Tesi realitzada a l'Institut de Microelectrònica de Barcelona (IMB-CNM-CSIC) / We have characterized electroluminescent devices based on silicon rich oxide and/or silicon rich nitride. We have discussed the photoluminescence and structural characterization of the active layers and the electrical and electroluminescent characterization of full devices. We have noted that the electroluminescence can appear in the form of discrete points scattered across the active area of the devices, in the form of emission along the rim of the active area, or homogeneously distributed across the area. These different kinds of emission have been related to the optical and electrical properties of the devices. In the two former cases, the electroluminescence comes with high current densities,of the order of 1 A/cm2, and low efficiencies of the order of 10-8. On the other hand, the homogeneous emission comes with lower current densities, of the order of 0.01 A/cm2, and better efficiencies, in the range 10-7–10-5. We have concluded that the homogeneous emission is optimal in terms of efficiency. Furthermore, a simple model has been proposed to explain the appearance and occasional coexistence of the different kinds of emission. The effect of a nitride layer on top of the SRO has been explored, concluding that it helps in achieving a uniform conduction that favors the homogeneous emission in the active layer. The conductivity states of the active layer associated with the different kinds of emission have been related with its CV behavior. The results of the study show that the homogeneous emission corresponds to well behaved CV curves, whereas the emission through points does not. The injection mechanisms in PECVD and ion implanted samples have been studied, concluding that no single emission mechanism can account for the injection at all regimes in the studied range of electric fields. Fowler-Nordheim or trap assisted tunneling have been found to play a significant role in PECVD samples. In implanted samples, Fowler-Nordheim dominates at low fields, whereas Poole-Frenkel is more likely to be the dominant mechanism at higher fields. Comparison of the photoluminescence and electroluminescence spectra of bilayers SRO/SRN, allows us to conclude that each layer contributes a different band in the total emission, which results in a wider distribution of the energy across the visible spectrum. The comparison between the photoluminescence and electroluminescence has revealed massive differences in their spectra, which have been attributed to interference effects. A computer software based in the Crawford method for the study of the interference effects in multilayer stacks has been presented. The program has been used to quantitatively study the interference effects in the emission of our devices. We can conclude that the photoluminescence and electroluminescence spectra are the same despite their apparent difference. Our analysis has also made it apparent that a quantitative understanding of the interference effects in the system is important in order to draw valid conclusions regarding the origins of the luminescence. We have presented the design, fabrication and characterization of a CMOS compatible optical transceiver, and two main challenges in the integration of the emitter, waveguide and detector have been successfully overcome, namely achieving a reasonably flat and uniform silicon oxide trench and a good detector. In the end, the transceiver has not worked as expected, most likely due to a poor SRN emitter. More work is required in order to better control the fabrication process of the SRN layers. However, we believe the basic design to be valid, given the low electrical coupling detected between the emitter and the detector components of the transceiver. / Aquesta tesi presenta un estudi de les propietats òptiques de capes d'òxid de silici enriquit en silici (SRO) i nitrur de silici enriquit en silici (SRN) que han sofert un procés tèrmic d'alta temperatura. Aquest procés indueix la creació de nanoaglomerats de silici en la matriu dielèctrica. Aquestes nanoestructures de silici presenten una superior eficiència en l'emissió respecte al silici en bloc, i a més a més emeten en el visible en comptes de l'infraroig. Això és interessant per a l'obtenció de dispositius fotònics integrats basats en silici que poden ser fabricats monolíticament en un procés compatible amb la tecnologia CMOS que domina la indústria microelectrònica. A més a més, hem estudiat les propietats òptiques i elèctriques de dispositius metall-aïllant-semiconductor en les quals l'aïllant és una capa d'SRO o SRN amb nanoaglomerats de silici. N'hem mesurat paràmetres d'interès com ara l'eficiència de conversió d'energia elèctrica-òptica o la potència òptica, i n'hem estudiat els mecanismes d'injecció que hi tenen lloc. S'han identificat tres tipus diferents d'emissió: per punts, per la vora del dispositiu, i emissió homogènia, i hem determinat que l'emissió homogènia és la més adecuada pel que fa a l'eficiència dels dispositius. Hem desenvolupat un programa que permet el càlcul de les interferències òptiques que tenen lloc als sistemes multicapa que conformen els dispositius estudiats, i que distorsionen l'espectre observat respecte al que les capes realment emeten. L'habilitat de poder calcular aquests efectes ens permet, en molts casos, eliminar l'efecte de les interferències i determinar l'autèntic espectre d'emissió de les capes i per tant estar en millors condicions d'assignar l'emissió als mecanismes correctes. Finalment, hem proposat un prototip per a un transceptor en el qual l'emissor, la guia d'ones i el detector estan integrats monolíticament en un procés CMOS. Hem fabricat el dispositiu i l'hem caracteritzat. Tot i que no hem aconseguit acoblament òptic entre l'emissor i el detector, creiem que el disseny bàsic queda validat, ja que els principals obstacles en l'obtenció del dispositiu han sigut superats amb èxit.

