The search for analytical tools suitable for wide-scale application of DNA analysis is an hot research topic, although thanks to well-established microarray based technology, analysis of DNA sequences and SNP detection can be worked out through a fairly laboratory routine. DNA analysis has nowadays become of increasing interest for several different purposes, mainly thanks to the successful employment of microarray technology, characterized by high sensitiveness and high-throughput analysis, which rapidly advanced genetics leading to devel- opment of many fields of application of DNA analysis, which keeps high the trend in alternative technologies, which could overcome inherent limitations of microarrays technology. In this regard, many efforts have been spent to study electrochemical/electrical based detection strategies by means of which it could be possible to accomplish sensitive analysis by using portable equipments, cheaper and more practical than optical ones, and with scalable-devices compatibles with standard microelectronic processing. Emerging nano-probes with increased chemical-physical properties are considered with growing interest in DNA biosensors as ideal candidates to enhance electrochemical/electrical based detection systems. Among these, nano-gaps adjusted to fit DNA, or in general analyte molecules sizes, are very promising because they can enable direct electrical detec- tion schemes, thus providing a straightforward electronic analogue of the successful DNA microarray standard. Electrical properties of DNA have been the principal focus of many experimental and theoretical research, since early experimental founding confirmed an old hypothesis, for its relevance in the biological function of DNA, being related both with damage and base repair, but also for the appealing potential for biosensor and, in general, in bioelectronic applications. Thanks to its peculiar interactions, it allows versatile manipulations of the structure, compared to other organic and synthetic polymers which have been considered for such purposes. Even though many questions still are open on electrical properties of DNA, it is generally accepted that DNA's conductivity is intimately linked with details of the sequences involved, its length and the overall environment in which molecule is found. The sensitivity to structure's alteration, as that induced by the presence of a mutation, confirmed by experimental and theoretical works allows to exploit DNA electrical properties for biosensor applications. Relying on this agreed description of DNA electrical properties features, the general aim of this thesis was to explore the possibility of developing a platform for the direct transduction of DNA hybridization event based on a nano-gap device and electrical signaling enabled by long range electron transport through DNA molecules. / La detección de hibridación de cadenas de ADN es un reto relevante científicamente y tecnológicamente, que puede aprovechar de las posibilidades proporcionadas por los alcances en los procesos de nano fabricación y caracterización, inspiradores de la idea de una medicina en el punto de atención. El propósito de este trabajo es de establecer un sistema de detección de hibridación de ADN, y polimorfismo de un solo nucleótido (SNP), basado en la medida eléctrica de la reasistencia de un nano-gap funcional izado con el ADN diana. El desarrollo y test del sistema se ha llevado a cabo fijando diferentes objetivos. Un estudio preliminar de la literatura relacionada con las propiedades eléctricas del ADN se ha conducido con la finalidad de establecer el marco de factibilidad del proyecto. De acuerdo con los resultados de este estudio ha sido posible idear el sistema y optimizar su eficacia respeto a las experiencias reportadas. Fijar una estrategia de fabricación de los dispositivos capaz de proveer nano-gaps aptos a la medida de conductividad muy baja, según una rutina de fácil implementación y con alta reproducibilidad de los resultados. Estos se han caracterizados mediante el utilizo de diferentes técnicas basadas primariamente en métodos de detección Óptica y Eléctrica/Electro-química. Obtener la bio-funcionalización selectiva de los electrodos en el nano-gap testando y caracterizando métodos diferentes. Probar el principio de funcionamiento del sistema a través de la medida de la conductividad en los nano-gap durante las diferentes etapas de funcionalización con los bio-receptores y el DNA target. Optimizar el sensor testando su selectividad respeto a la presencia de mutaciones, la sensibilidad a medir diferentes concentraciones del target, y finalmente la posibilidad de regeneración del dispositivo después desnaturalización del ADN hibridado

L’Aneurisma Aòrtic Abdominal (AAA) és una malaltia vascular que afecta amb rellevància la població dels països industrialitzats. És una malaltia que té pocs símptomes i en cas de ruptura de l’artèria aorta té una taxa de mortalitat molt alta per dessagnació interna. Les principals característiques d’aquesta alteració vascular són la dilatació de les parets del vas aòrtic com a conseqüència de la degradació de les diferents capes del mur vascular i una hipervascularització de l’artèria. Aquests dos processos estan estretament relacionats amb el procés inflamatori que es desenvolupa a la paret de l’artèria. Hem investigat la via de la PGE2 en l’AAA i la seva relació amb la hipervascularització associada a aquesta malaltia. Hem analitzat mostres de pacients d’AAA sotmesos a intervenció quirúrgica i les hem comparat amb les mostres de donants multiorgànics. Els pacients havien estat estratificats en funció del diàmetre màxim de l’aorta: low diameter (LD) (>55mm), moderate diameter (MD) (55-69,9mm), i high diameter (HD) (≥70mm). L’AAA es caracteritza per una abundant microvasculatura en la capa mitjana i adventícia amb una infiltració perivascular de cèl·lules CD45 positives. Els nivells d’mRNA de la ciclooxigenasa (COX)-2 i de la isoforma microsomal de la prostaglandin E sintasa (mPGES-1) estan incrementats en les mostres d’AAA (4,4 i 1,4 vegades respectivament). Els dos enzims estan localitzats en les cèl·lules endotelials (EC), en les cèl·lules vasculars llises (VSMC) i en els leucòcits. Aquests enzims, així com els marcadors d’EC, tenen una expressió màxima en el grup LD de pacients d’AAA, mentre que l’expressió dels marcadors de leucòcits mostren un màxim en el grup MD de pacients d’AAA. Aquests resultats indiquen que la hipervascularització i la up-regulation de la COX-2/mPGES-1 precedeixen al màxim d’infiltració leucocitària. Els nivells de metabòlits de PGE2 circulants i secretats pel teixit d’aneurisma in vitro són més alts en les mostres d’AAA que no pas en les mostres control (plasma-controls, 19.9±2.2 pg/ml; plasma-AAA, 38,8±5,5 pg/ml; teixit aòrtic-control 16,5±6,4 pg/mg; teixit aòrtic-AAA, 72,9±6,4 pg/mg). Els receptors de la PGE2 EP2 i EP4 estan sobreexpressats en les mostres d’AAA, sent el receptor EP4 l’únic receptor substancialment expressat en les cèl·lules endotelials i colocalitzat amb l’mPGES-1 en la microvasculatura. A més, el