Relational and Allegorical Semantics for Constraint Logic Programming

El cálculo de relaciones binarias fue creado por De Morgan en 1860 para ser posteriormente desarrollado en gran medida por Peirce y Schröder. Tarski, Givant, Freyd y Scedrov demostraron que las álgebras relacionales son capaces de formalizar la lógica de primer orden, la lógica de orden superior así como la teoría de conjuntos. A partir de los resultados matemáticos de Tarski y Freyd, esta tesis desarrolla semánticas denotacionales y operacionales para la programación lógica con restricciones usando el álgebra relacional como base. La idea principal es la utilización del concepto de semántica ejecutable, semánticas cuya característica principal es el que la ejecución es posible utilizando el razonamiento estándar del universo semántico, este caso, razonamiento ecuacional. En el caso de este trabajo, se muestra que las álgebras relacionales distributivas con un operador de punto fijo capturan toda la teoría y metateoría estándar de la programación lógica con restricciones incluyendo los árboles utilizados en la búsqueda de demostraciones. La mayor parte de técnicas de optimización de programas, evaluación parcial e interpretación abstracta pueden ser llevadas a cabo utilizando las semánticas aquí presentadas. La demostración de la corrección de la implementación resulta extremadamente sencilla. En la primera parte de la tesis, un programa lógico con restricciones es traducido a un conjunto de términos relacionales. La interpretación estándar en la teoría de conjuntos de dichas relaciones coincide con la semántica estándar para CLP. Las consultas contra el programa traducido son llevadas a cabo mediante la reescritura de relaciones. Para concluir la primera parte, se demuestra la corrección y equivalencia operacional de esta nueva semántica, así como se define un algoritmo de unificación mediante la reescritura de relaciones. La segunda parte de la tesis desarrolla una semántica para la programación lógica con restricciones usando la teoría de alegorías—versión categórica del álgebra de relaciones—de Freyd. Para ello, se definen dos nuevos conceptos de Categoría Regular de Lawvere y _-Alegoría, en las cuales es posible interpretar un programa lógico. La ventaja fundamental que el enfoque categórico aporta es la definición de una máquina categórica que mejora e sistema de reescritura presentado en la primera parte. Gracias al uso de relaciones tabulares, la máquina modela la ejecución eficiente sin salir de un marco estrictamente formal. Utilizando la reescritura de diagramas, se define un algoritmo para el cálculo de pullbacks en Categorías Regulares de Lawvere. Los dominios de las tabulaciones aportan información sobre la utilización de memoria y variable libres, mientras que el estado compartido queda capturado por los diagramas. La especificación de la máquina induce la derivación formal de un juego de instrucciones eficiente. El marco categórico aporta otras importantes ventajas, como la posibilidad de incorporar tipos de datos algebraicos, funciones y otras extensiones a Prolog, a la vez que se conserva el carácter 100% declarativo de nuestra semántica. ABSTRACT The calculus of binary relations was introduced by De Morgan in 1860, to be greatly developed by Peirce and Schröder, as well as many others in the twentieth century. Using different formulations of relational structures, Tarski, Givant, Freyd, and Scedrov have shown how relation algebras can provide a variable-free way of formalizing first order logic, higher order logic and set theory, among other formal systems. Building on those mathematical results, we develop denotational and operational semantics for Constraint Logic Programming using relation algebra. The idea of executable semantics plays a fundamental role in this work, both as a philosophical and technical foundation. We call a semantics executable when program execution can be carried out using the regular theory and tools that define the semantic universe. Throughout this work, the use of pure algebraic reasoning is the basis of denotational and operational results, eliminating all the classical non-equational meta-theory associated to traditional semantics for Logic Programming. All algebraic reasoning, including execution, is performed in an algebraic way, to the point we could state that the denotational semantics of a CLP program is directly executable. Techniques like optimization, partial evaluation and abstract interpretation find a natural place in our algebraic models. Other properties, like correctness of the implementation or program transformation are easy to check, as they are carried out using instances of the general equational theory. In the first part of the work, we translate Constraint Logic Programs to binary relations in a modified version of the distributive relation algebras used by Tarski. Execution is carried out by a rewriting system. We prove adequacy and operational equivalence of the semantics. In the second part of the work, the relation algebraic approach is improved by using allegory theory, a categorical version of the algebra of relations developed by Freyd and Scedrov. The use of allegories lifts the semantics to typed relations, which capture the number of logical variables used by a predicate or program state in a declarative way. A logic program is interpreted in a _-allegory, which is in turn generated from a new notion of Regular Lawvere Category. As in the untyped case, program translation coincides with program interpretation. Thus, we develop a categorical machine directly from the semantics. The machine is based on relation composition, with a pullback calculation algorithm at its core. The algorithm is defined with the help of a notion of diagram rewriting. In this operational interpretation, types represent information about memory allocation and the execution mechanism is more efficient, thanks to the faithful representation of shared state by categorical projections. We finish the work by illustrating how the categorical semantics allows the incorporation into Prolog of constructs typical of Functional Programming, like abstract data types, and strict and lazy functions.