Mercury (Hg) is naturally present in the Earth’s crust, however the historical use of this metal by the human being has spread and increased its presence in the environment. Both inorganic and organic species can be found in aquatic ecosystems, which are very sensitive to Hg pollution. In anoxic waters and sediments, sulphate-reducing bacteria can convert inorganic Hg into methylmercury (MeHg), a very toxic organic form which has the ability to bioaccumulate and biomagnify throughout trophic chains. Thus, to assess the risk associated to Hg pollution, the development of techniques to monitor Hg levels in water is necessary, as well as investigating MeHg elimination pathways. In this doctoral thesis, two aspects related to the biogeochemical cycle of Hg in freshwater were addressed. On one hand, a passive sampling technique –Diffusive Gradients in Thin films (DGT)– was developed both for determination of total Hg (THg) and MeHg in freshwater. Apart from providing a time-average Hg concentration, these samplers are able to measure the labile fraction of Hg, since they supposedly mimic biological membranes. Thus, the DGT technique is considered a good monitoring tool to estimate the bioavailability of Hg in water. On the other hand, MeHg photodegradation in freswhwaters dominated by dissolved organic matter (DOM) was studied. Regarding the DGT technique, several preliminary tests were carried out both at the laboratory and in the field to test the validity of a commercial type of samplers to measure the labile dissolved Hg in continental waters. Later, the performance of this commercial type was compared to that of two in-house manufactured samplers; both of them with the same receiving gel consisting of a resin with 3-mercaptopropyl groups embedded in a polyacrylamide gel, but one with an agarose gel (A-DGT) and the other with polyacrylamide gel (P-DGT) as the diffusive layer. The uptake kinetics of Hg(II) and MeHg, both in the absence and in the presence of DOM, were studied. The diffusion coefficient, D, of Hg in the DGT diffusive layer varied among Hg species and also depended on the absence/presence of DOM in the solution. This confirms the need to use the Hg species of interest and simulate the characteristics of the water to be sampled when performing the DGT calibration if the aim is to accurately measure the labile Hg fraction. The P-DGT was chosen as the most appropriate to determine both THg and MeHg in natural waters. Thereby, this type of sampler was used in a case study to assess the removal, methylation and lability of Hg(II) in a experimental scale plant for wastewater treatment consisting in several constructed wetlands with different conformation in series. With respect to the MeHg photodegradation issue, this phenomenon was studied in waters from a lake-wetland gradient in the boreal Sweden. The influence of DOM on this process by attenuating light, forming reactive oxygen species and binding MeHg to its thiol groups to form complexes, was examined. It was observed that the desmethylation rate constant (kpd Full Spectrum) varied significantly among the three studied waters, but the wavelength-specific rate constants (kpdPAR, kpdUVA and kpdUVB) were indistinguishable. Therefore, kpd PAR, kpd UVA and kpd UVB can be considered universal, at least in waters dominated by DOM and in which MeHg is complexed by organic thiols, if the photon fluxes of PAR, UVA and UVB radiation are separately determined and the wavelength-specific light attenuation by DOM is corrected for. Furthermore, the relationship between the photodegradation and bioavailability of MeHg was examined in an experiment involving different types of natural and artificial freshwater, but no apparent connection was observed between them. / En aquesta tesi doctoral s'aborden dos aspectes relacionats amb al cicle biogeoquímic del Hg en aigües continentals. Per una banda, es va desenvolupar un sistema de mostreig passiu denominat gradients de difusió en capa fina (DGT), per la determinació del Hg total i del MeHg en fase aquosa. Aquests mostrejadors proporcionen la concentració mitjana de Hg durant el temps de mostreig i mesuren la fracció làbil de Hg. Per tant, la tècnica de DGT pot ser considerada una bona eina per avaluar la biodisponibilitat de Hg a l’aigua. D'altra banda, es va estudiar la fotodegradació de MeHg en aigües continentals. Pel que fa a la tècnica DGT, es van dur a terme diverses proves preliminars tant al laboratori com en el camp per provar la validesa d'un tipus comercial de mostrejador per mesurar el Hg dissolt i col•loidal làbil en aigua dolça. Aquest es va comparar amb dos tipus de mostrejadors DGT manufacturats al laboratori (A-DGT i P-DGT). Es van estudiar les cinètiques d’acumulació de Hg(II) i MeHg tant en absència com en presència de DOM. El P-DGT va ser escollit com el més apropiat per determinar ambdós THg i MeHg en aigües naturals i va ser utilitzat en un estudi de cas per avaluar l'eliminació, metilació i labilitat de Hg(II) en una aiguamoll construït a escala experimental pel tractament d’aigües residuals urbanes. La fotodegradació de MeHg va ser estudiada en aigües d'un gradient llac-aiguamoll en la Suècia boreal; i es va evaluar la influència de DOM en el procés. Es va observar que la constant de velocitat de fotodesmetilació (kpd Full Spectrum) va variar significativament entre les aigües estudiades, però les constants específiques per a cada longitud d'ona (kpdPAR, kpdUVA and kpdUVB) van ser indistingibles. Per això, kpdPAR, kpdUVA and kpdUVB poden ser considerades universals en aigües amb un alt contingut en DOM i on el MeHg estigui complexat per grups tiol orgànics. Finalment, amb la utilització de la tècnica DGT es va estudiar la possible influència que pot existir entre la fotodegradació i la biodisponibilitat de MeHg en diversos tipus d'aigues dolces naturals i artificials, però no es va observar cap connexió aparent entre elles.

Tesi realitzada a l'Institut de Diagnosi Ambiental i Estudis de l'Aigua (IDAEA - CSIC) / In the past two decades we witnessed a decrease in both the number of oil spill incidents, and of the quantity of oil released in these incidents, which led to a diminished interest for basic oil spill science. With the introduction of more stringent oil spill legislation, much of the spill response, assessment and restoration activities were passed to governmental agencies and other stakeholders. Their capabilities were perhaps sufficient to deal with the most frequently occurring small-scale spills, however, recent large, catastrophic incidents such as the sinking of Prestige in 2002, or the Deepwater Horizon blowout in 2010, renewed the need for fundamental science in order to be able to fully understand and estimate the scope of the impacts such spills can have on the environment, economy and society. This is particularly important in the context of new explorations and discoveries of hydrocarbon resources in pristine regions such as Arctic, where extreme weather and the lack of infrastructure emphasize even more the need for a comprehensive assessment of all of the possible effects the future oil production could cause. The objectives of this thesis were set to provide new approaches and methodologies, and to improve and reevaluate the previously existing ones, in a way which can contribute to this comprehensive and proactive strategy. Their scope is comprehensive because it covers all the important aspects of marine oil spills – the sources, environmental fate and possible toxic effects. In addition, particular relevance of this thesis is drawn from the fact that the studies presented here include the investigation of real major oil spills (Prestige, DWH), and of a broad range of oils and oil products that are currently produced and transported worldwide. In order to fulfill the abovementioned general objectives, the following specific objectives had to be accomplished: Firstly, a physicochemical database of frequently transported crude and refined oils was created using elemental analysis, thin-layer liquid chromatography (TLC) with flame ionization detector (FID) analysis of principal oil compound groups, gas chromatography-mass spectrometry (GC-MS) fingerprinting of polycyclic aromatic hydrocarbons (PAHs) and biomarkers, and available oil assays. This database was then applied to assess their possible fate in the case of a spill, and to model three spill scenarios in different European regional seas using ADIOS2 software from NOAA (National Oceanic and Atmospheric Administration). Fingerprints of selected oils were assessed and statistically compared to discover the most relevant compositional differences that could facilitate the identification of oil spill sources. Secondly, the GC-MS methodology used to create the fingerprint database of selected oils was evaluated in an international interlaboratory ring test. The objective was to test the capability of this fingerprinting methodology to identify the type and source of weathered (biodegraded) oil