DEVELOPMENT AND APPLICATION OF SHORT-TERM MUTAGENICITY AND CYTOTOXICITY BIOASSAYS FOR INTEGRATED HEALTH ASSESSMENT STUDIES OF COAL FLY ASH EMISSIONS

Two respirable coal fly ash samples ((LESSTHEQ) 3(mu)m), one from a pressurized fluidized-bed combustion miniplant and one from a conventional combustion power plant, were investigated for physical properties, chemical composition and biological activity. Electron microscopy illustrated irregularity in fluidized-bed combustion fly ash and sphericity in conventional combustion fly ash. Elemental analysis of these samples showed differences in trace elements. Both fly ash samples were toxic in rabbit alveolar macrophage and Chinese hamster ovary cell systems in vitro. The macrophages were more sensitive to toxicity of fly ash than the ovary cells. For measuring the cytotoxicity of fly ash, the most sensitive parameters were adenosine triphosphate in the alveolar macrophage system and viability index in the hamster ovary system. Intact fluidized-bed combustion fly-ash particles showed mutagenicity only in strains TA98 and TA1538 without metabolic activation in the Ames Salmonella assay. No mutagenicity was detected in bioassay of conventional combustion fly ash particles. Solvent extraction yielded more mass from fluidized-bed combustion fly ash than from conventional combustion fly ash. The extracts of fluidized-bed combustion fly ash showed higher mutagenic activity than conventional combustion fly ash. These samples contained direct-acting, frameshift mutagens.^ Fly ash samples collected from the same fluidized-bed source by cyclones, a fabric filter, and a electrostatic precipitator at various temperatures were compared for particle size, toxicity, and mutagenicity. Results demonstrated that the biological activity of coal fly ash were affected by the collection site, device, and temperature.^ Coal fly ash vapor-coated with 1-nitropyrene was developed as a model system to study the bioavailability and recovery of nitroaromatic compounds in fly ash. The effects of vapor deposition on toxicity and mutagenicity of fly ash were examined. The nitropyrene coating did not significantly alter the ash's cytotoxicity. Nitropyrene was bioavailable in the biological media, and a significant percentage was not recovered after the coated fly ash was cultured with alveolar macrophages. 1-Nitropyrene loss increased as the number of macrophages was increased, suggesting that the macrophages are capable of metabolizing or binding 1-nitropyrene present in coal fly ash. ^

Characterization of anti -sulfatide autoantibodies in demyelinating diseases

Multiple sclerosis (MS) is the most common autoimmune disease of the central nerve system and Guillain Barré Syndrome (GBS) is an inflammatory neuropathy involving the peripheral nerves. Anti-myelin immunoglobins may play a role in the demyelination processes of the both diseases. Sulfatide is an abundant glycolipid on myelin and is a candidate target antigen for disease related autoantibodies. The objective of this study was to characterize anti-sulfatide antibodies and compare antibodies from GBS and MS patients with fetal antibodies. Our hypothesis is that some B cells producing disease-associated autoantibodies are derived from or related to B cells of the fetal repertoire. Here we report that reactivity of plasma IgM against sulfatide was elevated in twelve MS patients compared with twelve normal subjects. This result implies that anti-sulfatide antibodies are disease-related. A total of sixteen human B lymphocyte clones producing anti-sulfatide autoantibodies were isolated from MS patients, GBS patients and a human fetus. Seven of the clones were from three MS patients, four of the clones were from three GBS patients and five were from the spleen of a twenty-week human fetus. Sequences have been obtained for the heavy and light chain variable regions (VDJ and VJ regions) of all of the anti-sulfatide immunoglobulins. Seven of the sixteen antibodies used VH3 for the variable region gene of the heavy chain consistent with the rate of VH3 usage in randomly selected B cells. Somatic mutations were significantly more frequent in the patient antibodies than in the fetus and somatic mutations in CDR's (Complementarity Determining Region) were significantly more frequent than in framework regions. No significant difference was found between patients and fetus in length of VH CDRIII. However, it is reported that antibodies from randomly selected normal adult B cells have longer CDRIII lengths than those of the fetus (Sanz I, 1991 Journal of Immunology Sep 1;147(5):1720-9). Our results are consistent with derivation of the precursors of B cells producing these autoantibodies from B cells related to those of the fetal repertoire. These findings are consistent with a model in which quiescent B cells from clones produced early in development undergo proliferation in dysregulated disease states, accumulating somatic mutations and increasing in reactivity toward self-antigens. ^ Epitope mapping and molecular modeling were done to elucidate the relationships between antibody structure and binding characteristics. The autoantibodies were tested for binding activity to three different antigens: sulfatide, galactoceramide and ceramide. Molecular modeling suggests that antibodies with positive charge surrounded by or adjacent to hydrophobic groups in the binding pocket bind to the head of sulfatide via the sulfate group through electrostatic interactions. However, the antibodies with hydrophobic groups separated from positive charges appear to bind to the hydrophobic tail of sulfatide. This observation was supported by a study of the effect of NaCl concentration on antigen binding. The result suggested that electrostatic interactions played a major role in sulfate group binding and that hydrophobic interactions were of greater importance for binding to the ceramide group. Our three-dimensional structure data indicated that epitope specificity of these antibodies is more predictable at the level of tertiary than primary structure and suggested positive selection based on structure occurred in the. formation of those autoantibodies. ^