receptor EP4 media l’angiogènesi in vitro activada per la PGE2. Amb aquest estudi aportem de novo dades de l’expressió de l’mPGES-1 en mostres d’AAA humanes. Tots els nostres resultats suggereixen que l’eix COX-2/mPGES-1/EP4 en la microvasculatura pot tenir una especial rellevància en la hipervascularització associada a l’AAA. / The Abdominal Aortic Aneurysm (AAA) is a vascular disease that affects with relevance to the population of industrialized countries. It is usually an asymptomatic disease and in case of rupture of the aorta it has a very high mortality rate by internal hemorrhage. The main features of this disorder are vascular dilation of the aortic vessel walls as a result of the degradation of the different layers of the vascular wall and arterial hypervascularization. These two processes are closely related to the inflammatory process that develops in the wall of the artery. We investigated the PGE2 pathway in the AAA and its relationship with hypervascularization associated with this disease. We analyzed samples of AAA patients undergoing surgery in comparison with samples from multi-organ donors. Patients were stratified according to the maximum diameter of the aorta: low diameter (LD) (> 55mm) moderate diameter (MD) (55-69,9mm) and high diameter (HD) (≥70mm). The AAA is characterized by abundant microvasculature in the middle layer and adventitia with perivascular infiltration of CD45 positive cells. mRNA levels of cyclooxygenase (COX)-2 and the microsomal isoform of prostaglandin E synthase (mPGES-1) are increased in samples of AAA (4.4 and 1.4 times respectively). The two enzymes are located in endothelial cells (EC), vascular smooth muscle cells (VSMC) and leukocytes. These enzymes and markers of EC have maximum expression in the LD group of AAA patients, whereas the expression of leukocyte markers show a maximum in the MD group of AAA patients. These results indicate that hypervascularization and up-regulation of COX-2 / mPGES-1 precedes the maximum leukocyte infiltration. The levels of circulating metabolites PGE2 secreted by in vitro aneurysm tissue are higher in samples AAA than in control samples (plasma-controls, 19.9 ± 2.2 pg / ml, plasma-AAA, 38 8 ± 5.5 pg / ml; aortic tissue-control 16.5 ± 6.4 pg / mg; aortic tissue-AAA, 72.9 ± 6.4 pg / mg). PGE2 receptors EP2 and EP4 were overexpressed in samples AAA, EP4 being the only receptor expressed substantially in EC and colocalizes with mPGES-1 in the microvasculature. In addition, the EP4 receptor mediates in vitro angiogenesis activated by PGE2. This study provides de novo data of the mPGES-1 expression in samples of human AAA and, taken together, our results suggest that the axis COX-2/mPGES-1/EP4 in the microvasculature could have a key role in AAA-associated hypervascularization.

Uno de los temas de mayor interés en el ámbito de la superconductividad es la fabricación de cintas superconductoras (CCs) de YBa2Cu3O6+δ (YBCO) debido a las excelentes propiedades superconductoras que poseen y a las prometedoras perspectivas en cuanto a aplicaciones se refiere. Sin embargo, para poder generalizar el uso de dichas CCs, se requiere de un proceso de fabricación de bajo coste. En este contexto, la técnica de deposición por solución química se presenta como una alternativa muy prometedora. Las CCs pueden cumplir los requisitos actuales exigidos en diferentes aplicaciones, pero hay otras que están fuera de sus capacidades, especialmente aquellas relacionadas con aplicaciones de potencia en las que están presentes campos magnéticos de gran intensidad. El movimiento de los vórtices que tienes lugar en presencia de tales campos magnéticos hace que el YBCO sea poco efectivo en estos casos. El objetivo de este trabajo es mejorar las propiedades del YBCO de manera que se puedan satisfacer los requerimientos de estas aplicaciones de potencia. Para ello, hemos estudiado, principalmente, dos estrategias: la nanoestructuración de la matriz del YBCO añadiendo nanopartículas (NPs) obteniendo nanocomposites superconductores y la optimización del proceso de oxigenación del YBCO para conseguir aumentar todo lo posible la temperatura crítica y la densidad de corriente crítica. La preparación de los nanocomposites de YBCO se llevó a cabo siguiendo dos métodos diferentes de “deposición y crecimiento secuencial”: el método “in-situ” en el que las NPs se forman de manera espontánea durante el proceso de crecimiento, y el método “ex-situ”, que es un novedoso procedimiento desarrollado durante esta tesis en el cual las NPs se sintetizan primeramente formando una solución coloidal para luego quedar atrapadas en la matriz del YBCO durante los procesos térmicos. El uso del método “in-situ” se ha enfocado al estudio de como diferentes NPs (BaZrO3, Y2O3, Ba2YTaO6 and mezclas de éstas) afectan la microestructura del YBCO creando defectos cristalinos que incrementan la fuerza de anclaje. Hemos estudiado también la influencia de estos defectos, en particular, de las dobles cadenas Cu-O, en las propiedades finales de los nanocomposites de YBCO y GdBCO. En el caso del método “ex-situ”, el primer paso fue sintetizar diferentes soluciones coloidales de NPs magnéticas (MnFe2O4 and CoFe2O4) y no magnéticas (CeO2 and ZrO2). Se comprobó la estabilidad de las soluciones YBCO+NPs mediante medidas de DLS y de TEM para asegurar que las NPs conservaban su tamaño inicial sin formar aglomerados. El proceso de pirólisis fue optimizado para cada tipo de NPs teniendo en cuenta que los ligandos usados para estabilizar las NPs pueden influenciar de manera drástica la homogeneidad de las capas pirolizadas. Por último, el proceso de crecimiento fue también investigado para cada tipo de NPs. El estudio del proceso de oxigenación en la capas de YBCO se llevó a cabo usando medidas de resistencia “in-situ”, que permiten monitorizar la evolución de la resistencia en las capas durante los distintos procesos térmicos. Hemos estudiado como la temperatura, el flujo de gas y la presión parcial de oxigeno afectaba al proceso de difusión. De acuerdo con nuestros resultados, las reacciones que tienen lugar en la superficie de la capa antes de que en oxígeno se difunda en el interior de la misma, son el factor que limita la cinética del proceso de oxigenación. Por último El efecto de la adición de plata como catalizador y la difusión en nanocomposites también se ha estudiado. / One of the hot topics in the field of superconductivity is the YBa2Cu3O6+δ (YBCO) Coated Conductors (CCs) fabrication due to the excellent superconducting properties and promising application prospects. However, in order to spread worldwide the use of YBCO coated conductors, a low cost fabrication is required. Chemical Solution Deposition has emerged as a promising alternative that can accomplish this requirement. Despite that YBCO CCs can satisfy the requirements in many different applications, the fact is that there are other uses that are out of it reach with its current status, especially those power applications in which high magnetic fields are applied. The vortex movement which takes place at such high magnetic fields