samples. Thirdly, the weathering of oil samples from Prestige and Deepwater Horizon spills, in particular the photooxidation, was studied. Samples weathered in field and in laboratory experiments were analyzed using TLC-FID, GC-MS, comprehensive two dimensional gas chromatography (GCxGC) with FID, and Fourier transform infrared spectrometry (FT-IR) to discover compositional changes on the bulk level as well as on the molecular level. PAHs and triaromatic steranes (TAS) were of particular interest, as well as the effects of the photooxidation on the robustness of the oil fingerprinting methodology. Finally, the effects of selected fresh and weathered (evaporated, photooxidized) crude and refined oils were studied, using the effect-directed analysis (EDA). The samples were sequentially fractionated using open-column liquid chromatography and normal-phase semipreparative HPLC, and the obtained fractions were subjected to bioassays to test their AhR agonist and AR antagonist activity. The most active fractions were then analyzed using GCxGC coupled to time-of-flight mass spectrometry (TOFMS), and this data was related to bioassay results using N-way partial least square (N-PLS) chemometric model, in order to identify the compounds responsible for the observed effects. / A pesar de las tendencias positivas en las últimas décadas, los vertidos ocasionados por la exploración, extracción y transporte de petróleo siguen siendo una importante amenaza para los ecosistemas marinos y especialmente costeros. Esta Tesis se ocupa de todos los aspectos importantes sobre los vertidos marinos de petróleo: el origen, el destino ambiental y sus posibles efectos. Para permitir su comprensión global, se utilizaron diferentes metodologías complementarias. En primer lugar, se ha creado una base de datos físico-químicos de diferentes petróleos (crudos y refinados) que se transportan frecuentemente usando el análisis elemental, la cromatografía en capa fina (TLC) acoplada a un detector de ionización de llama (FID) de los principales grupos de compuestos de petróleo, la toma de huellas químicas de los hidrocarburos aromáticos policíclicos (HAP) y los biomarcadores mediante cromatografía de gases acoplada a espectrometría de masas (GC-MS), y ensayos de petróleo disponibles. A continuación, se aplicó esta base de datos para evaluar su posible destino en el caso de un vertido, y para modelar tres escenarios de vertidos en diferentes mares regionales europeos usando el software ADIOS2 de la Administración Nacional Oceánica y Atmosférica (NOAA). Las huellas químicas de los petróleos seleccionados fueron evaluadas y comparadas estadísticamente para investigar las diferencias de composición más relevantes que podrían facilitar la identificación del origen de vertido. En segundo lugar, la metodología de GC-MS utilizada para crear la base de datos de las huellas químicas de los petróleos seleccionados se ha evaluado en una prueba interlaboratorio internacional. El objetivo fue investigar la capacidad que tiene esta metodología de toma de huellas químicas para identificar el tipo y el origen de las muestras envejecidas (biodegradadas) de petróleo. En tercer lugar, se ha estudiado el envejecimiento de las muestras de petróleo de los vertidos de Prestige (2002) y de la plataforma Deepwater Horizon (2010), en particular, debido a la fotooxidación. Se analizaron muestras envejecidas en el campo y en experimentos de laboratorio mediante TLC-FID, GCMS, cromatografía de gases bidimensional integrada (GCxGC) acoplada a un FID, y espectroscopia infrarroja por transformada de Fourier (FT-IR) para investigar los cambios de composición tanto a nivel global como a nivel molecular. Los HAP y esteranos triaromáticos fueron de especial interés, así como los efectos de la fotooxidación en la robustez de la metodología de toma de huellas químicas de petróleo. Finalmente, se estudiaron los efectos de las muestras no tratadas y envejecidas (evaporadas, fotooxidadas) de los petróleos crudos y refinados seleccionados, utilizando el análisis dirigido por los efectos tóxicos (EDA). Las muestras se fraccionaron secuencialmente usando la cromatografía líquida en columna abierta y la cromatografía líquida de alta eficacia (HPLC) semipreparativa en fase normal. Las fracciones obtenidas se sometieron a bioensayos para investigar su actividad agonista de los receptores AhR y la actividad antagonista de los receptores AR. En el siguiente paso, las fracciones más activas fueron analizadas mediante GCxGC acoplada a espectrometría de masas en tiempo de vuelo (TOFMS), y estos datos se relacionaron con los resultados de los bioensayos utilizando un modelo quimiométrico de regresión por mínimos cuadrados parciales en N direcciones (N-PLS), con el fin de identificar los compuestos responsables de los efectos observados.

Tesi realitzada a l'Institut de Ciències de la Terra “Jaume Almera” (ICTJA-CSIC) / This thesis is organized as a compendium of three scientific articles, describing the geological characterization of the Hontomín site for Geological Storage of CO2 by means of 3D seismic data, acquired for this purpose, as well as the available well-log and regional data. The three articles form the core of this thesis and constitute the main scientific effort developed therein. These are: • Alcalde, J., Martí, D., Calahorrano, A., Marzán, I., Ayarza, P., Carbonell, R., Juhlin, C. and Pérez-Estaún, A. 2013a. Active seismic characterization experiments of the Hontomín research facility for geological storage of CO2, Spain. International Journal of Greenhouse Gas Control, 19, 785-795. • Alcalde, J., Martí, D., Juhlin, C., Malehmir, A., Sopher, D., Saura, E., Marzán, I., Ayarza, P., Calahorrano, A., Pérez-Estaún, A., and Carbonell, R. 2013b. 3D Reflection Seismic Imaging of the Hontomín structure in the Basque-Cantabrian Basin (Spain). Solid Earth4, pp. 481-496. • Alcalde, J., Marzán, I., Saura, E., Martí, D., Ayarza, P., Juhlin, C., Pérez-Estaún, A., and Carbonell, R. 2014. 3D geological characterization of the Hontomín CO2 storage site, Spain: multidisciplinary approach from seismics, well-logging and regional data. Tectonophysics (accepted). The thesis begins with an Introduction (Chapter I), in which the motivations and aims of the thesis are presented. These include the problematic derived from anthropogenic emissions of CO2, and present Carbon Capture and Storage technology as an effective method to reach energetic sustainability. This chapter also includes the state-of-the-art seismic reflection method applied to CO2 storage, as well as an outline of the regional and local geology of the study area. The first article (Alcalde et al., 2013a) constitutes Chapter II of the thesis. It presents and describes the active seismic experiments conducted at the Hontomín site for the seismic characterization. The data acquisition is described in detail, with an emphasis on the most relevant factors that affected the quality of the acquired data. These factors include the geomorphological/topographical aspects of the study area, logistical issues during the acquisition. The effects on the seismic records of a near-surface velocity inversion are also discussed. This contribution also shows a preliminary seismic image of the subsurface, which allows outlining the general dome shape of the target structure. The second article (Alcalde et al., 2013b) comprises Chapter III of the thesis. It outlines the processing applied to the seismic data that led to the final migrated seismic image. It includes a detailed discussion about which processes were more effective in enhancing the quality of the obtained image. The image was judged to be suitable for interpretation and constitutes the primary seismic model, to be used as reference baseline during the monitoring stage. Furthermore, the top of the Jurassic dome structure was mapped, allowing us to provide an overall estimation of the size of the target structure, which is a 107 m2 elongated dome with a maximum CO2 storage capacity of 1.2 Gt. The third article (Alcalde et al., 2014), included in Chapter IV of the thesis, focuses on the interpretation of the seismic image and the building of a 3D geological model. The quality of the seismic data required a geologically driven approach to enable interpretation. This approach used a conceptual model as reference, which was inferred in the first place from the correlation of the available well-log data and later improved by the seismic facies analysis and the regional geological data. The conceptual model was used to interpret the seismic data and resulted in a 9-layered 3D geological model and a thorough description of the fault system present in the area. / Esta tesis tiene como objetivo la caracterización geológica 3D de la Planta de Desarrollo Tecnológico para el Almacenamiento Geológico de CO2 de Hontomín (Burgos). Esta caracterización se ha llevado a cabo mediante el procesado y la interpretación de datos de sísmica de reflexión 3D adquiridos para ese propósito en verano de 2010.