Chemical composition of layer silicates from the Sado Ridge, Sea of Japan

Detailed mineralogical investigations of high-Fe layer silicates from loose sediments (glauconite sands) of the Sado Ridge revealed that green aggregates found on submarine rises of the Japan Sea floor have different genesis. It was demonstrated that round dark green grains approximate micas in composition. Primary volcanic rocks presumably have undergone extensive secondary alterations and then were disintegrated. Their disintegration products (protoceladonite) filling pores were redeposited and buried in sediments for a long time. Angular green grains mainly represented by smectite also formed at lower temperatures during disintegration of altered volcanosedimentary rocks. These younger grains had no prolonged exposure. Pseudomorphs of siliceous microplankton consist of both hydromica and smectites. They are presumably authigenic products formed with participation of microorganisms or electrostatic processes (spherical shape), or their combination. The formation mechanism of minerals filling cavities in pyroclastics is not entirely clear.

Desarrollo de estructuras nanofotonicas de campo cercano para intensificacion localizada de luz en celulas solares de banda intermedia - Near-field nanophotonic structures for localized light enhancement in intermediate band solar cells

This doctoral thesis explores some of the possibilities that near-field optics can bring to photovoltaics, and in particular to quantum-dot intermediate band solar cells (QD-IBSCs). Our main focus is the analytical optimization of the electric field distribution produced in the vicinity of single scattering particles, in order to produce the highest possible absorption enhancement in the photovoltaic medium in their surroundings. Near-field scattering structures have also been fabricated in laboratory, allowing the application of the previously studied theoretical concepts to real devices. We start by looking into the electrostatic scattering regime, which is only applicable to sub-wavelength sized particles. In this regime it was found that metallic nano-spheroids can produce absorption enhancements of about two orders of magnitude on the material in their vicinity, due to their strong plasmonic resonance. The frequency of such resonance can be tuned with the shape of the particles, allowing us to match it with the optimal transition energies of the intermediate band material. Since these metallic nanoparticles (MNPs) are to be inserted inside the cell photovoltaic medium, they should be coated by a thin insulating layer to prevent electron-hole recombination at their surface. This analysis is then generalized, using an analytical separation-of-variables method implemented in Mathematica7.0, to compute scattering by spheroids of any size and material. This code allowed the study of the scattering properties of wavelengthsized particles (mesoscopic regime), and it was verified that in this regime dielectric spheroids perform better than metallic. The light intensity scattered from such dielectric spheroids can have more than two orders of magnitude than the incident intensity, and the focal region in front of the particle can be shaped in several ways by changing the particle geometry and/or material. Experimental work was also performed in this PhD to implement in practice the concepts studied in the analysis of sub-wavelength MNPs. A wet-coating method was developed to self-assemble regular arrays of colloidal MNPs on the surface of several materials, such as silicon wafers, amorphous silicon films, gallium arsenide and glass. A series of thermal and chemical tests have been performed showing what treatments the nanoparticles can withstand for their embedment in a photovoltaic medium. MNPs arrays are then inserted in an amorphous silicon medium to study the effect of their plasmonic near-field enhancement on the absorption spectrum of the material. The self-assembled arrays of MNPs constructed in these experiments inspired a new strategy for fabricating IBSCs using colloidal quantum dots (CQDs). Such CQDs can be deposited in self-assembled monolayers, using procedures similar to those developed for the patterning of colloidal MNPs. The use of CQDs to form the intermediate band presents several important practical and physical advantages relative to the conventional dots epitaxially grown by the Stranski-Krastanov method. Besides, this provides a fast and inexpensive method for patterning binary arrays of QDs and MNPs, envisioned in the theoretical part of this thesis, in which the MNPs act as antennas focusing the light in the QDs and therefore boosting their absorption