makes YBCO CCs useless for these particular applications. The aim of this work is to improve the properties of YBCO satisfying the demands of these power applications. For this, we studied, mainly, two different strategies: nanostructuration of the original YBCO matrix by adding NPs (superconducting nanocomposites) and optimization of the YBCO oxygenation process to enhance as much as possible the critical temperature and critical current density. The preparation of YBCO nanocomposites was done following two different “Sequential deposition and growth” approaches: the in-situ approach in which the NPs are spontaneously segregated during the growth process; and the ex-situ approach, a new methodology developed in this thesis in which the NPs are firstly synthesized in a colloidal solution and then embedded in the YBCO matrix. Using the in-situ approach we have made an extensive study of how different NPs (BaZrO3, Y2O3, Ba2YTaO6 and mixtures of these) affect the microstructure of the YBCO creating defects that increase the pinning properties. We have also studied the influence of these defects, in particular, the stacking faults (double chains of Cu-O), on the final properties of the YBCO and GdBCO nanocomposites. With the ex-situ approach we have started by synthesizing different colloidal solutions of both magnetic (CoFe2O4) and non-magnetic (CeO2 and ZrO2) NPs. The stability of YBCO+NPs solutions was checked using TEM and DLS analyses to ensure that the NPs are maintaining the initial size without forming agglomerates. The pyrolysis process was optimized for each type of NPs. We realized that the stabilization agents can critically influence the homogeneity of the pyrolyzed films. Finally, the growth process was also optimized for each type of NPs trying to solve different difficulties that appeared: coarsening, pushing or reactivity. The study of the oxygen diffusion process in YBCO thin films was done using in-situ resistivity measurements that allow to monitor the evolution of the resistance in the thin films in different annealing conditions. We have studied how the temperature, the gas flow and the oxygen partial pressure affect the diffusion process. According to our results, we can conclude that the surface reactions that take place before the oxygen bulk diffusion is the limiting factor for the oxygen diffusion. The effect of the silver addition to the YBCO as oxygen catalyst was also tested. Finally, the first study about the oxygen diffusion process in nanocomposite films gave an idea of how the oxygen diffusion works in this kind of materials.

Sexual division of labour involving the use of teeth in non-masticatory activities in the Tigara population form Point Hope did not affect the wear of the upper and lower first molars and, therefore, food chewing was the main factor causing dental wear in this population. No sexual differences were found in the percentage of dentine exposure of the first molars, which is indicative that both sexes in the Tigara populations consumed very similar diets despite sex differences in the dental wear on the anterior dentition have been reported. The percentage of dentine exposure was positively correlated with the age group categories of the individual in the Tigara population, proving that dental wear is a cumulative process throughout lifespan. Crown relief of the first molars was negatively correlated with the percentage of dentine exposure, which shows that dental wear causes a decrease in cusp and crown heights. Crown relief is a continuous variable significantly correlated with age at death. Crown complexity, on the other hand, was greater in teeth with high levels of dentine exposure, showing that wear facets significantly contribute to food processing during mastication. No significant correlations were found between the percentage of dentine exposure and the density and average length of buccal scratches. However, a trend towards shorter scratches on buccal enamel surfaces was observed with decreasing values of crown relief, which demonstrates that the progressive accumulation of buccal scratches caused by enamel abrasion, which results in a reduction of their average length, is a parallel process with respect to the reduction of crown height. No significant differences on dentine exposure by sex were observed in any of the traditional modern human populations studied, which might be indicative that dental wear on molar teeth is not an adequate measure of the impact of sexual division of labour on the diet of both sexes. No significant differences in dental wear was found between the hunter-gatherer and agro-pastoral groups, despite they had very distinct diets and cultural practices in relation to food acquisition and processing. Such lack of significant wear differences among populations could be indicative that different diets may result in similar wear patterns and that the physical properties of chewed food particles might be more informative on dental wear processes than discrete classifications of dietary habits. First upper molar shape differences from all the modern human populations studied reflected the patterns of human migration and dispersal, although retaining a significant phylogenetic signal. The shape of the upper first molar in the Hutu population may be considered ancestral to the other groups compared that show a derived conditions consisting in more quadrangular and less oval shaped molars. Molar shape variability clearly discriminated the Sundadont and Sinodont populations. The Sinodont upper first molar would be characterized by more regular, rounded outlines, whereas the Sundadont would show more oval and irregular crown shapes. / Los dientes constituyen un material de estudio multidisciplinar y son usados en varias áreas de la ciencia: odontología, anatomía comparativa, paleontología, paleoantropología, genética y ciencias forenses, entre otras. La presente tesis tiene como objetivo principal investigar la variabilidad dental en populaciones de humanos modernos desde una perspectiva multi-metodológica. El enfoque principal fue el desgaste dental, aunque también se analizaron otras características, como la variabilidad métrica, la forma dental, el microdesgaste, el relieve o la complejidad de la corona. Objetivos: Valorar si la división sexual del trabajo presente en los esquimales de Point Hope puede afectar al desgaste del primer molar; Analizar las correlaciones entre marcadores del macrodesgaste, microdesgaste, relieve y complejidad de la corona dental para explorar las diferentes líneas de estudio de la pérdida del esmalte y sus correlaciones; Investigar la posible influencia de la división sexual del trabajo sobre la dienta en diferentes poblaciones de cazadores-recolectores y agricultores; Analizar la forma de los primeros molares en varios grupos de poblaciones humanas modernas mediante la innovadora técnica de la morfología geométrica tridimensional. La investigación ha sido realizada únicamente con el material disponible en las colecciones dentales de la Universidad de Barcelona y la Universidad de Alicante. Se analizaron 251 primeros molares procedentes de 188 individuos de 9 poblaciones diferentes de humanas modernas (Agta, Aborígenes Australianos, Batéké-Balali, Esquimo, Hutu, Javaneses, Khoe, Navajo y San). Al examinar las posibles influencias de la división sexual del trabajo en la dieta en otras poblaciones de economía tradicional, no se ha encontrado tampoco diferencias significativas entre hombres y mujeres en ningún de los grupos analizados. Tampoco se han encontrado variaciones en el desgaste entre los patrones de subsistencia cazador-recolector y agricultor. El estudio de la forma dental muestra una importante variación de la forma del primer molar superior entre los grupos.

