Recientemente, el uso de técnicas de manipulación genética ha abierto la puerta a la obtención de microorganismos con fenotipos mejorados, lo que a su vez ha llevado a unas mejoras significativas en la síntesis de algunos productos bioquímicos. Sin embargo, la mutación y selección de estos nuevos organismos se ha llevado a cabo, en la mayoría de casos, por ensayo y error. Es de esperar que estos procesos puedan ser mejorados si se usan principios de diseño cuantitativos para guiar la búsqueda hacia el perfil enzimático ideal. Esta tesis está dedicada al desarrollo de un conjunto de herramientas de optimización avanzadas para asesorar en problemas de ingeniería metabólica y otras cuestiones emergentes en biología de sistemas. Concretamente, nos centramos en problemas en qué se modelan las redes metabólicas usando expresiones cinéticas. La utilidad de los algoritmos desarrollados para resolver tales problemas es demostrada por medio de varios casos de estudio. / In recent years, the use of genetic manipulation techniques has opened the door for obtaining microorganisms with enhanced phenotypes, which has in turn led to significant improvements in the synthesis of certain biochemical products. However, mutation and selection of these new organisms has been performed, in most cases, in a trial-and-error basis. It is expected that these processes could be further improved if quantitative design principles were used to guide the search towards the ideal enzymatic profiles. This thesis is devoted to developing a set of advanced global optimization tools to assess metabolic engineering problems and other questions arising in systems biology. In particular, we focus on problems where metabolic networks are modeled making use of kinetic expressions. The usefulness of the algorithms developed to solve such problems is demonstrated by means of several case studies.

A fracture mechanics protocol appropriate for small fibers (35 micron diameter) is presented, which allows for the determination of the strength limitations of high performance nylon 6,6 fibers. Specifically, linear elastic fracture mechanics (LEFM) techniques are employed in addition to elastic-plastic fracture mechanics (EPFM) theories to achieve this. We assume that a minute semi-elliptical flaw of an unknown size exists in the specimen, as a result of the detrimental effects of the manufacturing process (melt spinning). Next, we seek to propagate this flaw in a stable manner through an ancillary process such as high cycle or low cycle fatigue (load-unload). After propagation, uniaxial tensile experiments are performed on the fatigued samples, by which the crack growth eventually becomes catastrophic during the process. After performing scanning electron microscopy (SEM) techniques and reviewing fractography, we are able to determine the critical flaw size and ligament length that leads to unstable crack propagation. These results are substituted into the appropriate LEFM equations and are in close agreement with material properties for nylon 6,6. A discussion is provided that draws parallel to the topics discussed in the literature investigation and the experimental results of this study.

PA 66 nanocomposites and PA 66 blends were prepared using Cloisite 15A, Cloisite 25A and Cloisite 30B as organoclays and Lotader 2210 (E-BA-MAH), Lotader AX8840 (E-GMA) and Lotader AX8900 (E-MA-GMA) as impact modifiers. The effects of the composition, types of the components and the addition order of the nanocomposites on the morphology, mechanical, flow and thermal properties were investigated. Melt compounding step was carried out twice in a co-rotating twin-screw extruder. This was called as All-S mixing sequence when all the components were melt mixed, simultaneously. The concentration of the elastomer was determined as 5 wt% and the organoclay as 2 wt% to minimize agglomeration of the organoclay and decrease in the mechanical properties. The components which exhibited the best mechanical results and organoclay delamination in All-S mixing sequences were compounded by using different addition orders. Substantial increases were not observed in the tensile, impact, flexural and hardness test results of the nanocomposites compared to the polymer matrix that was twice extruded. Addition order of the components affected the properties of the nanocomposites and dispersion of the elastomeric domains and the organoclay. The best mechanical test results were obtained for All-S mixing sequence of (PA 66-15A-2210). The degree of organoclay dispersion is better in Cloisite 15A and Cloisite 25A containing nanocomposites than the ones which have Cloisite 30B. Low melt flow index values aided dispersion of the organoclay whereas the slight changes in the crystallinity did not significantly contribute to the changes in the mechanical properties of the nanocomposites or the blends.