Electromagnetic Instability Studies in Fusion Plasmas Edge

Este trabajo esta dedicado al estudio de las estructuras macroscópicas conocidas en la literatura como filamentos o blobs que han sido observadas de manera universal en el borde de todo tipo de dispositivos de fusión por confinamiento magnético. Estos filamentos, celdas convectivas elongadas a lo largo de las líneas de campo que surgen en el plasma fuertemente turbulento que existe en este tipo de dispositivos, parecen dominar el transporte radial de partículas y energía en la región conocida como Scrape-off Layer, en la que las líneas de campo dejan de estar cerradas y el plasma es dirigido hacia la pared sólida que forma la cámara de vacío. Aunque el comportamiento y las leyes de escala de estas estructuras son relativamente bien conocidos, no existe aún una teoría generalmente aceptada acerca del mecanismo físico responsable de su formación, que constituye una de las principales incógnitas de la teoría de transporte del borde en plasmas de fusión y una cuestión de gran importancia práctica en el desarrollo de la siguiente generación de reactores de fusión (incluyendo dispositivos como ITER y DEMO), puesto que la eficiencia del confinamiento y la cantidad de energía depositadas en la pared dependen directamente de las características del transporte en el borde. El trabajo ha sido realizado desde una perspectiva eminentemente experimental, incluyendo la observación y el análisis de este tipo de estructuras en el stellarator tipo heliotrón LHD (un dispositivo de gran tamaño, capaz de generar plasmas de características cercanas a las necesarias en un reactor de fusión) y en el stellarator tipo heliac TJ-II (un dispositivo de medio tamaño, capaz de generar plasmas relativamente más fríos pero con una accesibilidad y disponibilidad de diagnósticos mayor). En particular, en LHD se observó la generación de filamentos durante las descargas realizadas en configuración de alta _ (alta presión cinética frente a magnética) mediante una cámara visible ultrarrápida, se caracterizó su comportamiento y se investigó, mediante el análisis estadístico y la comparación con modelos teóricos, el posible papel de la Criticalidad Autoorganizada en la formación de este tipo de estructuras. En TJ-II se diseñó y construyó una cabeza de sonda capaz de medir simultáneamente las fluctuaciones electrostáticas y electromagnéticas del plasma. Gracias a este nuevo diagnóstico se pudieron realizar experimentos con el fin de determinar la presencia de corriente paralela a través de los filamentos (un parámetro de gran importancia en su modelización) y relacionar los dos tipos de fluctuaciones por primera vez en un stellarator. Así mismo, también por primera vez en este tipo de dispositivo, fue posible realizar mediciones simultáneas de los tensores viscoso y magnético (Reynolds y Maxwell) de transporte de cantidad de movimiento. ABSTRACT This work has been devoted to the study of the macroscopic structures known in the literature as filaments or blobs, which have been observed universally in the edge of all kind of magnetic confinement fusion devices. These filaments, convective cells stretching along the magnetic field lines, arise from the highly turbulent plasma present in this kind of machines and seem to dominate radial transport of particles and energy in the region known as Scrapeoff Layer, in which field lines become open and plasma is directed towards the solid wall of the vacuum vessel. Although the behavior and scale laws of these structures are relatively well known, there is no generally accepted theory about the physical mechanism involved in their formation yet, which remains one of the main unsolved questions in the fusion plasmas edge transport theory and a matter of great practical importance for the development of the next generation of fusion reactors (including ITER and DEMO), since efficiency of confinement and the energy deposition levels on the wall are directly dependent of the characteristics of edge transport. This work has been realized mainly from an experimental perspective, including the observation and analysis of this kind of structures in the heliotron stellarator LHD (a large device capable of generating reactor-relevant plasma conditions) and in the heliac stellarator TJ-II (a medium-sized device, capable of relatively colder plasmas, but with greater ease of access and diagnostics availability). In particular, in LHD, the generation of filaments during high _ discharges (with high kinetic to magnetic pressure ratio) was observed by means of an ultrafast visible camera, and the behavior of this structures was characterized. Finally, the potential role of Self-Organized Criticality in the generation of filaments was investigated. In TJ-II, a probe head capable of measuring simultaneously electrostatic and electromagnetic fluctuations in the plasma was designed and built. Thanks to this new diagnostic, experiments were carried out in order to determine the presence of parallel current through filaments (one of the most important parameters in their modelization) and to related electromagnetic (EM) and electrostatic (ES) fluctuations for the first time in an stellarator. As well, also for the first time in this kind of device, measurements of the viscous and magnetic momentum transfer tensors (Reynolds and Maxwell) were performed.

Influence of the molecular architecture on the secondary relaxations of Poly(styrene-co-methylmethacrylate) copolymers

The processes of adsorption of grafted copolymers onto negatively charged surfaces were studied using a dissipative quartz crystal microbalance (D-QCM) and ellipsometry. The control parameters in the study of the adsorption are the existence or absence on the molecular architecture of grafted polyethyleneglycol (PEG) chains with different lengths and the chemical nature of the main chain, poly(allylamine) (PAH) or poly(L-lysine) (PLL). It was found out that the adsorption kinetics of the polymers showed a complex behavior. The total adsorbed amount depends on the architecture of the polymer chains (length of the PEG chains), on the polymer concentration and on the chemical nature of the main chain. The comparison of the thicknesses of the adsorbed layers obtained from D-QCM and from ellipsometry allowed calculation of the water content of the layers that is intimately related to the grafting length. The analysis of D-QCM results also provides information about the shear modulus of the layers, whose values have been found to be typical of a rubber-like polymer system. It is shown that the adsorption of polymers with a charged backbone is not driven exclusively by the electrostatic interactions, but the entropic contributions as a result of the trapping of water in the layer structure are of fundamental importance.