Programa de Doctorat en Nanociències / This project presents the study of luminescent devices and materials based on silicon for its use in the fabrication of an optical system that integrates light emitter, waveguide, and light sensor in a single chip obtained by the use of standard CMOS techniques and materials. The atomic and structural characteristics of the materials are analysed and related to its luminescent response. Taking into account the results from the active material characterization, the design, fabrication, and characterization of electroluminescent devices based on such materials is presented. Finally, the design, fabrication and characterization of a complete CMOS compatible Integrated Optical System consisting of a transceiver, is discussed and analysed. The active materials used for light emission were different Silicon Rich Silicon Dioxide(SRO) and SRO-Si3 N4 bi-layers, obtained by a variety of CMOS compatible techniques and fabrication parameters. Two contributing mechanisms to photoluminescence in SRO were identified in all cases, respectively linked to the presence of radiative defects, and to Quantum Confinement phenomena. It is proposed and tested a model to describe the latter, based on the effective mass approximation, and the relation between the amount of Si-Si links and the volume of nano-agglomerates present in the material. In bi-layer samples, an additional luminescence band was observed, found to be generated in the transition material between silicon nitride and dioxide, and related to energy states introduced by defects. Samples with SRO thickness ten times higher than that of nitride, presented a clear dominance of the photoluminescence related to the dioxide. The centres responsible for electroluminescence in the electronicd evices were found to be fundamentally the same as those for photoluminescence despite the differences in measured spectra, and it was concluded that the influence of the architecture on the light output is of significant importance. It was shown that bi-layered devices delivered better results in terms of efficiency, light emission control, distribution and stability. The carrier transport mechanisms observed in the devices were dominated by material breakdown in single-layered devices, and Trap-assisted Tunnelling in the bi-layers. The Optical System integrating the light emitter, a waveguide, and a light detector, was designed and fabricated based on the results from the fabrication and analysis of the stand alone light emitting devices. During the design stage, it was corroborated by computer simulations that the characteristics of thelight emittedby thedevices thatpresented thehighest e.ciency and reliability, were suitable for its transmission trough the pro­posed waveguide architecture. The detection capabilities of the designed light sensors were also theoretically corroborated to be appropriated for the detection of the emitted light type. The proper functioning of the elements conforming the finally fabricated system was probed. Differences were found in the operation of the stand alone light emitting devices and those integrated, but the resulting luminescence was within the boundaries of the transmittable spectrum. The operation of the Integrated Optical System was tested and preliminarily studied, obtaining positive results in its stimulus-detection response, fulfilling the main objective of the work, and opening the door for further studies which can lead to the optimization of the design for particular applications. / Este proyecto aborda el estudio de dispositivos y materiales luminiscentes basados en silicio para su uso en la fabricación de un sistema óptico que integre emisor de luz, guía de ondas, y sensor en un solo chip obtenido mediante el uso de técnicas y materiales estándar para la fabricación CMOS. Las características atómicas y estructurales de los materiales son analizados y relacionados con su respuesta luminiscente. Considerando los resultados de la caracterización del material activo, se presenta el diseño, fabricación, y caracterización de dispositivos electroluminiscentes basados en dichos materiales. Finalmente, se discute y analizan el diseño, fabricación, y caracterización de un transceptor como Sistema Óptico Integrado. Los materiales activos para la emisión de luz fueron distintos Dióxidos de Silicio enriquecidos con Silicio (SRO por sus siglas en inglés) y bi-capas SRO-Si3 N4, obtenidos mediante una variedad de técnicas compatibles con los procesos CMOS y distintos parámetros para los mismos. Se identificaron dos mecanismos que contribuyen a la fotoluminiscencia del SRO en todos los casos, relacionados con defectos radiativos y fenómenos de Confinamiento Cuántico, respectivamente. Se sugiere y pone a prueba un modelo para describir este último, basado en la aproximación de la masa efectiva y la relación entre la cantidad de enlaces Si-Si y el volumen de nano-aglomerados. En muestras bi-capa, se observó una banda adicional de luminiscencia, cuya generación fue identificada en el material de transición entre el nitruro de silicio y el óxido, y relacionada con estados de energía introducidos por defectos. Muestras con un espesor de SRO diez veces mayores a aquel del nitruro presentaron una clara dominación de la luminiscencia relacionada con el óxido. Se halló que los centros responsables por la electroluminiscencia en los dispositivos electrónicos son fundamentalmente los mismos que los responsables de la fotoluminiscencia a pesar de las diferencias en los espectros medidos, y se concluyó que la influencia de la arquitectura sobre el espec­tro de salida es de importancia significativa. Se mostró que dispositivos bi-capa entregan mejores resultados en términos de eficiencia, control sobre la luz emitida, distribución de la misma, y estabilidad en el funcionamiento. Se observó que los mecanismos de transporte de carga hallados en los dispositivos están dominados por ruptura del material en el caso de dis­positivos de una sola capa, y Tuneleo Asistido por Trampas en el caso de dispositivos bi-capa. El Sistema Óptico que integra el emisor, una guía de ondas, y el detector de luz, fue diseñado y fabricado con base en los resultados de la fabricación y análisis de los dispositivos emisores de luz aislados. Durante la etapa de diseño, se corroboró mediante simulaciones por computadora que las características de la luz emitida por los dispositivos que presentaron la máxima eficiencia y fiabilidad fueran apropiadas para su transmisión a través de la guía de ondas propuesta. También se corroboró teóricamente que las capacidades de detección de los sensores diseñados fuera la adecuada para el tipo de luz emitida. Se exploró el apropiado funcionamiento de los elementos del sistema finalmente fabricado. Se encontraron diferencias en la operación de los dispositivos emisores de luz aislados y aquellos integrados, pero la luminiscencia resultante se halló dentro de los límites del espectro transmisible. La operación del Sistema Óptico Integrado fue probada y estudiada de manera preliminar, con la obtención de resultados positivos en su respuesta estímulo-detección, cumpliendo así con el objetivo principal del trabajo, y abriendo la puerta para estudios posteriores que pueden guiar a la optimi­zación del diseño del sistema para aplicaciones particulares.