Ancient Egyptian belief in an afterlife influenced a wide variety of architectural and art forms. In the Eighteenth Dynasty at Thebes, non-royal officials were equipped with tombs that were decorated to aid in their everlasting sustenance and rebirth in the hereafter as well as commemorate them to living visitors. Part of this continuation of life involved the participation of the funerary cult of the deceased, as well as the prompting of visitors to speak the owner’s name and provide the required offerings—allowing (and encouraging) public access to the decorated tomb chapel. However, some visitors wished to harm the deceased’s perpetuation of life. In order to obliterate the memory of the tomb owner in the minds of the living and his existence in the afterlife, enemies carefully hacked the tomb owner’s images out of the decoration program in an act of damnatio memoriae. The owners of Theban tombs 66, 75, and 76 fell victim to this intentional destruction by contemporary hands.

El presente trabajo de Tesis tiene como finalidad el desarrollo el desarrollo de nuevos bioprocesos basados en el uso de líquidos iónicos, dióxido de carbono supercrítico y tecnología de membranas con el fin de mejorar la eficiencia de los procesos y minimizar la generación de residuos. Los líquidos iónicos miscibles con agua han mostrado ser excelentes medios para la síntesis de ésteres mediante reacciones de transesterificación catalizadas por lipasas, en condiciones de bajo contenido en agua. La resolucion racémica de rac-1-feniletanol y rac-2-pentanol mediante la reacción de transesterificación con ésteres vinílicos catalizada por la enzima comercial lipasa B de Candida antarctica inmovilizada (Novozym 435) se llevó a cabo satisfactoriamente en un reactor de membrana que contenía una membrana líquida soportada basada en líquidos iónicos. Además se desarrolló un proceso sintético que combina el dióxido de carbono supercrítico, los líquidos iónicos y la tecnología de membrana. En estos sistemas bifásicos IL/scCO2, la selectividad de los procesos se incrementó en relación a la obtenida en dióxido de carbono supercrítico en ausencia de IL. / The main objective of this thesis is to develop new bioprocesses based on ionic liquids, carbon dioxide and membrane technology as combined reaction and separation media in order to improve the efficiency of the processes and minimize waste generation and energy consumption. A wide range of dialkylimidazolium-based ionic liquids were successfully used as reaction media for lipase catalyzed transesterification in low water conditions. The kinetic resolutions of rac-1-fenilethanol and rac-2-pentanol by transesterification with vinyl esters catalyzed by a commercial immobilized CaLB (Novozyme 435) were successfully carried out in the membrane bioreactor with supported liquid membrane based on ionic liquids. Moreover, a synthetic biocatalytic process combining scCO2, ILs and membrane technology was investigated. In the IL/scCO2 biphasic systems, the immobilized enzyme (free Candida antarctica lipase B) showed an increase in the selectivity of the process compared with supercritical carbon dioxide assayed in the absence of IL.