Mejoras tecnológicas en el reciclado de residuos de construcción y demolición (RCD)

La tesis doctoral “Mejoras Tecnológicas en el Reciclado de Residuos de Construcción y Demolición (RCD)” investiga la utilización de los separadores hidráulicos para mejorar la calidad de los áridos reciclados, y se demuestra que es un equipo más eficiente que las técnicas actuales basadas en la simple separación por densidad. En la tesisn se ha realizado inicialmente una revisión de la situación del sector, para a continuación centrarse en los sistemas de separación utilizados en las plantas de valorización españolas. Una vez analizados éstos y en particular los de tipo hidráulico, de los que se resume un estudio comparativo, se ha procedido a ensayar a escala de Laboratorio el comportamiento de un separador hidráulico de aceleración diferencial con diversos materiales procedentes de tres plantas de reciclaje. Adicionalmente fueron probadas otras técnicas, como es la separación magnética para mejorar la calidad de los productos reciclados. En vista de los buenos resultados de la investigación, se procede a escalar los ensayos con equipo piloto y distintas composiciones de naturaleza cerámica y hormigón. El equipo utilizado fue un jig de 3´x 1´ en el que se ensayaron las tres muestras con resultados diferentes. La limpieza de los materiales impropios y el yeso fue positiva en las tres muestras, y únicamente la separación entre sí de los componentes pétreos, resultó dependiente de su proporción en la mezcla, obteniéndose los mejores resultados en las muestras con menor cantidad de materiales cerámicos. Finalmente, se procede a analizar en un laboratorio reconocido las propiedades de los áridos reciclados obtenidos en la separación hidráulica por jig, y constatar las mejoras conseguidas para su utilización como materiales de construcción en usos ligados y no ligados. Todo lo anterior permite afirmar que los equipos de separación hidráulica con aceleración diferencial (jig) presentan una innovación tecnológica en el reciclado de los residuos de construcción y demolición (RCD). ABSTRACT The doctoral thesis “Technological Improvements in Recycling of Construction and Demolition Waste (C&DW)” researches the hydraulic separators utilization in order to improve the recycled aggregates quality, demonstrating that the equipment is more efficient than the current techniques based on the simple density separation. This doctoral thesis has been initially done reviewing the situation of the sector and focusing afterwards on the separation systems used at the Spanish recovery facilities. Once analyzed these and, particularly, the hydraulic type ones, from which a comparative study has been summarized, the behavior of a differential acceleration hydraulic separator with various materials coming from three recycling plants has been tested at laboratory scale. Additionally other techniques have been tested, such as the magnetic separation to improve the quality of recycled products. In view of the good investigation results, the testing process scaled up by using pilot equipment and different ceramics and concrete compositions. The equipment utilized was a jig 3” x 1”, in which the three samples were tested with different results. The unsuitable materials and gypsum cleanliness was positive on the three samples and only the separation among the stony components turned out to be dependent of its proportion in the mixing, obtaining the best results in the samples with less quantity of ceramic materials. Finally, the properties of the recycled aggregates obtained by jig hydraulic separation are analyzed at a recognized laboratory and the improvements gained for their utilization as construction materials, in bounded and unbounded uses, are stated. The facts cited are a basis for affirming that the hydraulic separator equipments with differential acceleration (jig) offer a technological innovation in the Recycling of Construction and Demolition Waste (C&DW).

Crecimiento, fabricación y caracterización de heteroestructuras y nanocolumnas ordenadas basadas en nitruros del grupo III para aplicaciones sensoras