Air pollution is a major environmental and public health concern, especially in urban areas where both emission sources and population are concentrated. The pollution sources and the evolution of aerosols and gaseous pollutants once emitted into the atmosphere depend on geographical, climatological and meteorological conditions of the study area. In the Western Mediterranean Basin, the coastal city of Barcelona (Spain) is characterized by a warm dry climate, scarce precipitation and high urban density, as well as being geographically constrained by the coastal range thus hindering the dispersion of pollutants. Within this context, the intensive SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies) campaign developed in October 2010 in Barcelona consisted on concurrent aerosol measurements at different sites in the city region, with the aim of studying the aerosol temporal variability and spatial distribution, progressively moving away from urban aerosol sources. Several sites were selected: Road Site (RS) and Urban Background (UB) were located on ground levels, whereas Torre Mapfre (TM) and Torre Collserola (TC), representative of the urban/suburban environment were located at certain height (150 m a.s.l. and 415 m a.s.I., respectively). Finally, the Regional Background site (RB) located 50 km from the city allowed for the study of the transport of urban emissions outside the city. Results from simultaneous measurements of aerosol size distributions at the RS, UB, TC and RB with a Scanning Mobility Particle Sizer (SMPS) were studied after performing a k-means cluster analysis on the combined data sets. This allowed the classification of all size distributions in 9 clusters: three clusters account for traffic conditions (30% of the time), three account for background pollution (54%) and three described specific special cases (16%). Traffic emissions heavily impact the closest sites, and some of these particles evaporate when the air mass move away from the traffic hot spots. The analysis of long term SMPS data sets in the high insolation urban environments of Barcelona, Madrid, Brisbane, Rome and Los Angeles also by k-means clustering analysis revealed traffic and nucleation events as the two most relevant sources of ultrafine particles (44-63% and 14-19% of the time, respectively). Moreover, nucleation particles accounted for 21% of total N, evidencing the importance of nucleation processes to ultrafine particles concentrations in high insolation urban areas. The urban nucleation events consist on particles bursts starting around midday and lasting 3-4 hours while growing to 20-40 nm, opposite to regional nucleation “banana shape” events which usually grow to larger sizes. Regarding the composition of the PM1 fraction (PM mass levels below 1 μm) at the RS and UB during SAPUSS, a source apportionment PMF analysis was carried out. The resulting 9 factors could be broadly grouped in the following categories: road traffic (23-36% of PM1 mass), industrial and shipping emissions (42%), secondary aerosols (29%) and biomass burning (1%). The joint analysis of organic and inorganic species was able to identify a high number of sources resulting in in a more complete and realistic study of the aerosol sources in Barcelona. The study of the PM10 fraction (PM mass levels below 10 μm) at the RS, UB, TM and TC during SAPUSS by means of a PMF source apportionment study enabled the assessment of the spatial variability in vertical and horizontal levels. The 8 resulting factors accounted for primary traffic emissions (Exhaust and wear and Road dust, 19- 38% of PM10 mass), primary inorganic aerosols (Mineral dust and Aged marine, 28- 39%), industry (Heavy oil and Industrial, 5-7%) and secondary aerosols (Sulphate and Nitrate,28-36%). The main factors influencing the different sources concentration at each site were: proximity to the emission source, air mass origin and meteorological parameters. The complete study of aerosol fractions affecting the urban area of Barcelona and similar urban environments (Madrid, Brisbane, Roma and Los Angeles), from ultrafine to coarse particles, enables the identification of the main sources affecting each size fraction in particular and aerosols in general. Owing to the results obtained and the different techniques applied, recommendations regarding air pollution studies and air quality measures have been proposed. / La contaminació atmosfèrica en ambients urbans és motiu de preocupació pel seu impacte en el medi ambient i en la salut de la població. Les fonts d'emissió d'aerosols atmosfèrics i la seva evolució a l'atmosfera depenen de factors geogràfics així com de les condicions climàtiques i meteorològiques de l'àrea d'estudi. A la conca Mediterrània Occidental, i a la ciutat de Barcelona en particular, el clima càlid, l'escassa precipitació, l'alta densitat de població i determinats factors geogràfics que poden dificultar la dispersió dels contaminants i influenciar molt marcadament els nivells i composició dels aerosols. En aquest context es va desenvolupar la campanya intensiva SAPUSS (Solving Aerosol Problems by Using Synergistic Strategies) a Barcelona a l'octubre de 2010, que consistia en mesures simultànies d'aerosols a diversos llocs de la ciutat, amb l'objectiu d'estudiar la variabilitat espacial i temporal dels aerosols. L'estudi dels nivells d'aerosols en funció de la mida de les partícules a 4 ciutats més amb un clima d'alta insolació similar al de Barcelona (Madrid, Brisbane, Roma i Los Angeles) ha permès avaluar les fonts que afecten a la variabilitat de partícules ultrafines en aquests ambients urbans. En particular s'han estudiat les característiques dels episodis de nucleació urbans (formació de noves partícules), així com la seva freqüència. També s'han caracteritzat les principals fonts d'aerosols de diàmetre inferior a 1µm i 10 iim (PM1 i PM10, respectivament) en diverses ambients urbans de Barcelona durant SAPUSS. Això ha permès estudiar la variabilitat a nivells horitzontal i vertical dins l'atmosfera urbana. L'estudi de les fonts que afecten els aerosols de l' àrea urbana de Barcelona i ambients similars en funció de la seua mida (des de les ultrafines fins a les grolleres) ha permès identificar les principals fonts que afecten a cada fracció en particular i als aerosols en general i per tant proposar mesures aplicables per a l'avaluació i millora de la qualitat de l'aire.