Single-molecule techniques allow to following biomolecular reactions with unprecedented resolution. Particularly, optical tweezers can be used to manipulate and apply forces to individual molecules tethered between plastic beads that are optically-trapped. Optical trapping is achieved by using highly focused laser beams that exert a gradient force onto the micrometer-sized dielectric particles that become confined close to the focal position of the laser. By specifically attaching the ends of the molecule under study to two optically-trapped beads, it is possible to manipulate and apply forces to an individual molecule. Typical experiments with optical tweezers consist in manipulating nucleic acids (DNA, RNA) or proteins one at a time. For instance DNA molecules can be stretched to measure its elastic properties, or unzipped to measure their base-pairing energies. Many small anticancer drugs target nucleic acids to exert their cytotoxic activity against cancer cells. To understand their mechanism of action it is important to know in which positions, how strong, and how fast do they bind to different specific sites in DNA. Single-molecule optical tweezers experiments can be used to unravel the binding thermodynamics and kinetics of many of these ligands, especially those difficult to characterize with bulk techniques. Thiocoraline is one of such drugs, and binds DNA through bis-intercalation. Experiments with optical tweezers show that the kinetics of intercalation are very slow (hours) and strongly force-dependent: force facilitates binding but slows down unbinding. Experiments performed in different conditions also reveal that the binding pathway proceeds through a mono-intercalated intermediate that causes the observed slow kinetics. In this sense, we present a three-state model that offers a theoretical framework from which the kinetic rates of the reaction can be extracted, and that could be useful to characterize other bis-intercalators. We also show that DNA unzipping experiments can be used to determine the preferred binding sequences of Thiocoraline, finding that it preferentially clamps CpG steps. This methodology is potentially very useful as it provides direct access to the preferred binding sites of small ligands due to its thermodynamic stability with one base pair resolution and without the requirement of restriction enzymes or radioactive labeling. This single-molecule footprinting technique is also adapted to a magnetic tweezers instrument in order to perform parallelized measurements. The fact that bis-intercalation does not modify the persistence length of dsDNA is also found in the pulling experiments. From the elasticity measurements, we also extract equilibrium quantitates of the interaction by using classic statistical models. This combination of DNA stretching and unzipping assays can also be used to follow how the anticancer agent Kahalalide F self-assembles and compacts DNA. Kahalalide F forms nanometric particles that are positively charged able to bind and condense DNA. The binding reaction shows to phases: an initial compaction of electrostatic origin, and its subsequent stiffening due to the hydrophobic collapse of the complex. The combination of quantitative force-spectroscopy measurements with AFM images of the complexes and other bulk tech- niques (DLS, EM) provides a consistent picture of the compaction and aggregation process. Modeling of the experiments provides the thermodynamic parameters of the interaction that are complemented with kinetic measurements. A simple technique to study ssDNA with optical tweezers is also presented and used to study how the stiffness of the polyanion affects the compaction process. We exploit this methodology to understand how the stiffness of the polyanion affects the compaction kinetics, and later on, we also show its utility to study the elasticity of ssDNA under varying ionic conditions. Finally, the utility of this methodology to study self-assembly and aggregation is explored with amyloidogenic peptides involved in neurodegenerative disorders. / Les tècniques de molècula individual permeten seguir les reaccions biomoleculars amb una resolució sense precedents, proveint als científics d’una sèrie d’instruments per a mesurar magnituds físiques i investigar sistemes experimentals difícilment accessibles amb les tradi­cionals mesures en volum (és a dir a on les mesures es realitzen amb mols de reactiu). Particularment, les pinces òptiques permeten manipular i aplicar forces a molècules individuals i determinar-ne així les seves propietats elàstiques i termodinàmiques. L’atrapament òptic es basa en l’ús d’un feix làser focalitzat per exercir una força òptica a les microesferes (diàmetre ~ 3 µm), que queden confinades a prop del punt focal a causa de la conservació del moment lineal. Els experiments de micromanipulació es realitzen unint els extrems de la molècula que es vol estudiar a la superfícies de dues microesferes diferents, podent així aplicar forces a la molècula quan desplacem una microesfera respecte de l’altra. Per ancorar les molècules a la superfície de les microesferes s’utilitzen unions moleculars que tenen una alta a.nitat (p.ex. enllaç biotina-estreptavidina). Típicament els experiments amb pinces òptiques consisteixen en la micromanipulació d’àcids nucleics (ADN, ARN) o proteïnes de forma individual. Per exemple, una molècula d’ADN pot ésser estirada per a estudiar-ne les propietats elàstiques, o oberta mecànicament (separant les dues cadenes que formen la doble hèlix) per a mesurar les energies lliures d’aparellament entre bases. Un gran nombre d’agents anticancerígens tenen com a diana els àcids nucleics, a on s’hi uneixen afi i efecte de dur a terme la seva acció citotòxica (p. ex. interferint amb processos cel·lulars essencials com són la replicació, la transcripció o els mecanismes de reparació). Per entendre el seu mecanisme d’acció és important conéixer en quines posicions, amb quina a.nitat, i amb quina cinètica s’uneixen a diferents seqüències d’ADN. Els experiments de molècula individual amb pinces òptiques permeten determinar la termodinàmica i cinètica d’unió de molts d’aquests lligands, especialment aquells difícils de caracteritzar mitjançant mesures en volum. És per això que un dels objectius principals d’aquesta tesi ha estat aprofitar les potencialitats de les mesures de molècula individual per a caracteritzar pèptids anti­cancerígens poc solubles i difícils d’estudiar amb tècniques alternatives: des de la cinètica i termodinàmica d’unió, a l’especi.citat en seqüència i la cinètica d’autoacoblament.