Esta memoria está basada en el crecimiento y caracterización de heteroestructuras Al(Ga)N/GaN y nanocolumnas ordenadas de GaN, y su aplicación en sensores químicos. El método de crecimiento ha sido la epitaxia de haces moleculares asistida por plasma (PAMBE). En el caso de las heteroestructuras Al(Ga)N/GaN, se han crecido barreras de distinto espesor y composición, desde AlN de 5 nm, hasta AlGaN de 35 nm. Además de una caracterización morfológica, estructural y eléctrica básica de las capas, también se han fabricado a partir de ellas dispositivos tipo HEMTs. La caracterización eléctrica de dichos dispositivos (carga y movilidad de en el canal bidimensional) indica que las mejores heteroestructuras son aquellas con un espesor de barrera intermedio (alrededor de 20 nm). Sin embargo, un objetivo importante de esta Tesis ha sido verificar las ventajas que podían tener los sensores basados en heteroestructuras AlN/GaN (frente a los típicos basados en AlGaN/GaN), con espesores de barrera muy finos (alrededor de 5 nm), ya que el canal de conducción que se modula por efecto de cambios químicos está más cerca de la superficie en donde ocurren dichos cambios químicos. De esta manera, se han utilizado los dispositivos tipo HEMTs como sensores químicos de pH (ISFETs), y se ha comprobado la mayor sensibilidad (variación de corriente frente a cambios de pH, Ids/pH) en los sensores basados en AlN/GaN frente a los basados en AlGaN/GaN. La mayor sensibilidad es incluso más patente en aplicaciones en las que no se utiliza un electrodo de referencia. Se han fabricado y caracterizado dispositivos ISFET similares utilizando capas compactas de InN. Estos sensores presentan peor estabilidad que los basados en Al(Ga)N/GaN, aunque la sensibilidad superficial al pH era la misma (Vgs/pH), y su sensibilidad en terminos de corriente de canal (Ids/pH) arroja valores intermedios entre los ISFET basados en AlN/GaN y los valores de los basados en AlGaN/GaN. Para continuar con la comparación entre dispositivos basados en Al(Ga)N/GaN, se fabricaron ISFETs con el área sensible más pequeña (35 x 35 m2), de tamaño similar a los dispositivos destinados a las medidas de actividad celular. Sometiendo los dispositivos a pulsos de voltaje en su área sensible, la respuesta de los dispositivos de AlN presentaron menor ruido que los basados en AlGaN. El ruido en la corriente para dispositivos de AlN, donde el encapsulado no ha sido optimizado, fue tan bajo como 8.9 nA (valor rms), y el ruido equivalente en el potencial superficial 38.7 V. Estos valores son más bajos que los encontrados en los dispositivos típicos para la detección de actividad celular (basados en Si), y del orden de los mejores resultados encontrados en la literatura sobre AlGaN/GaN. Desde el punto de vista de la caracterización electro-química de las superficies de GaN e InN, se ha determinado su punto isoeléctrico. Dicho valor no había sido reportado en la literatura hasta el momento. El valor, determinado por medidas de “streaming potential”, es de 4.4 y 4 respectivamente. Este valor es una importante característica a tener en cuenta en sensores, en inmovilización electrostática o en la litografía coloidal. Esta última técnica se discute en esta memoria, y se aplica en el último bloque de investigación de esta Tesis (i.e. crecimiento ordenado). El último apartado de resultados experimentales de esta Tesis analiza el crecimiento selectivo de nanocolumnas ordenadas de GaN por MBE, utilizando mascaras de Ti con nanoagujeros. Se ha estudiado como los distintos parámetros de crecimiento (i.e. flujos de los elementos Ga y N, temperatura de crecimiento y diseño de la máscara) afectan a la selectividad y a la morfología de las nanocolumnas. Se ha conseguido con éxito el crecimiento selectivo sobre pseudosustratos de GaN con distinta orientación cristalina o polaridad; templates de GaN(0001)/zafiro, GaN(0001)/AlN/Si, GaN(000-1)/Si y GaN(11-20)/zafiro. Se ha verificado experimentalmente la alta calidad cristalina de las nanocolumnas ordenadas, y su mayor estabilidad térmica comparada con las capas compactas del mismo material. Las nanocolumnas ordenadas de nitruros del grupo III tienen una clara aplicación en el campo de la optoelectrónica, principalmente para nanoemisores de luz blanca. Sin embargo, en esta Tesis se proponen como alternativa a la utilización de capas compactas o nanocolumnas auto-ensambladas en sensores. Las nanocolumnas auto-ensambladas de GaN, debido a su alta razón superficie/volumen, son muy prometedoras en el campo de los sensores, pero su amplia dispersión en dimensiones (altura y diámetro) supone un problema para el procesado y funcionamiento de dispositivos reales. En ese aspecto, las nanocolumnas ordenadas son más robustas y homogéneas, manteniendo una alta relación superficie/volumen. Como primer experimento en el ámbito de los sensores, se ha estudiado como se ve afectada la emisión de fotoluminiscencia de las NCs ordenadas al estar expuestas