From the fundamental point of view, NPs formed by MFe2O4 with (M= Co, Fe) are ideal system models to study the new magnetic phenomena associated with the so-called particle-like behaviour, which emerges from the size reduction towards the nanometre scale and contrasts with the well-established magnetic properties of their bulk-counterparts. It is well known that most of the particle-like behaviour and in general the large variability of the magnetic properties observed in this kind of nanomaterials are related to structural features of the NPs rather than being originated from intrinsic finite-size or surface effects, at least for NPs bigger than a few nanometers. These structural features, such as crystallographic defects, polycrystalline nature of the NPs, lack of crystallinity at the particle surface, etc., have strong influence on their magnetic properties and can be modified at will through the synthesis method. Therefore, whenever this particle-like behaviour is unwanted for applications with highly demanding requirements, the choice of a suitable synthesis method is of key importance to obtain NPs of high-crystalline quality. On the contrary, particle-like behaviour controlled by the crystalline nature of the NPs could be useful to tailor their magnetic properties for specific applications. Among the common synthesis methods, high-temperature decomposition of metal-organic precursors results the best alternative due to the remarkable final properties of the obtained NPs, such as narrow size distribution, high crystallinity and relatively simple tuning of their size and shape. So this will be the chemical route chosen in this work to study the capabilities of this synthesis method to control the final properties of the NPs through their nanostructure. In addition, to get a deeper insight in the magnetic and structural properties of those materials and to shed light on relevant issues that are still under discussion (dynamic response, magnetic frustration or inter¬particle interactions) it could be useful to combine experimental techniques enabling the characterization of the system from macroscopic scales towards single-particle structures. Within this framework, we present this work that is divided into three main parts. First, it is studied the effect of the concentration of two common reactants, involved in the thermal decomposition method, on the final properties of magnetic NPs based on iron oxides aiming at optimizing the synthesis procedure and getting a good control of the structure of the final product. In the second part, those NPs obtained in the former way are applied to demonstrate the crucial role of the nanostructure on the physical properties of nanoparticulate systems; specially, the strong interplay existent between structure and both magnetic frustration and interparticle interactions. Finally, in the third part, MFM experiments with an external applied magnetic field have been performed to directly observe the reversal of the magnetization of isolated particles and the dynamic behaviour of small aggregates.

In this thesis we have made progress on the study of higher dimensional gravity by focusing on the properties of black holes and branes and their dynamics. We have developed two main projects: • provide several maps between different spacetimes • determine the hydrodynamical behavior of fluids dual to some classes of black holes This work improves the current understanding of GR in spacetimes with general dimension and gives hints for holography in spacetimes different from AdS. Here we give a brief summary of the work developed underling the main results achieved. In Chapter 2, we introduce the techniques applied for studying black brane hydrodynamics. In the long-wavelength regime, black hole dynamics can be related to fluid dynamics and one can develop effective theories which capture the hydrodynamical description of such black holes. We review two of these: the fluid/gravity correspondence and the blackfold approach. We have hence learnt that black holes behave as fluids under certain circumstances. One can therefore compute the effective stress energy tensor associated to the fluid, extract the corresponding dissipative transport coefficients and possibly perform a stability analysis. In Chapter 3, we have introduced the AdS/Ricci flat correspondence, which is a relation between a class of AdS spacetimes and Einstein solutions with zero cosmological constant. Remarkably, we have developed an extension of such correspondence to spacetimes with positive cosmological constant, including scalar matter. This AdS/dS correspondence may possibly give hints to improve our understanding of holography in dS space. We have also found a new Kerr/AdS solution with hyperbolic horizon from a known Kerr/dS one through the map. The hydrodynamics of fluids using the KK dimensional reduction was studied in Chapter 4. Choosing a generic relativistic fluid, performing a boost in N internal dimensions, compactifing them and reducing on an N dimensional torus we have obtained a charged fluid with N charges. Therefore, we have investigated the variation of the transport coefficients, the shear and bulk viscosity, of the original theory and we were also able to compute the thermal conductivity. The same analysis has been applied to a particular fluid: the fluid dual to a black p-brane. We were able to compute the shear viscosity, bulk viscosity and thermal conductivity matrix for a black p-brane with N charges in the compact directions. This method is particularly interesting since it allows studying the hydrodynamics of charged objects without performing a perturbative analysis but only applying dimensional reduction techniques. Using the AdS/Ricci flat correspondence we have checked that our mapped transport coefficients coincide with the ones obtained for a known charged AdS black branes. In Chapter 5 we have investigated the hydrodynamics properties of fundamentally charged (dilatonic) black branes and branes with Maxwell charge smeared over their worldvolume. We have determined the dissipative behavior of the effective fluids associated to those branes in terms of the transport coefficients of the effective stress energy tensor. Studying the response to small long-wavelength perturbations we have analyzed the dynamical stability of both classes of charged black branes. We have moreover modified the AdS/Ricci flat correspondence to include charged cases using a non-diagonal KK reduction. In this thesis we have shown how higher dimensional gravity is surprisingly rich of new phenomena and bizarre features. Playing with spacetime dimension is the key to probe GR. Hopefully, we will able to improve our comprehension of this mysterious and powerful theory. Holography is an extremely useful tool available for this aim. Mapping apparently unrelated theories living in different number of dimensions has revealed various successful predictions and results but above all opens new perspective for our perception and understanding of GR. / Esta tesis se centra principalmente en el estudio de la gravedad en dimensiones superiores con un enfoque en las relaciones entre diferentes tipos de espaciotiempo y el análisis y