L’optimització en enginyeria de processos és un àrea molt estesa que ha anat evolucionant al llarg del temps i ha passat de ser una metodologia d'interès purament acadèmic a una tecnologia que té, i que contínua tenint, gran impacte en la indústria. En aquesta tesi ens hem centrat en el desenvolupament mètodes basats en dues eines típiques d'optimització: programació matemàtica i metaheurístiques. Els objectius d'aquesta tesi són: el primer és desenvolupar una metaheuristica híbrida per a l'optimització del disseny de cadenes de subministrament, d'un sol objectiu (cost o benefici), on tots els paràmetres són coneguts a priori; el segon és desenvolupar un algorisme efectiu per a reducció d'objectius facilitant la resolució de problemes multi-objectiu; i finalment s'han implementat una sèrie de millores en el mètode de la restricció èpsilon per millorar l'eficiència en la resolució de problemes multi-objectiu. Tots els algorismes presentats han estat comparats i avaluats amb els mètodes establerts per la literatura. / La optimización en ingeniería de procesos es un área muy extensa que ha ido evolucionando a lo largo del tiempo y ha pasado de ser una metodología de interés puramente académico a una tecnología que tiene, y que continua teniendo, gran impacto en la industria. En esta tesis nos hemos centrado en el desarrollo de métodos basados en dos herramientas típicas de optimización: programación matemática y metaheurísticas. Los objetivos de esta tesis son: el primero es desarrollar una metaheuristica híbrida para la optimización del diseño de cadenas de suministro, de un solo objetivo (coste o beneficio), donde todos los parámetros son conocidos a priori; el segundo es desarrollar un algoritmo efectivo para la reducción de objetivos facilitando la resolución de problemas multi-objetivo; y finalmente se han implementado una serie de mejoras en el método de la restricción epsilon para mejorar la eficiencia en la resolución de problemas multi-objetivo. Todos los algoritmos presentados han sido comparados y evaluados con los métodos establecidos por la literatura. / Optimization has become a major area in process systems engineering. It has evolved from a methodology of academic interest into a technology that has and continues to make significant impact in industry. In this thesis we have focused on development of tools based on two standard optimization methods: mathematical programming and metaheuristics. The objectives of this thesis are: firstly, the development of a hybrid metaheuristic for optimizing the design of supply chains, single objective (cost or benefit), where all parameters are known previously; secondly, the development of an effective algorithm for objective reduction facilitating the resolution of multi-objective problems; and finally, we improved the epsilon-constraint algorithm in multi-objective optimization. All the algorithms presented have been assessed with the methods established in the literature.

L'objectiu principal del nostre treball és el desenvolupament de nous materials catalítics i mètodes prometedors, eficients i respectuosos amb el medi ambient, per la degradació i la mineralització de contaminants orgànics mitjançant Processos d'Oxidació Avançada (POA) per al tractament d'aigües residuals. Amb aquest propòsit, diverses famílies de catalitzadors han estat sintetitzades per diferents mètodes i s'ha evaluat la seva activitat catalítica en els processos d'oxidació avançada d'ozonització catalítica i el procés Fenton heterogeni, tant per al tractament de compostos farmacèutics emergents com l'àcid clofíbric (CFA) com compostos recalcitrants d'origen industrial com fenol, en condicions ambientals. Entre tots els catalitzadors estudiats en el procés d'ozonització catalítica, el catalitzador d'òxid de Cu-Al preparat per un mètode de co-precipitació, ha mostrat una excel·lent activitat i estabilitat en l'ozonització catalítica de CFA, assolint un 82% i 96% de mineralització en 2 i 6 h, respectivament. En quant al procés Fenton, catalitzadors d'òxid de Fe presentant fases d'hematita i maghemita, i a les que s'han afegit petites quantitats de Pd (Pd/FeOOH) han mostrat molt bons resultats en l'eliminació de CFA mitjançant un procés Fenton heterogeni. En el procés combinat d'adsorció+oxidació, la zeolita ZSM5 contenint Fe i Pd (Pd/Fe-ZSM5) ha presentat una bona activitat en l'eliminació de fenol mitjançant adsorció i oxidació per un procés Fenton heterogeni. / El objetivo principal de nuestro trabajo es el desarrollo de nuevos materiales catalíticos y métodos prometedores, eficientes y respetuosos con el medio ambiente para la degradación y la mineralización de contaminantes orgánicos por medio de Procesos de Oxidación Avanzada (POA) para el tratamiento de aguas residuales. Con este propósito, varias familias de catalizadores han sido sintetizados por diferentes métodos y se ha evaluado su actividad catalítica en los procesos de oxidación avanzada de ozonización catalítica y el proceso Fenton heterogéneo, tanto para la eliminación de compuestos farmacéuticos emergentes como el ácido clofíbrico (CFA), como compuestos recalcitrantes de origen industrial, como fenol, en condiciones ambientales. Entre todos los catalizadores estudiados en el proceso de ozonización catalítica, el catalizador de óxido de Cu-Al preparado por un método de co-precipitación, ha mostrado una excelente actividad y estabilidad en la ozonización catalítica de CFA, alcanzando un 82% y 96% de mineralización en 2 y 6 h, respectivamente. En cuanto al proceso Fenton, catalizadores de óxido de Fe conteniendo fases de hematita y maghemita y a los que se le ha añadido pequeñas cantidades de Pd (Pd/FeOOH) han mostrado muy buenos resultados en la eliminación de CFA mediante un proceso Fenton heterogéneo. En el proceso combinado de adsorción+oxidación, la zeolita ZSM5 conteniendo Fe y Pd (Pd/Fe-ZSM5) ha presentado un buen desempeño en la eliminación de fenol mediante adsorción y oxidación por un proceso Fenton heterogéneo. / The main aim of our work is to develop new catalytic materials and promising, efficient and environmental-friendly methods for the degradation and mineralization of organic pollutants by means of Advanced Oxidation Processes (AOPs) for wastewater treatment. For this purpose various families of catalysts were synthesized by different methods and their potential catalytic activity have been evaluated in Advanced Oxidation Processes (AOPs) such as ozonation and Fenton-like process for treating emerging pharmaceutical compounds like clofibric acid (CFA) and recalcitrant compounds like phenol at ambient conditions. Among all the catalysts screened, the Cu-Al oxide catalyst prepared by a co-precipitation method, showed an excellent activity and stability in catalytic ozonation of CFA, achieving 82% and 96% mineralization in 2 and 6h, respectively. As for the Fenton process, catalysts containing Fe oxides presenting hematite and maghemite phases, and to which small amounts of Pd were added (Pd/FeOOH) have shown very good results in the removal of CFA by means of heterogeneous Fenton process. In the combined process of adsorption+oxidation, ZSM5 zeolite containing Fe and Pd (Pd/Fe-ZSM5) has presented good performance in the removal of phenol by adsorption and oxidation by heterogeneous Fenton-like process.