al aire o al vacio. Se observa una fuerte caída en la intensidad de la fotoluminiscencia cuando las nanocolumnas están expuestas al aire (probablemente por la foto-adsorción de oxigeno en la superficie), como ya había sido documentado anteriormente en nanocolumnas auto-ensambladas. Este experimento abre el camino para futuros sensores basados en nanocolumnas ordenadas. Abstract This manuscript deals with the growth and characterization of Al(Ga)N/GaN heterostructures and GaN ordered nanocolumns, and their application in chemical sensors. The growth technique has been the plasma-assisted molecular beam epitaxy (PAMBE). In the case of Al(Ga)N/GaN heterostructures, barriers of different thickness and composition, from AlN (5 nm) to AlGaN (35 nm) have been grown. Besides the basic morphological, structural and electrical characterization of the layers, HEMT devices have been fabricated based on these layers. The best electrical characteristics (larger carriers concentration and mobility in the two dimensional electron gas) are those in AlGaN/GaN heterostructures with a medium thickness (around 20 nm). However, one of the goals of this Thesis has been to verify the advantages that sensors based on AlN/GaN (thickness around 7 nm) have compared to standard AlGaN/GaN, because the conduction channel to be modulated by chemical changes is closer to the sensitive area. In this way, HEMT devices have been used as chemical pH sensors (ISFETs), and the higher sensitivity (conductance change related to pH changes, Ids/pH) of AlN/GaN based sensors has been proved. The higher sensibility is even more obvious in application without reference electrode. Similar ISFETs devices have been fabricated based on InN compact layers. These devices show a poor stability, but its surface sensitivity to pH (Vgs/pH) and its sensibility (Ids/pH) yield values between the corresponding ones of AlN/GaN and AlGaN/GaN heterostructures. In order to a further comparison between Al(Ga)N/GaN based devices, ISFETs with smaller sensitive area (35 x 35 m2), similar to the ones used in cellular activity record, were fabricated and characterized. When the devices are subjected to a voltage pulse through the sensitive area, the response of AlN based devices shows lower noise than the ones based on AlGaN. The noise in the current of such a AlN based device, where the encapsulation has not been optimized, is as low as 8.9 nA (rms value), and the equivalent noise to the surface potential is 38.7 V. These values are lower than the found in typical devices used for cellular activity recording (based on Si), and in the range of the best published results on AlGaN/GaN. From the point of view of the electrochemical characterization of GaN and InN surfaces, their isoelectric point has been experimentally determined. Such a value is the first time reported for GaN and InN surfaces. These values are determined by “streaming potential”, being pH 4.4 and 4, respectively. Isoelectric point value is an important characteristic in sensors, electrostatic immobilization or in colloidal lithography. In particular, colloidal lithography has been optimized in this Thesis for GaN surfaces, and applied in the last part of experimental results (i.e. ordered growth). The last block of this Thesis is focused on the selective area growth of GaN nanocolumns by MBE, using Ti masks decorated with nanoholes. The effect of the different growth parameters (Ga and N fluxes, growth temperature and mask design) is studied, in particular their impact in the selectivity and in the morphology of the nanocolumns. Selective area growth has been successful performed on GaN templates with different orientation or polarity; GaN(0001)/sapphire, GaN(0001)/AlN/Si, GaN(000- 1)/Si and GaN(11-20)/sapphire. Ordered nanocolumns exhibit a high crystal quality, and a higher thermal stability (lower thermal decomposition) than the compact layers of the same material. Ordered nanocolumns based on III nitrides have a clear application in optoelectronics, mainly for white light nanoemitters. However, this Thesis proposes them as an alternative to compact layers and self-assembled nanocolumns in sensor applications. Self-assembled GaN nanocolumns are very appealing for sensor applications, due to their large surface/volume ratio. However, their large dispersion in heights and diameters are a problem in terms of processing and operation of real devices. In this aspect, ordered nanocolumns are more robust and homogeneous, keeping the large surface/volume ratio. As first experimental evidence of their sensor capabilities, ordered nanocolumns have been studied regarding their photoluminiscence on air and vacuum ambient. A big drop in the intensity is observed when the nanocolumns are exposed to air (probably because of the oxygen photo-adsortion), as was already reported in the case of self-assembled nanocolumns. This opens the way to future sensors based on ordered III nitrides nanocolumns.