Hiord: A type-free higher-order logic programming language with predicate abstraction

A new formalism, called Hiord, for defining type-free higherorder logic programming languages with predicate abstraction is introduced. A model theory, based on partial combinatory algebras, is presented, with respect to which the formalism is shown sound. A programming language built on a subset of Hiord, and its implementation are discussed. A new proposal for defining modules in this framework is considered, along with several examples.

On the lateral excitation of shear modes in AlN layered resonators

In this paper we describe the fabrication and frequency characterization of different structures intended for the lateral excitation of shear modes in AlN c-axis-oriented films, which are at the same time designed to minimize the excitation of longitudinal modes. Laterally excited resonators were built on partially metallic (SiO2, W) and insulating (SiOC, Si3N4) acoustic mirrors built on silicon substrates, and on insulating mirrors (SiO2, TaOx) built on insulating glass plates. TiOx seed layers were used to stimulate the growth of highly c-axis oriented AlN films, which was confirmed by XRD and SAW measurements. Coplanar Mo electrodes of different geometries were defined on top of the AlN films to excite the shear modes. All the structures analyzed displayed a clear longitudinal mode, corresponding to an acoustic velocity of 11000 m/s, but a null or extremely weak shear response corresponding to a sound velocity of around 6350 m/s. The simulation of the frequency response based on Mason's model confirms that the shear resonance is extremely weak. The observed longitudinal modes are attributed either to the field applied between the electrodes and a conductive plane (metallic layer or Si substrate) or to the electric field parallel to the c-axis in the edges of the electrodes or in tilted grains. The low excitation of shear modes is attributed to the very low values of electric field strength parallel to the surface.

X-Ray Diffraction, Calorimetric and Dielectric Relaxation Study of the Amorphous and Smectic States of a Main Chain Liquid Crystalline Polymer

Los polímeros cristales líquidos (LCP) son sistemas complejos que forman mesofases que presentan orden orientacional y polímeros amorfos. Con frecuencia, el estado amorfo isotrópico no puede ser estudiado debido a la rápida formación de mesofases. En este trabajo se ha sintetizado y estudiado un nuevo LCP: poli(trietilenglicol metil p, p '-bibenzoato), PTEMeB. Este polímero presenta una formación de mesofase bastante lenta haciendo posible estudiar de forma independiente tanto los estados amorfo y de cristal líquidos. La estructura y las transiciones de fase del PTEMeB han sido investigados por calorimetría (DSC), con MAXS / WAXS con temperatura variable que emplean radiación de sincrotrón y con difracción de rayos X. Estos estudios han mostrado la existencia de dos transiciones vítreas, relacionadas con las fases amorfa y cristal líquido. Se ha realizado un estudio de relajación dieléctrica en amplios intervalos de temperatura y presión. Se ha encontrado que la transición vítrea dinámica de la fase amorfa es más lenta que la del cristal líquido. El estudio de la relajación ? nos ha permitido seguir la formación isoterma de la mesofase a presión atmosférica. Además, con el estudio el comportamiento dinámico a alta presión se ha encontrado que se produce la formación rápida de la mesofase inducida por cambios bruscos de presión. Liquid crystalline polymers (LCPs) are complex systems that include features of both orientationally ordered mesophases and amorphous polymers. Frequently, the isotropic amorphous state cannot be studied due to the rapid mesophase formation. Here, a new main chain LCP, poly(triethyleneglycol methyl p,p'-bibenzoate), PTEMeB, has been synthesized. It shows a rather slow mesophase formation making possible to study independently both the amorphous and the liquid crystalline states. The structure and phase transitions of PTEMeB have been investigated by calorimetry, variable-temperature MAXS/WAXS employing synchrotron radiation, and X-ray diffraction in oriented fibers. These experiments have pointed out the presence of two glass transitions, related to the amorphous or to the liquid crystal phases. Additionally, the mesophase seems to be a coexistence of orthogonal and tilted smectic phases. A dielectric relaxation study of PTEMeB over broad ranges of temperature and pressure has been performed. The dynamic glass transition turns out to be slower for the amorphous state than for the liquid crystal. Monitoring of the α relaxation has allowed us to follow the isothermal mesophase formation at atmospheric pressure. Additionally, the dynamical behavior at high pressures has pointed out the fast formation of the mesophase induced by sudden pressure changes.

