types, namely primary rat cortical neurons and retinal pigment epithelium (RPE) cells, are presented as applications. Even though the dyes have distinct fragment ions in the high mass range, it was not possible to detect the fluorophores by 3D ToF-SIMS imaging of freeze-dried cells. However, it was possible to detect distinct differences in the kind of ions detected for freeze-dried primary rat cortical neurons and RPE cells albeit in the low mass range. To obtain meaningful results, however, it is paramount that sample preparation does not induce significant physical or chemical changes. We present the first comprehensive comparison between large 3D ToF-SIMS images of freeze-dried and frozen-hydrated cells using PCA to facilitate the data analysis of these large data sets. A higher degree of colocalisation of the K+ signal with cell regions is observed for frozen-hydrated cells, which indicates a lower degree of membrane damage and migration of diffusible chemical species. Frozen-hydrated cell samples are therefore considered to best reflect the native cell state, but freeze-dried cell samples allow far easier sample handling. The mass spectrum of frozen-hydrated cellular material also has increased ion intensities for higher-mass fragments, which is an additional advantage, because the poor signal-to-noise ratio of molecular species with m/z > 200 is a major bottleneck in the advancement of ToF-SIMS imaging as a diagnostic tool.