caracterización de agujeros negros. Para este último objetivo hemos desarrollado y adaptado teorías efectivas que nos permiten estudiar la dinámica de agujeros negros en ciertos regímenes. Hemos presentado dos de ellas: la "fluid/gravity correspondence" y el metodo de "blackfold". Se puede demostrar entonces que los agujero negros admiten una descripción hidrodinámica y se puede calcular el tensor energía-impulso asociado al fluido dual al agujero negro y extraer los coeficientes de transporte al primer orden en derivadas. Hemos utilizado estas técnicas para analizar propiedades hidrodinámicas de branas negras en el caso en que las branas llevan cargas de diferentes tipos. En particular, consideramos los casos en que la brana negra está acoplada a un potencial de (p+1)-forma, que llamamos brana con carga fundamental, y brana acoplada a un campo de Maxwell. También hemos investigado las propiedades de estabilidad de estos sistemas hidrodinámicos . Otra línea de investigación es el estudio de la hidrodinámica de fluidos utilizando la reducción dimensional de Kaluza Klein. Empezamos considerando un fluido genérico y luego hemos particularizado el cálculo al fluido dual a una p-brana negra. Hemos investigado como varían los coeficientes de transporte de la teoría inicial como la "shear and bulk viscosity" y además hemos conseguido calcular la matriz de conductividad térmica. Como último proyecto hemos desarrollo mapas entre espaciotiempos diferentes. En particular hemos extendido el "AdS/Ricci-flat correspondence" para espacios de Einstein con curvatura positiva y negativa. Una vez derivado el mapa, lo hemos aplicado a espacios de Sitter (dS) y AdS y a agujeros negros de Schwarzschild-dS/AdS. Además, hemos estudiado perturbaciones en la frontera de AdS, que a través del mapa nos dan sugerencias sobre una posible construcción de holografía en espacio de dS. De hecho, la frontera de un espacio asintóticamente AdS se mapea en una brana en el centro de dS y las perturbaciones cerca de la frontera tienen como fuente un tensor energía-impulso confinado en esta brana.

En términos generales, la flexoelectricidad es la respuesta de la polarización a un gradiente de deformación. A diferencia del efecto piezoeléctrico, este efecto está presente en todos los materiales independientemente de su estructura cristalina. En esta tesis doctoral, hemos estudiado la polarización inducida por deformación en cristales dieléctricos y semiconductores, la cual surge desde dos mecanismos: flexoelectricidad macroscópica y flexoelectricidad superficial. Los dos mecanismos son del mismo orden en dieléctricos normales y hasta ahora sus respectivas contribuciones han sido indistinguibles entre ellas. La investigación desarrollada en esta tesis muestra que es posible separar las dos contribuciones, además de mostrar que la deformación induce reorientación de las nanoregiones polares las cuales también pueden incrementar el coeficiente flexoelectrico efectivo sobre el valor intrínseco. La polarización puede ser generada por la separación de las cargas enlazadas entre los átomos o la celda unidad, pero también por la separación de cargas superficiales debido a las cargas libres. Hasta ahora cuando se refiere a flexoelectricidad, únicamente es tomada en cuenta la respuesta de las cargas enlazadas; sin embargo, en esta tesis doctoral se ha reportado que la polarización debida a las cargas libres también pueden contribuir, generando una gran respuesta flexoeléctrica efectiva en materiales semiconductores. Antes de esta investigación, habían numerosas controversias respecto a la verdadera magnitud del coeficiente flexoelectrico y el origen de la discrepancia entre los valores predichos teóricamente y experimentalmente. En el presente trabajo hemos buscado dilucidar esta situación y cuantificar el valor intrínseco del coeficiente flexoelectrico e identificar el origen de contribuciones adicionales a este. El mensaje principal de esta tesis es que el coeficiente macroscópico flexoeléctrico efectivo permanece en valores relativamente pequeño con un riguroso límite superior de f ≈ 10V para el coeficiente de flexoacoplo de incluso los mejores materiales, pero hay otra gran cantidad de fenómenos de polarización inducida debida a gradientes de deformación que pueden incrementar la respuesta total de este: nanoregiones polares, piezoelectricidad superficial y movimiento de cargas libres son las tres que hemos identificado, pero no descartamos la existencia de otras. Entre estos, la incorporación de cargas libres a la respuesta flexoeléctrica total en semiconductores es cuantitativamente la más grande y la más prometedora dando lugar a aplicaciones macroscópicas debida a su elevada magnitud del coeficiente flexoeléctrico y permitiendo a su vez que compita con la piezoelectricidad. / In general terms, flexoelectricity is the response of polarization to a strain gradient. In contrast to the piezoelectric effect, this effect is present in all materials regardless of their crystal structure. In this doctoral dissertation, we studied the bending-induced polarization in dielectric and semiconductor single crystals that arises from two mechanisms: bulk flexoelectricity and surface flexoelectricity. Both mechanisms are of the same order in ordinary dielectrics and, before this work, their respective contributions were considered indistinguishable one from another. The research in this thesis shows that it is possible to separate the two contributions. Additionally, we show that bending-induced reorientation of polar nanoregions can also enhance the effective flexoelectric coefficients well above the intrinsic value. Polarization can be generated by dielectric separation of bound charge within atoms or unit cells, but also by a space charge separation of free carriers. Until now, when referring to flexoelectricity, only the response from bound charge was taken into account; however, in this thesis dissertation we report that free charge also can also contribute, generating very big effective flexoelectric responses in semiconductor materials. Before this research, there were numerous controversies regarding the true magnitude of flexoelectricity and the origin of discrepancies between theoretically predicted values and actual experimentally measured ones. The present work has seeked to address this situation by quantifying the true value of the intrinsic flexoelectiricy and identifying the origin of additional contributions. The take-home message from this thesis is that true bulk flexoelectricity remains a relatively small effect with a stringent upper bound of f ≈10V for the flexocoupling coefficient of even the best materials, but that there are a number of other gradient-induced polarization phenomena that can greatly enhance the total response: polar nanoregions, surface piezoelectricity and movement of free charges are the three we have identified, but we do not discard the existence of others. Among these, the incorporation of free carriers to the total flexoelectric response in semiconductors is quantitatively the largest, and it also offers most promising route to elevating flexoelectricity to a level where it can compete with piezoelectricity even in bulk applications.