Dentro de la síntesis de óxidos, la obtención de nanopartículas se muestra como una alternativa atractiva a los métodos tradicionales ya que el aumento de superfície específica generado al disminuir el tamaño de grano, provoca una mejora sustancial en aquellas propiedades que se relacionan con la superfície de la partícula, como la sinterizabilidad. Se utilizan métodos de combustión de geles de acrilamida para la síntesis de diferentes familias de óxidos magnéticos, superconductores, conductores iónicos y mixtos, etc. El hecho de partir de una disolución proporciona una gran homogeneidad estructural y composicional a los productos así obtenidos, mientras que la combustión de geles de acrilamida se revela como un método ágil, versatil y robusto de síntesis, permitiendo la fabricación de lotes relativamente grandes en un breve lapso de tiempo.En este trabajo, en primer lugar, se estudia el propio método para determinar cuáles son los factores significativos en la síntesis utilizando el diseño de experimentos para maximizar la información que se puede extraer del sistema con el menor número posible de experimentos. A continuación se aplica la combustión de geles de acrilamida para la síntesis de diversos óxidos : Conductores iónicos, conductores mixtos, óxidos magnéticos, óxidos magnetorresistivos y óxidos superconductores.En capítulos posteriores se procede a estudiar la síntesis mediante combustión de geles de poliacrilamida como una alternativas que sortea la toxicidad de la acrilamida.Finalmente se describe un dispositivo de spray-pirólisis para la síntesis en continuo a escala piloto. / Concerning to the oxide synthesis, nanoparticle obtention seems to be an interesting alternative to traditional synthesis methods because the specific surface increase alows an improvement of sintering and other surface-related properties.We used acrylamide gel combustion methods to obtain different materials as superconductive oxides, ionic and mixed conductors, magnetic spinels, etc. Departing from a solution provides higher chemical and structural homogeneity than traditional routes, while the combustion scheme brings the hability of large batch production.In this work we used the design of experiments to determine which, from all possible variables, are statisticaly relevants with the mínimum number of experiments. The conclusions of this study was applied to the synthesis of metalic oxides with technological interest as: Ionic conductors, Mixed conductors, Magnetic oxides, Magnetorresistive oxides, Superconductive oxides.In further chapters we try to avoid acrylamide toxicity using polyacrylamide as gel former.Finally we designed and tested a spray-pirolisis device as the way to scale the process to pre-industrial scale.