This PhD thesis belongs to the area of discrete dynamical systems in the complex plane, i.e. the iteration of analytic functions in one complex variable. Given a rational map f from the Riemann sphere onto itself, we consider the dynamical system given by its iterates. The Riemann sphere splits into two totally f-invariant subsets: the Fatou set, which is defined to be the set of points z where the family {f^n} is normal in some neighborhood of z, and its complement, the Julia set. The dynamics of the points in the Fatou set are stable in the sense of normality or equicontinuity whereas the dynamics in the Julia set present chaotic behavior. This thesis focuses on the study of the family of Blaschke products Ba(z)=z^3(z-a)/(1-\bar{a}z), where a and z are complex numbers. We study its parameter and its dynamical planes using intensive use of quasiconformal surgery techinques, which allow us to build rational maps with prescribed dynamics using quasiregular maps as models. The thesis is structured as follows. In Chapter 1 we give an overview on the preliminary results used throughout the thesis. In Chapter 2 we give an introduction to quasiconformal surgery. In Chapter 3 we give an overview of the dynamical plane of the Blaschke products Ba. We begin by studying their basic properties. Afterwards we show that the maps Ba cannot have doubly connected rotation domains (Herman rings) (Proposition 3.2.3) and prove a criterion of connectivity of the Julia set of Ba (Theorem 3.2.1). In Chapter 4 we introduce the family Mb of cubic polynomials with a superattracting fixed point. Then we show how to build polynomials Mb from Blaschke products Ba , obtaining a map Γ from a subset of the parameter plane of the Ba to the parameter plane of the polynomials Mb. We also prove that the map Γ is continuous and restricts to a homeomorphism on every disjoint hyperbolic component. In Chapter 5 we study the parameter plane of the Blaschke products Ba. We first describe the symmetries in the parameter plane. Then we classify the different hyperbolic dynamics which may take place and the sets of parameters for which they may happen. Afterwards we build a polynomial-like map for all non-escaping parameters contained in swapping regions which, under certain conditions, may relate the dynamics of Ba with the one of the antipolynomials pc(z) =\bar{z}^2+c (Theorem 5.3.4). Finally we parametrize all disjoint hyperbolic components whose disjoint cycles are bounded and do not lie on the unit circle (Theorem 5.4.2). In Chapter 6 we study the tongues of the Blaschke products Ba. We first prove some of their topological properties such as their connectivity modulo symmetry, their simple connectivity and the existence of a unique tip for every tongue (Theorem 6.2.1). Then we show how bifurcations take place along curves in a neighborhood of every tongue (Theorem 6.3.2). Finally we study how tongues extend in the annulus of parameters a such that 1<|a|<2. In Chapter 7 we study how the degree 4 Blaschke products Ba generalize to degree m+2 families of rational maps for m>2. / Aquesta tesi doctoral pertany a l’àmbit dels sistemes dinàmics discrets al pla complex, és a dir, la iteració de funcions analítiques en una variable complexa. Donada una funció racional f de l'esfera de Riemann en ella mateixa, considerem el sistema dinàmic donat pels seus iterats. L'esfera de Riemann es divideix en dos conjunts completament invariants per f el conjunt de Fatou, definit com el conjunt de punts z on la família {f^n} és normal en algun entorn de z, i el seu complement, el conjunt de Julià. La dinàmica de les òrbites del conjunt de Fatou és estable en el sentit de normalitat o equicontinuitat mentre que la dinàmica al conjunt de Julià presenta un caràcter caòtic. Aquesta tesi se centra en l'estudi de la família de productes de Blaschke Ba(z)=z^3(z-a)/(1-\bar{a}z), on a i z són nombres complexos. Estudiem el seu pla de paràmetres i el seu pla dinàmic fent us intensiu de les eines de cirurgia quasiconforme, que ens permeten construir funcions racionals amb una dinàmica prescrita fent servir funcions quasiregulars com a models. Al capítol 1 fem un repàs dels resultats preliminars usats al llarg del text. Primer expliquem els conceptes bàsics de la dinàmica de les funcions racionals. Després fem un repàs de les aplicacions del cercle, tot introduint els conceptes de producte de Blaschke i llengües. Finalment, presentem la fórmula de Riemann-Hurwitz i com s’aplica a la dinàmica de funcions racionals. Al capítol 2 donem una introducció a la cirurgia quasiconforme. Primer de tot definim els conceptes d’aplicació quasiconforme, estructures quasiconformes i “pullback” sota funcions que preserven l’orientació i introduïm el Teorema Mesurable de Riemann. Tot seguit mostrem com els conceptes previs són generalitzats per a funcions que giren l’orientació i veiem com això s’aplica a aplicacions que són simètriques respecte del cercle unitat. Finalment introduïm els conceptes d’aplicació polynomial-like i antipolynomial-like. Al capítol 3 donem una visió general del pla dinàmic dels productes de Blaschke Ba. Comencem estudiant les seves propietats bàsiques. Tot seguit mostrem que les funcions Ba. no poden tenir dominis de rotació doblement connexos (anells de Herman) (Proposició 3.2.3) i provem un criteri de connectivitat del conjunt de Julià dels Ba (Teorema 3.2.1). Al capítol 4 introduïm la família Mb de polinomis cúbics amb un punt fix superatractor. A continuació veiem com construir polinomis Mb a partir de productes de Blaschke Ba, tot obtenint una aplicació Γ que envia un subconjunt de l’espai de paràmetres de Ba a l’espai de paràmetres dels polinomis Mb. També provem que l’aplicació Γ és continua i és un homeomorfisme restringida a cada component hiperbòlica disjunta. Al capítol 5 estudiem l’espai de paràmetres dels productes de Blaschke Ba. Primer de tot en descrivim les simetries. A continuació classifiquem els diferents tipus de comportaments hiperbòlics que es poden donar i veiem a quines regions de l’espai de paràmetres poden aparèixer. Tot seguit construïm una aplicació polynomial-like al voltant de tot paràmetre de no escapament contingut en una regió d’intercanvi que, sota certes condicions, pot relacionar la dinàmica de Ba amb la dels antipolinomis pc(z)=\bar{z}^2+c (Teorema 5.3.4). Finalment parametritzem tota component hiperbòlica disjunta els cicles atractors de la qual són acotats i no rauen al cercle unitat (Teorema 5.4.2). Al capítol 6 estudiem les llengües dels productes de Blaschke Ba. Inicialment provem algunes de les seves propietats topològiques bàsiques com ara la seva connectivitat mòdul simetria, la seva connectivitat simple i l’existència d’una única punta per a cada llengua (Teorema 6.2.1). Tot seguit mostrem com es produeixen les bifurcacions en un entorn de la punta de cada llengua (Teorema 6.3.2). Finalment estudiem com les llengües s’estenen per a paràmetres a tals que 1<|a|< 2. Al capítol 7 estudiem com els productes de Blaschke Ba generalitzen a funcions racionals de grau m+2 per m>2.