The main objective of this thesis is the development of Raman scattering based methodologies for the analysis of advanced electrodeposition-based CIGS technologies, with the identification and characterization of parameters relevant for the efficiency of the solar cells and modules that can be used for quality control and process monitoring applications. The work aims to propose methodologies and tools that can be implemented for the monitoring of the processes at on-line level, contributing to increase the yield and reliability of the processes involved in the fabrication of these devices. The thesis is structured around five papers that have been published in peer-reviewed journals, according to the requirements for the achievement of the degree of Doctor in the Doctoral Program of Engineering and Advanced Technologies in the University of Barcelona. The thesis is structured in seven chapters. The first chapter is an introduction into Chalcopyrite photovoltaic technologies, including their background, current production strategies and optical characterization by Raman scattering based techniques. The main processes used for the fabrication of the CIGS solar cells and modules are described. Later in the introduction Raman scattering is presented as the main technique used in this work and the approach of this thesis to develop process monitoring techniques to assess parameters for each of the layers in the devices is described. Raman spectra are sensitive to chemico-physical and structural parameters of the layers that determine the device efficiency, as the crystalline quality and presence of defects, the chemical composition, as well as stress and strain effects and presence of secondary phases. The second chapter is dedicated to the disclosure of the Raman experimental set-ups that have been developed and that have been used to obtain the data presented in this work and the experimental conditions chosen to ensure reliability in the measurements. A more detailed description of the application of Raman spectroscopy are disclosed in the following chapters, that address the detection of secondary phases in the absorber layers that are relevant for device performance in high efficiency devices (Chapter 3), the chemical characterization of the surface region of the absorbers (Chapter 4), the assessment of the thickness of the CdS buffer layers (Chapter 5) and the electrical conductivity of the window layers (Chapter 6). The secondary phases studied in Chapter 2 are the OVC ones in Cu(In,Ga)Se2 alloys and CuAu polytypes in CuInS2 based cells; determining and clarifying their impact on the optoelectronic characteristics of the cells. This work reports for the first time in the literature clear experimental evidences of the impact of the presence of the OVC phases on the optoelectronic characteristics of the cells. Although the efficiencies achieved within CuInS2 (CIS) solar cells are lower (12.7% ) than the yielded by CIGS devices, the larger bandgap of the CIS semiconductor (1.55 eV) gives interest to these devices for the increase of the open circuit voltage Voc. In this work, the role of the presence of CuAu polytypic domains in advanced cells made by electrochemical processes is investigated. The fourth chapter addresses the development of methodologies for the quantitative analysis of the chemical composition of the surface region of the absorber layers, including the Ga/(In+Ga) relative content in Cu(In,Ga)Se2 absorbers and the S/(S+Se) relative content in Cu(In,Ga)(S,Se)2 absorbers. These are the parameters that allow suitable control of the value of the band gap in the surface region of the absorbers. Next chapters address the Raman scattering assessment of the CdS buffer and Al-doped ZnO window layers, being the control of the thickness of the buffer and conductivity of the window layer are relevant for the device efficiency. The final chapter summarizes the main conclusions / El principal objetivo de esta tesis es el desarrollo de metodologías basadas en la espectroscopia Raman para el análisis de tecnologías fotovoltaicas Cu(In,Ga)(S,Se)2 avanzadas basadas en procesos electroquímicos, con la identificación y caracterización de parámetros relevantes para la eficiencia de las celdas solares y módulos. El trabajo desarrolla y propone metodologías y herramientas que pueden ser implementadas para aplicaciones de control de calidad y monitorización de procesos a nivel "on-line", contribuyendo a incrementar el rendimiento y la fiabilidad de los procesos involucrados en la fabricación de estos dispositivos. La tesis está estructurada en siete capítulos. El primer capítulo es una introducción a las tecnologías fotovoltaicas de la calcopirita, incluyendo las estrategias actuales de producción y su caracterización óptica por medio de técnicas basadas en espectroscopia Raman; más tarde en el capítulo se presenta la espectroscopia Raman como la técnica principal utilizada en el trabajo y se describe el enfoque abordado en la tesis para el desarrollo de técnicas para la monitorización de los procesos. Los espectros Raman permiten obtener información de parámetros estructurales y químico-físicos de las diferentes capas en la estructura que determinan la eficiencia del dispositivo, como la calidad cristalina y presencia de defectos, composición química, estrés y presencia de fases secundarias. El Segundo capítulo describe los sistemas experimentales que se han desarrollado en el trabajo, y las condiciones experimentales determinadas para garantizar la fiabilidad de las medidas. Una descripción más detallada de la aplicación de la espectroscopia Raman se describe en los siguientes capítulos, que abordan la detección de fases secundarias en la capa del absorbedor que son relevantes para la eficiencia de la celda en dispositivos de alta eficiencia (Capítulo 3), la caracterización química de la región superficial de las capas absorbedoras (Capítulo 4), el espesor de las capa buffer de CdS (capítulo 5) y la conductividad eléctrica de las capas ventana (capítulo 6). El último capítulo de la tesis resume las principales conclusiones del trabajo.