The nanoindentation or indenter testing technique (ITT) is a functional and fast technique that can give us a lot of information about the mechanical properties of different materials at nanometric scale, from soft to brittle materials. The principle of the technique is the evaluation of the response of a material to an applied load. In a composite material, if the size of the residual imprint resulting from a certain load is lower than the size of the studied phase, then it is possible to determine its mechanical properties, and therefore its contribution to the global mechanical properties of the composite. Depending on the tipped indenter used, different equations should be applied to study the response of the material, and thus calculate stress-strain curves, and parameters such as hardness, Young's modulus, toughness, yield strength and shear stress. These equations are related to the different deformation mechanisms (elastic and elasto-to-plastic) that the material undergoes. In the case of most of the ceramic composites, when a spherical tipped nanoindenter is used, elastic deformation takes place, and Hertz equations can be used to calculate the yield strength, shear stress and the strain-stress curves. On the other hand, when a Berckovich indenter is used, plastic deformation takes place, then Oliver and Pahrr equations must be applied to evaluate the hardness, Young's modulus and toughness. Nevertheless, in the hardness study, Indentation Size Effect (ISE) must be considered.The mechanical properties of a ceramic superconductor material have been studied. YBa2Cu3O7-ä (YBCO or Y-123) samples textured by Bridgman and Top Seeding Melt Growth (TSMG) techniques have been obtained, and their mechanical properties studied by nanoindentation. This material presents a phase transition from tetragonal to orthorhombic that promotes a change in its electrical properties, from insulating to superconductor, and that can be achieved by partially oxygenating the material. On the other hand, the structure of the textured material is heterogeneous, and two different phases are present: Y-123 as a matrix and Y2BaCuO5 (Y-211) spherical or quasi-spherical inclusions. Moreover, the texture process induces an anisotropic structure, thus being the ab-planes the ones that transport the superconductor properties while the c-axis remains insulating. Nowadays, efforts are focused on the production of long length Superconductor Materials. Silver welding is a technique that allows us to join several TSMG samples thus trying to obtaining larger samples. Nevertheless, one important factor to be accounted for is the mechanical stability across the welding zone, which has been studied in this Thesis. Another attempt to produce long length superconductor materials is to shape thus as wires or plates. In this case, a metallic sheet, covered with different buffer layers is used as substrate on which YBCO layers can be deposited by PED for example. These structures have been also studied in the present Thesis.

This thesis presents two successful applications of data-driven models developed for a reverse osmosis desalination pilot plant. The Support Vector Regression (SVR) modeling approach for steady state operation of the reverse osmosis pilot plant M3 has performed better results than the commonly used first principle-based models. In the same way, the dynamic models have enabled the short-term prediction and simulation of the M3 plant behavior under non-steady state operation, with such a high accuracy that it makes the approach suitable for advanced reverse osmosis plant control algorithms, fault tolerant control and process optimization. In fact, SVR models have been proved to perform excellent results as part of a fault detection and isolation tool for the M3 plant. In addition, an alternative to SVR models which uses Self-Organizing Maps has been also demonstrated for fault detection and isolation, including a useful visual tool for the rapid fault detection during plant operation. / Aquesta tesi presenta dues aplicacions de models basats en dades desenvolupades per a una planta pilot de dessalinització d’aigua mitjançant osmosi inversa. S’ha modelat l’operació estacionària de la planta M3 utilitzant Support Vector Regression (SVR), obtenint uns resultats millors que els dels models basats en primers principis. Així mateix, els models dinàmics han permès la simulació i la predicció a curt termini de l’M3 en condicions no estacionàries amb tal precisió que els fa idonis per a la seva aplicació en optimització de processos i algoritmes avançats de control. De fet, models SVR han estat utilitzats en un sistema de detecció i aïllament de fallades per a l’M3, obtenint excel•lents resultats. Addicionalment, també s’ha desenvolupat un sistema de detecció i aïllament de fallades alternatiu als models SVR que utilitza Self-Organizing-Maps i a més inclou una eina visual per a la ràpida detecció de fallades durant l’operació de la planta.