Brain delivery is a major unmet challenge because most drugs cannot cross the blood-brain barrier (BBB). Despite the restrictive nature of this barrier, brain vasculature reaches essentially every neural cell to supply it with nutrients. BBB-shuttles are molecules that take advantage of endogenous transport mechanisms to deliver cargoes into the brain parenchyma. However, the efficiency and selectivity of current shuttles needs to be improved. It has recently been shown that one way to enhance their transport capacity is to make them protease-resistant. The main goals of this thesis were to find new protease-resistant BBB-shuttle peptides and also to increase the transport monoclonal antibodies across the barrier. A source of peptides with high resistance to proteases is venoms. Moreover, some components, such as the potassium channel blocker apamin, have an effect on the CNS without disrupting the BBB, which makes them good BBB-shuttle candidates. Firstly, we proved that apamin and the most similar analogue described not to be toxic had a similar permeability in a bovine cell-based BBB model, which indicated that the residues implied in toxicity were not required for the transport across the BBB. Then we generated a simplified analogue, MiniAp-1, which crossed the cell monolayer mainly through an active mechanism with higher permeability than apamin. This result encouraged us to prepare additional analogues and one of them, MiniAp-4, had a permeability 3-fold that of apamin. This increase in transport could be partly explained by its high resistance to serum proteases and its different conformational preferences with respect to the other analogues. We then demonstrated that MiniAp-4 significantly improved the transport of GFP, quantum dots and gold nanoparticles in a human cellbased model of the BBB. Finally, we showed that this peptide was capable of enhancing 7.6-fold the delivery of cyanine-5.5 in mice brain. Furthermore, we detected the targeted probe in the brain parenchyma. In parallel, we aimed to increase the transport of monoclonal antibodies against glioblastoma across the BBB. We set up five reactions to conjugate peptide shuttles to different parts of two antibodies. Modification of the transaminated N-termini through oxime ligation provided a peptide/antibody ratio (PAR) lower than 1. Conjugation of the fucose present in the glycan chains yielded a PAR of 2 with one antibody but was not applied to the other because of its complex glycosylation pattern. Conversely, we achieved a PAR of 4 on partially reduced interchain cystines of both antibodies. Hence, we used this method to generate a small library of BBB-shuttle-antibody conjugates. The thioether bond linking the shuttles to the antibodies proved stable at least for 24 h in human serum. We also linked peptides containing cysteines to the lysines using cuppercatalyzed azide-alkyne cycloaddition (CuAAC). No conjugation significantly reduced antibody affinity except for N-terminal ligation. When the library of conjugates was assayed in the human cell-based BBB model we observed a significant increase of the transport with most peptides. MiniAp-1 and RVG29 were the shuttles providing the highest enhancement. Regarding the modification site, conjugation to lysines using CuAAC was the most suitable, probably because shuttles are more accessible to their receptors. In conclusion, in this thesis we have shown that cyclic mini-apamins, with reduced toxicity and immunogenicity, are highly resistant to serum proteases and are capable of crossing a tight brain endothelial cell monolayer. MiniAp-4 efficiently delivers diverse cargoes across the BBB in a human cell-based model and in mice. We have also proved that some BBB-shuttles, particularly MiniAp-1 and RVG29, can enhance the transport of monoclonal antibodies in a cell-based model and that peptides linked to the lysines using CuAAC provide the highest increase. / La major part de fàrmacs dissenyats per tractar malalties del sistema nerviós central no són efectius perquè no poden creuar la barrera hematoencefàlica (BHE). Una de les estratègies més prometedores per superar aquest obstacle és l’ús de llançadores peptídiques. Tanmateix, l’eficiència i selectivitat d’aquests encara s’ha de millorar. Els objectius principals de la tesi eren, per una banda, trobar noves llançadores resistents a proteases i, per l’altra, augmentar el transport d’anticossos monoclonals a través de la BHE. Tenint en compte que l’apamina és un pèptid del verí de l’abella que creua la BHE, vam iniciar l’estudi demostrant que els residus implicats en la toxicitat no eren necessaris pel transport. Aleshores vam generar anàlegs simplificats i MiniAp-4 va mostrar el millor compromís entre estabilitat en sèrum, permeabilitat i immunogenicitat. Aquest pèptid va incrementar el transport de la GFP, quantum dots i nanopartícules d’or en un model cel·lular humà de BHE. A més, va augmentar en 7,6 vegades la concentració de cianina-5.5 en el cervell de ratolins. Pel que fa el transport d’anticossos, vam posar a punt diversos mètodes per conjugar els pèptids llançadora a diferents parts de la immunoglobulina, incloent els extrems Nterminals, les cadenes glicosídiques, les lisines i les cisteïnes. Cap conjugació va disminuir l’afinitat dels anticossos pels seus epítops exceptuant la del N-terminal. Vam escollir la modificació de les cisteïnes utilitzant química tiol-maleimida i també la de les lisines mitjançant cicloaddició alquí-azida catalitzada per coure (CuAAC) per generar conjugats emprant diverses llançadores. Alguns d’aquests van mostrar un transport significativament més elevat que l’anticòs sol en el model cel·lular humà de BHE, en especial una mini-apamina i el RVG29 enllaçats mitjançant CuAAC. La major eficiència de les llançadores amb aquesta unió és atribuïble a la major accessibilitat per interaccionar amb els seus receptors. Per concloure, en aquesta tesi hem generat anàlegs d’apamina resistents a protaeses, més reduïts, menys tòxics i menys immunogènics. A més, MiniAp-4 és capaç de transportar diversos compostos a través de la BHE in vitro i in vivo. També hem demostrat que el transport d’anticossos es pot augmentar mitjançant diferents llançadores peptídiques, incloent les mini-apamines. / La mayor parte de fármacos diseñados para tratar enfermedades del sistema nervioso central no son efectivos porque no pueden cruzar la barrera hematoencefálica (BHE). Una de las estrategias más prometedoras para superar este obstáculo es el uso de lanzadoras peptídicas. Sin embargo, la eficiencia y selectividad de dichas lanzadoras aún debe mejorar. Los objetivos principales de la tesis eran encontrar nuevas lanzadoras resistentes a proteases y aumentar el transporte de anticuerpos monoclonales a través de la BHE. Teniendo en cuenta que la apamina es un péptido del veneno de la abeja que cruza la BHE, iniciamos el estudio demostrando que los residuos implicados en la toxicidad no eran necesarios para el transporte. Luego generamos análogos simplificados y MiniAp-4 mostró un mejor compromiso entre estabilidad en suero, permeabilidad y inmunogenicidad. Este péptido incrementó el transporte de GFP, quantum dots y nanopartículas de oro en un modelo celular humano de BHE. A demás, aumentó en 7,6 veces la concentración de cianina-5.5 en el cerebro de ratones. Por lo que se refiere al transporte de anticuerpos, pusimos a punto varios métodos de conjugación de los péptidos lanzadora a distintas partes de la inmunoglobulina, incluyendo extremos N-terminales, cadenas de oligosacáridos, lisinas y cisteínas. Ninguna conjugación disminuyó la afinidad de los anticuerpos por sus epítopos exceptuando la del N-terminal. Escogimos la modificación de cisteínas mediante química tiol-maleimida y también la de lisinas utilizando cicloadición alquino-azida catalizada por cobre (CuAAC) para generar conjugados usando varias lanzadoras. Algunos de ellos mostraron un transporte significativamente más elevado que el anticuerpo sin modificar en el modelo humano de BHE, en especial una mini-apamina y RVG29 enlazados mediante CuAAC. La mayor eficiencia de las lanzadoras unidas de este modo es atribuible a la mayor accesibilidad para interaccionar con sus receptores. En conclusión, en esta tesis hemos generado análogos de apamina resistentes a proteasas, más reducidos así como menos tóxicos e inmunogénicos. Además, MiniAp-4 es capaz de transportar distintos compuestos a través de la BHE in vitro e in vivo. También hemos demostrado que el transporte de anticuerpos se puede aumentar mediante el uso de lanzadores peptídicas varias, incluyendo las mini-apaminas.