Computational study of ligand binding in lipid transfer proteins: Structures, interfaces, and free energies of protein-lipid complexes

Plant nonspecific lipid transfer proteins (nsLTPs) bind a wide variety of lipids, which allows them to perform disparate functions. Recent reports on their multifunctionality in plant growth processes have posed new questions on the versatile binding abilities of these proteins. The lack of binding specificity has been customarily explained in qualitative terms on the basis of a supposed structural flexibility and nonspecificity of hydrophobic protein-ligand interactions. We present here a computational study of protein-ligand complexes formed between five nsLTPs and seven lipids bound in two different ways in every receptor protein. After optimizing geometries inmolecular dynamics calculations, we computed Poisson- Boltzmann electrostatic potentials, solvation energies, properties of the protein-ligand interfaces, and estimates of binding free energies of the resulting complexes. Our results provide the first quantitative information on the ligand abilities of nsLTPs, shed new light into protein-lipid interactions, and reveal new features which supplement commonly held assumptions on their lack of binding specificity.

Métodos acotados de aplicación de reglas de evolución para la implementación de Sistemas P de Transición

La característica fundamental de la Computación Natural se basa en el empleo de conceptos, principios y mecanismos del funcionamiento de la Naturaleza. La Computación Natural -y dentro de ésta, la Computación de Membranas- surge como una posible alternativa a la computación clásica y como resultado de la búsqueda de nuevos modelos de computación que puedan superar las limitaciones presentes en los modelos convencionales. En concreto, la Computación de Membranas se originó como un intento de formular un nuevo modelo computacional inspirado en la estructura y el funcionamiento de las células biológicas: los sistemas basados en este modelo constan de una estructura de membranas que actúan a la vez como separadores y como canales de comunicación, y dentro de esa estructura se alojan multiconjuntos de objetos que evolucionan de acuerdo a unas determinadas reglas de evolución. Al conjunto de dispositivos contemplados por la Computación de Membranas se les denomina genéricamente como Sistemas P. Hasta el momento los Sistemas P sólo han sido estudiados a nivel teórico y no han sido plenamente implementados ni en medios electrónicos, ni en medios bioquímicos, sólo han sido simulados o parcialmente implementados. Por tanto, la implantación de estos sistemas es un reto de investigación abierto. Esta tesis aborda uno de los problemas que debe ser resuelto para conseguir la implantación de los Sistemas P sobre plataformas hardware. El problema concreto se centra en el modelo de los Sistemas P de Transición y surge de la necesidad de disponer de algoritmos de aplicación de reglas que, independientemente de la plataforma hardware sobre la que se implementen, cumplan los requisitos de ser no deterministas, masivamente paralelos y además su tiempo de ejecución esté estáticamente acotado. Como resultado se ha obtenido un conjunto de algoritmos (tanto para plataformas secuenciales, como para plataformas paralelas) que se adecúan a las diferentes configuraciones de los Sistemas P. ABSTRACT The main feature of Natural Computing is the use of concepts, principles and mechanisms inspired by Nature. Natural Computing and within it, Membrane Computing emerges as an potential alternative to conventional computing and as from the search for new models of computation that may overcome the existing limitations in conventional models. Specifically, Membrane Computing was created to formulate a new computational paradigm inspired by the structure and functioning of biological cells: it consists of a membrane structure, which acts as separators as well as communication channels, and within this structure are stored multisets of objects that evolve according to certain evolution rules. The set of computing devices addressed by Membrane Computing are generically known P systems. Up to now, no P systems have been fully implemented yet in electronic or biochemical means. They only have been studied in theory, simulated or partially implemented. Therefore, the implementation of these systems is an open research challenge. This thesis addresses one of the problems to be solved in order to deploy P systems on hardware platforms. This specific problem is focused on the Transition P System model and emerges from the need of providing application rules algorithms that independently on the hardware platform on which they are implemented, meets the requirements of being nondeterministic, massively parallel and runtime-bounded. As a result, this thesis has developed a set of algorithms for both platforms, sequential and parallel, adapted to all possible configurations of P systems.

SolarPaces 2013: Innovations on direct steam generation in linear fresnel collectors

Direct Steam Generation (DSG) in Linear Fresnel (LF) solar collectors is being consolidated as a feasible technology for Concentrating Solar Power (CSP) plants. The competitiveness of this technology relies on the following main features: water as heat transfer fluid (HTF) in Solar Field (SF), obtaining high superheated steam temperatures and pressures at turbine inlet (500ºC and 90 bar), no heat tracing required to avoid HTF freezing, no HTF degradation, no environmental impacts, any heat exchanger between SF and Balance Of Plant (BOP), and low cost installation and maintenance. Regarding to LF solar collectors, were recently developed as an alternative to Parabolic Trough Collector (PTC) technology. The main advantages of LF are: the reduced collector manufacturing cost and maintenance, linear mirrors shapes versus parabolic mirror, fixed receiver pipes (no ball joints reducing leaking for high pressures), lower susceptibility to wind damages, and light supporting structures allowing reduced driving devices. Companies as Novatec, Areva, Solar Euromed, etc., are investing in LF DSG technology and constructing different pilot plants to demonstrate the benefits and feasibility of this solution for defined locations and conditions (Puerto Errado 1 and 2 in Murcia Spain, Lidellin Newcastle Australia, Kogran Creek in South West Queensland Australia, Kimberlina in Bakersfield California USA, Llo Solar in Pyrénées France,Dhursar in India,etc). There are several critical decisions that must be taken in order to obtain a compromise and optimization between plant performance, cost, and durability. Some of these decisions go through the SF design: proper thermodynamic operational parameters, receiver material selection for high pressures, phase separators and recirculation pumps number and location, pipes distribution to reduce the amount of tubes (reducing possible leaks points and transient time, etc.), etc. Attending to these aspects, the correct design parameters selection and its correct assessment are the main target for designing DSG LF power plants. For this purpose in the recent few years some commercial software tools were developed to simulatesolar thermal power plants, the most focused on LF DSG design are Thermoflex and System Advisor Model (SAM). Once the simulation tool is selected,it is made the study of the proposed SFconfiguration that constitutes the main innovation of this work, and also a comparison with one of the most typical state-of-the-art configuration. The transient analysis must be simulated with high detail level, mainly in the BOP during start up, shut down, stand by, and partial loads are crucial, to obtain the annual plant performance. An innovative SF configurationwas proposed and analyzed to improve plant performance. Finally it was demonstrated thermal inertia and BOP regulation mode are critical points in low sun irradiation day plant behavior, impacting in annual performance depending on power plant location.