The present thesis deals with a deep analysis of the genetic structure of extant human worldwide populations, with a special focus on the Mediterranean. Different genetic markers, 18 Alu insertions and 367 single nucleotide polymorphisms (SNPs), were analysed for the first time in general populations and Bedouins from Jordan. The same SNPs were also genotyped in a consistent set of samples from the Mediterranean Basin. Specifically, Alu markers were used to assess the genetic diversity within Jordan and to define the relationships across present-day Middle Eastern, North African, and European populations. While SNPs located in the top coronary artery disease (CAD) risk regions (1p13, 1q41, 9p21, and 10q11) were used to explore the genetic variation and the LD patterns across 19 populations from Europe, Middle East and North Africa, together with Asian and African samples from the 1000 Genomes Project. Furthermore, Tunisian and Moroccan case-control samples were used to test for the first time the applicability of European GWAS results in these four genomic regions to North African populations. Finally, simulated genomic data were used to evaluate the consistency of association results across European, Asian and Sub-Saharan African case-control samples. Neutral and CAD risk markers pointed out a low but significant geographic structure in the Mediterranean area. As a particular case in the Mediterranean context, Bedouins and general population from Jordan showed statistical differences (p=0.038). The genetic heterogeneity detected is likely related to the fact that urban areas have been subject to several external influences but Bedouins have preserved their own genetic background because of their nomadic and isolated lifestyle. The general patterns of genetic variation observed in the four CAD risk regions analysed are in agreement with the genetic structure generated by demographic processes. Despite this fact, the present work also identified potential signals of positive and balancing selection in some specific risk markers and haplotypes. Actually, potential signatures of positive selection in the 9p21 region and of balancing selection in 9p21 and 10q11 have been observed. The regions under positive or balancing selection are shared across continents but the specific markers under selection are, in some cases, continent-specific. Results from the association study in North Africa revealed significant association signals in the four genomic regions analysed in Moroccan and Tunisian samples confirming the trans-ethnic importance of these genomic regions for the risk of CAD. However, in the meta-analyses performed with the North African case-control samples, only the 9p21 and 10q11 regions showed association signals and none of the North African risk SNPs was associated with CAD in Europe. These arguments suggest the existence of continent-specific CAD risk variants in these chromosomal regions. Significant differences in the LD and in the haplotype patterns confirm the heterogeneity in the genomic structure between North Africans and Europeans. In addition, differences in the LD structure persist even across Europeans, North Africans, Asians, and Sub-Saharan Africans. Finally, the simulation study highlighted an overall consistency in effect direction across populations of different ancestry, specially between Europeans and Asians. Because simulations assumed no actual differences in genetic effect size between populations and because the rate of between-population effect size differences generated by our study was considerably lower than the rate reported from empirical studies using real data, our study supports the existence of real differences in the genetic risk architecture of complex traits between populations. In general, this study confirmed that a substantial fraction of association signals are shared across people of different ancestries. However, some discrepancies in the effect size across populations highlighted the importance of accounting for population structure in association studies. / Esta tesis analiza la variación genética de muestras poblacionales europeas, africanas y asiáticas, con particular énfasis en la región mediterránea. Se usaron 18 marcadores Alu para evaluar la diversidad genética dentro de Jordania (en beduinos y en población general) y para definir la relación entre las actuales poblaciones del Mediterráneo. Por otra parte, 367 polimorfismos de un solo nucleótido (SNPs) localizados en cuatro regiones de riesgo para la enfermedad arterial coronaria (CAD) (1p13, 1q41, 9p21 y 10q11) se utilizaron para explorar la variación genética en 19 poblaciones de Europa, Oriente Medio y África del Norte, junto a las muestras asiáticas y africanas del Proyecto 1000 Genomas. Estas cuatro regiones de riesgo CAD fueron analizadas también en un conjunto de muestras de casos y controles de Marruecos y Túnez. Por último, se simularon muestras de casos y controles africanos, europeos, y asiáticos para evaluar el nivel de consistencia interpoblacional en los estudios de asociación. Como caso particular en el Mediterráneo, los beduinos y la población general de Jordania mostraron diferencias significativas (p=0,038). Los beduinos se agruparon con los norteafricanos, mientras que los jordanos generales se agruparon con las poblaciones más orientales del Mediterráneo. Los patrones generales de variación observados en las cuatro regiones de riesgo CAD mostraron una estructura genética plausiblemente modelada por procesos demográficos. A pesar de esto, el presente trabajo también detectó señales potenciales de selección natural positiva en la región 9p21 y de selección equilibradora en las regiones 9p21 y 10q11. También fueron detectadas asociaciones significativas en las cuatro regiones genómicas analizadas, previamente identificadas en europeos, en Marruecos y Túnez. Sin embargo, sólo las regiones 9p21 y 10q11 mostraron asociación en el meta-análisis realizado utilizando las muestras de casos y controles norteafricanos. El estudio de simulación destacó una alta replicabilidad de las señales de asociación entre los distintos continentes. Sin embargo, algunas discrepancias en el tamaño del efecto revelaron la posible existencia de diferencias interpoblacionales en la arquitectura del riesgo genético de caracteres complejos y destacaron la importancia de incluir la estructura poblacional en los estudios de asociación.