Comparative assessment of global irradiation from a satellite estimate model (CM SAF) and on-ground measurements (SIAR): a Spanish case study

An analysis and comparison of daily and yearly solar irradiation from the satellite CM SAF database and a set of 301 stations from the Spanish SIAR network is performed using data of 2010 and 2011. This analysis is completed with the comparison of the estimations of effective irradiation incident on three different tilted planes (fixed, two axis tracking, north-south hori- zontal axis) using irradiation from these two data sources. Finally, a new map of yearly values of irradiation both on the horizontal plane and on inclined planes is produced mixing both sources with geostatistical techniques (kriging with external drift, KED) The Mean Absolute Difference (MAD) between CM SAF and SIAR is approximately 4% for the irradiation on the horizontal plane and is comprised between 5% and 6% for the irradiation incident on the inclined planes. The MAD between KED and SIAR, and KED and CM SAF is approximately 3% for the irradiation on the horizontal plane and is comprised between 3% and 4% for the irradiation incident on the inclined planes. The methods have been implemented using free software, available as supplementary ma- terial, and the data sources are freely available without restrictions.

Comparative assessment of global irradiation from a satellite estimate model (CM SAF) and on-ground measurements (SIAR): a Spanish case study

An analysis and comparison of daily and yearly solar irradiation from the satellite CM SAF database and a set of 301 stations from the Spanish SIAR network is performed using data of 2010 and 2011. This analysis is completed with the comparison of the estimations of effective irradiation incident on three different tilted planes (fixed, two axis tracking, north-south hori- zontal axis) using irradiation from these two data sources. Finally, a new map of yearly values of irradiation both on the horizontal plane and on inclined planes is produced mixing both sources with geostatistical techniques (kriging with external drift, KED) The Mean Absolute Difference (MAD) between CM SAF and SIAR is approximately 4% for the irradiation on the horizontal plane and is comprised between 5% and 6% for the irradiation incident on the inclined planes. The MAD between KED and SIAR, and KED and CM SAF is approximately 3% for the irradiation on the horizontal plane and is comprised between 3% and 4% for the irradiation incident on the inclined planes. The methods have been implemented using free software, available as supplementary ma- terial, and the data sources are freely available without restrictions.

Categorical Structures in Non-Commutative Measure Theory.

In this paper, we investigate effect algebras and base normed spaces from the categorical point of view. We prove that the category of effect algebras is complete and cocomplete as well as the category of base normed spaces is complete, and discuss the contravariant functor from the category of effect algebras to the category of base normed spaces.

Towards cost reduction in concentrating solar power: innovative design for an efficient fresnel based solar field