Theory of a Probe in a Strong Magnetic Field. AT(30-1)-1238-MATT 599

A kinetic approach is used to develop a theory of electrostatic probes in a fully ionized plasma in the presence of a magnetic field. A consistent asymptotic expansion is obtained assuming that the electron Larmor radius is small compared to the radius of the probe. The order of magnitude of neglected terms is given. It is found that the electric potential within the tube of force defined by the cross section of the probe decays non-mono tonic ally from the probe; this bump disappears at a certain probe voltage and the theory is valid up to this voltage. The transition region, which extends beyond plasma potential, is not exponential. The possible saturation of the electron current is discussed. Restricted numerical results are given; they seem to be useful for weaker magnetic fields down to the zero-field limit. Extensions of the theory a r e considered.

Potential theory

In this chapter we will introduce the reader to the techniques of the Boundary Element Method applied to simple Laplacian problems. Most classical applications refer to electrostatic and magnetic fields, but the Laplacian operator also governs problems such as Saint-Venant torsion, irrotational flow, fluid flow through porous media and the added fluid mass in fluidstructure interaction problems. This short list, to which it would be possible to add many other physical problems governed by the same equation, is an indication of the importance of the numerical treatment of the Laplacian operator. Potential theory has pioneered the use of BEM since the papers of Jaswon and Hess. An interesting introduction to the topic is given by Cruse. In the last five years a renaissance of integral methods has been detected. This can be followed in the books by Jaswon and Symm and by Brebbia or Brebbia and Walker.In this chapter we shall maintain an elementary level and follow a classical scheme in order to make the content accessible to the reader who has just started to study the technique. The whole emphasis has been put on the socalled "direct" method because it is the one which appears to offer more advantages. In this section we recall the classical concepts of potential theory and establish the basic equations of the method. Later on we discuss the discretization philosophy, the implementation of different kinds of elements and the advantages of substructuring which is unavoidable when dealing with heterogeneous materials.

Multi-fluid Eulerian model of an electrospray in a host gas.

An Eulerian multifluid model is used to describe the evolution of an electrospray plume and the flow induced in the surrounding gas by the drag of the electrically charged spray droplets in the space between an injection electrode containing the electrospray source and a collector electrode. The spray is driven by the voltage applied between the two electrodes. Numerical computations and order-of-magnitude estimates for a quiescent gas show that the droplets begin to fly back toward the injection electrode at a certain critical value of the flux of droplets in the spray, which depends very much on the electrical conditions at the injection electrode. As the flux is increased toward its critical value, the electric field induced by the charge of the droplets partially balances the field due to the applied voltage in the vicinity of the injection electrode, leading to a spray that rapidly broadens at a distance from its origin of the order of the stopping distance at which the droplets lose their initial momentum and the effect of their inertia becomes negligible. The axial component of the electric field first changes sign in this region, causing the fly back. The flow induced in the gas significantly changes this picture in the conditions of typical experiments. A gas plume is induced by the drag of the droplets whose entrainment makes the radius of the spray away from the injection electrode smaller than in a quiescent gas, and convects the droplets across the region of negative axial electric field that appears around the origin of the spray when the flux of droplets is increased. This suppresses fly back and allows much higher fluxes to be reached than are possible in a quiescent gas. The limit of large droplet-to-gas mass ratio is discussed. Migration of satellite droplets to the shroud of the spray is reproduced by the Eulerian model, but this process is also affected by the motion of the gas. The gas flow preferentially pushes satellite droplets from the shroud to the core of the spray when the effect of the inertia of the droplets becomes negligible, and thus opposes the well-established electrostatic/inertial mechanism of segregation and may end up concentrating satellite droplets in an intermediate radial region of the spray.

Modeling iron-catecholates binding to NGAL protein

Neutrophil gelatinase associated lipocalin (NGAL) protein is attracting a great interest because of its antibacterial properties played upon modulating iron content in competition against iron acquisition processes developed by pathogenic bacteria that bind selective ferric iron chelators (siderophores). Besides its known high affinity to enterobactin, the most important siderophore, it has been recently shown that NGAL is able to bind Fe(III) coordinated by catechols. The selective binding of Fe(III)-catechol ligands to NGAL is here studied by using iron coordination structures with one, two, and three catecholate ligands. By means of a computational approach that consists of B3LYP/6-311G(d,p) quantum calculations for geometries, electron properties and electrostatic potentials of ligands, protein–ligand flexible docking calculations, analyses of protein–ligand interfaces, and Poisson–Boltzmann electrostatic potentials for proteins, we study the binding of iron catecholate ligands to NGAL as a central member of the lipocalin family of proteins. This approach provides a modeling basis for exploring in silico the selective binding of iron catecholates ligands giving a detailed picture of their interactions in terms of electrostatic effects and a network of hydrogen bonds in the protein binding pocket.