Combustion of diesel fuel in a diesel engine is a complex process where several pollutants are emitted in the engine exhausts. To solve this problem and at the same time accomplish with the increasingly stringent regulations for diesel composition, diesel reformulation with oxygenate compounds is proposed. Linear symmetrical ethers with more than 9 carbon atoms represent a group of oxygenate compounds with excellent properties as diesel additives. Its addition in small quantities to diesel enhances the blending cetane number, improves cold start performance of diesel engine and dilutes undesired components. C10-C16 linear ethers such as di-n-pentyl ether (DNPE), di-n-hexyl ether (DNHE) and di-n-octyl ether (DNOE) are three linear symmetrical ethers with excellent properties to be added to commercial diesel. This work proves that the synthesis of DNOE from 1-octanol dehydration over acid catalysts (acidic zeolites and polystyrene-divinylbenzene (PS-DVB) ion exchange resins) is possible at 413-473 K. At the same time, the present work continues with the series of synthesis of linear symmetrical ethers from n-alcohols started with DNPE and DNHE in previous works. A catalyst screening of acidic PS-DVB ion exchange resins showed best performances to yield DNPE, DNHE and DNOE selectively on low-crosslinked macroreticular and gel­type resins with high acid capacity. The ability to swell in the reaction media of low­crosslinked and gel-type resins contributes to create porosity ,allowing the diffusion of alcohols and ethers almost equally regardless the length of the molecules. On medium and large pore zeolites synthesis of linear symmetrical ether was found to be strongly related to the zeolites mesoporous surface and the acid sites number. Selectivity to linear ether decreased as the chain length increased which revealed a great steric hindrance for bulky molecules. The large pore zeolite H-BEA-25 showed the best yield of linear ether due to the combination of high conversion of alcohol and high selectivity to linear ether. In this work, the thermodynamic equilibrium constant of 1-octanol dehydration to DNOE was determined, proving that dehydration of 1-octanol to DNOE is an exothermic reaction. The study, allowed at the same time improving current methods to estimate molar entropy of DNOE. A kinetic study of the alcohol dehydration to linear ether was performed over zeolites and the thermostable resin Amberlyst 70. Over Amberlyst 70 a series of kinetic equations based on LHHW-RE mechanisms were fitted to rate data of 1-octanol dehydration to DNOE. Pure 1-octanol experiments revealed that kinetic models where 1-octanol and water are the adsorbed compounds in the resin and the fraction of free active sites is negligible fit the best. Influence of products (water and DNOE) and solvent (1,4-dioxane) was evaluated which revealed a strong inhibition effect of water. Inhibition effect of water was quantified by means of correction factors which described the fraction of active sites not blocked by water according to different adsorption isotherms. Freundlich isotherm was found to better describe the water inhibition effect in an scenario where one molecule of 1-octanol adsorbed reacts with another molecule of 1-octanol of the liquid phase in a Rideal-Eley mechanism. Activation energy determined accounting water deactivation was 110 ± 5 kJ·mol-1. Over zeolites, LHHW-RE kinetic models were fitted to rate data for DNHE and DNOE synthesis showing that the best kinetic models assume that the fraction of active sites is negligible. Within these models, two type of equations were found to best represent rate data, one assumes that alcohol and linear ether are adsorbed in the zeolite surface. The other equation assumes that alcohol and water are preferably adsorbed through the reaction. Apparent activation energy of 100-120 kJ·mol-1 were estimated for the reactions on tested zeolites. / La reformulació del combustible dièsel amb compostos oxigenats com els èters lineals de més de 9 carbonis permet augmentar la qualitat ambiental del combustible als motors dièsel. Els èters lineals simètrics com el di-n-pentil èter (DNPE), di-n-hexil èter (DNHE) i di-n-octil èter (DNOE) es presenten com tres compostos amb propietats excel·lents com additius pel dièsel ja que n’augmenten l’índex de cetà i en milloren les propietats fluidodinàmiques del dièsel. Aquest treball demostra que la deshidratació de 1-octanol a DNOE és possible sobre catalitzadors sòlids àcids (resines de bescanvi iònic de poliestirè reticulades amb divinilbenzè (PE-DVB) i zeolites) i a la vegada continua amb la sèrie de síntesis d’èters lineals simètrics a partir de n-alcohols començada amb el DNPE i DNHE en treballs previs. Les resines de bescanvi iònic PE-DVB macroreticulars amb baixos continguts de DVB i les resines tipus gel foren les resines que mes rendiment a DNPE, DNHE i DNOE van obtenir. Amb zeolites es va observar que la obtenció d’èters lineals simètrics amb estava fortament lligada a la superfície mesoporosa i al nombre de centres àcids de la zeolita. En aquest treball es va determinar la constant d’equilibri de la reacció de deshidratació de 1-octanol a DNOE i es va demostrar que la reacció mencionada és una reacció exotèrmica. Fruit de l’estudi d’equilibri es van poder corregir els mètodes actuals per estimar l’entropia molar del DNOE, proposant-ne un valor nou. Finalment es va desenvolupar un estudi cinètic sobre la resina termoestable Amberlyst 70 i sobre zeolites. A l’estudi de la deshidratació de 1-octanol a DNOE sobre Amberlyst 70 es va proposar un model cinètic basat en un mecanisme Rideal-Eley (RE) on una molècula de 1-octanol adsorbida al catalitzador reacciona amb una altra molècula de 1-octanol de la fase líquida. Així mateix es va constatar que la presència d’aigua exercia un fort efecte desactivador de la reacció i es va quantificar al model cinètic mitjançant un terme corrector basat en la isoterma Freundlich. Sobre les zeolites es van proposar dos tipus de models cinètics basats en mecanismes Langmuir-Hinselwood-Hougen-Watson (LHHW) i RE per les síntesis de DNOE i DNHE.

The work developed during this PhD has embraced several topics that I divide in three blocks. Each block contains two chapters in this dissertation. Additionally, a general introduction of the different topics is provided (Chapter 1). The first block corresponds to the study of colloidal synthetic routes to produce functional nanoparticles (Chapter 2 and 3). In the second block the developed nanoparticles are used to produce bulk nanostructured materials. The functional properties of the nanomaterials are also characterized in this second block. As the paradigmatic application for such bottom-up assembled nanostructured materials I considered thermoelectricity (Chapter 4 and 5). In the last block, I go one step beyond and design and prepare multiphase nanoparticles as building blocks for the bottom up production of nanocomposites with improved thermoelectric performance (Chapter 6 and 7). / El treball desenvolupat durant aquesta tesi doctoral engloba diverses temàtiques que s’han dividit en tres blocs. Cada bloc conté dos capítols. A més a més, com a Capítol 1 s’ha inclòs una introducció general de cadascuna de les temàtiques tractades. En el primer bloc, Capítols 2 i 3, s’estudien diferents síntesis col·loïdals per produir nanopartícules funcionals. En el segon bloc, Capítols 4 i 5, les nanopartícules desenvolupades s'utilitzen per produir materials nanoestructurats en bulk a partir del seu assemblatge. Les propietats funcionals d’aquests nanomaterials es caracteritzen també en aquest segon bloc. Com a aplicació paradigmàtica s’ha considerat la termoelectricitat. En l'últim bloc, Capítols 6 i 7, es va un pas més enllà i es dissenyen nanopartícules heterogènies com blocs de construcció per a la producció de nanocompostos amb millor rendiment termoelèctic.