Energía termosolar (de concentración) es uno de los nombres que hacen referencia en español al término inglés “concentrating solar power”. Se trata de una tecnología basada en la captura de la potencia térmica de la radiación solar, de forma que permita alcanzar temperaturas capaces de alimentar un ciclo termodinámico convencional (o avanzado); el futuro de esta tecnología depende principalmente de su capacidad para concentrar la radiación solar de manera eficiente y económica. La presente tesis está orientada hacia la resolución de ciertos problemas importantes relacionados con este objetivo. La mencionada necesidad de reducir costes en la concentración de radiación solar directa, asegurando el objetivo termodinámico de calentar un fluido hasta una determinada temperatura, es de vital importancia. Los colectores lineales Fresnel han sido identificados en la literatura científica como una tecnología con gran potencial para alcanzar esta reducción de costes. Dicha tecnología ha sido seleccionada por numerosas razones, entre las que destacan su gran libertad de diseño y su actual estado inmaduro. Con el objetivo de responder a este desafío se desarrollado un detallado estudio de las propiedades ópticas de los colectores lineales Fresnel, para lo cual se han utilizado métodos analíticos y numéricos de manera combinada. En primer lugar, se han usado unos modelos para la predicción de la localización y la irradiación normal directa del sol junto a unas relaciones analíticas desarrolladas para estudiar el efecto de múltiples variables de diseño en la energía incidente sobre los espejos. Del mismo modo, se han obtenido analíticamente los errores debidos al llamado “off-axis aberration”, a la apertura de los rayos reflejados en los espejos y a las sombras y bloqueos entre espejos. Esto ha permitido la comparación de diferentes formas de espejo –planos, circulares o parabólicos–, así como el diseño preliminar de la localización y anchura de los espejos y receptor sin necesidad de costosos métodos numéricos. En segundo lugar, se ha desarrollado un modelo de trazado de rayos de Monte Carlo con el objetivo de comprobar la validez del estudio analítico, pero sobre todo porque este no es preciso en el estudio de la reflexión en espejos. El código desarrollado está específicamente ideado para colectores lineales Fresnel, lo que ha permitido la reducción del tiempo de cálculo en varios órdenes de magnitud en comparación con un programa comercial más general. Esto justifica el desarrollo de un nuevo código en lugar de la compra de una licencia de otro programa. El modelo ha sido usado primeramente para comparar la intensidad de flujo térmico y rendimiento de colectores Fresnel, con y sin reflector secundario, con los colectores cilíndrico parabólicos. Finalmente, la conjunción de los resultados obtenidos en el estudio analítico con el programa numérico ha sido usada para optimizar el campo solar para diferentes orientaciones –Norte-Sur y Este-Oeste–, diferentes localizaciones –Almería y Aswan–, diferentes inclinaciones hacia el Trópico –desde 0 deg hasta 32 deg– y diferentes mínimos de intensidad del flujo en el centro del receptor –10 kW/m2 y 25 kW/m2–. La presente tesis ha conducido a importantes descubrimientos que deben ser considerados a la hora de diseñar un campo solar Fresnel. En primer lugar, los espejos utilizados no deben ser plano, sino cilíndricos o parabólicos, ya que los espejos curvos implican mayores concentraciones y rendimiento. Por otro lado, se ha llegado a la conclusión de que la orientación Este-Oeste es más propicia para localizaciones con altas latitudes, como Almería, mientras que en zonas más cercanas a los trópicos como Aswan los campos Norte-Sur conducen a mayores rendimientos. Es de destacar que la orientación Este-Oeste requiere aproximadamente la mitad de espejos que los campos Norte-Sur, puediendo estar inclinados hacia los Trópicos para mejorar el rendimiento, y que alcanzan parecidos valores de intensidad térmica en el receptor todos los días a mediodía. Sin embargo, los campos con orientación Norte-Sur permiten un flujo más constante a lo largo de un día. Por último, ha sido demostrado que el uso de diseños pre-optimizados analíticamente, con anchura de espejos y espaciado entre espejos variables a lo ancho del campo, pueden implicar aumentos de la energía generada por metro cuadrado de espejos de hasta el 6%. El rendimiento óptico anual de los colectores cilíndrico parabólicos es 23 % mayor que el rendimiento de los campos Fresnel en Almería, mientras que la diferencia es de solo 9 % en Aswan. Ello implica que, para alcanzar el mismo precio de electricidad que la tecnología de referencia, la reducción de costes de instalación por metro cuadrado de espejo debe estar entre el 10 % y el 25 %, y que los colectores lineales Fresnel tienen más posibilidades de ser desarrollados en zonas de bajas latitudes. Como consecuencia de los estudios desarrollados en esta tesis se ha patentado un sistema de almacenamiento que tiene en cuenta la variación del flujo térmico en el receptor a lo largo del día, especialmente para campos con orientación Este-Oeste. Este invento permitiría el aprovechamiento de la energía incidente durante más parte del año, aumentando de manera apreciable los rendimientos óptico y térmico. Abstract Concentrating solar power is the common name of a technology based on capturing the thermal power of solar radiation, in a suitable way to reach temperatures able to activate a conventional (or advanced) thermodynamic cycle to generate electricity; this quest mainly depends on our ability to concentrate solar radiation in a cheap and efficient way. The present thesis is focused to highlight and help solving some of the important issues related to this problem. The need of reducing costs in concentrating the direct solar radiation, but without jeopardizing the thermodynamic objective of heating a fluid up to the required temperature, is of prime importance. Linear Fresnel collectors have been identified in the scientific literature as a technology with high potential to reach this cost reduction. This technology has been selected because of a number of reasons, particularly the degrees of freedom of this type of concentrating configuration and its current immature state. In order to respond to this challenge, a very detailed exercise has been carried out on the optical properties of linear Fresnel collectors. This has been done combining analytic and numerical methods. First, the effect of the design variables on the ratio of energy impinging onto the reflecting surface has been studied using analytically developed equations, together with models that predict the location and direct normal irradiance of the sun at any moment. Similarly, errors due to off-axis aberration, to the aperture of the reflected energy beam and to shading and blocking effects have been obtained analytically. This has allowed the comparison of different shapes of mirrors –flat, cylindrical or parabolic–, as well as a preliminary optimization of the location and width of mirrors and receiver with no need of time-consuming numerical models. Second, in order to prove the validity of the analytic results, but also due to the fact that the study of the reflection process is not precise enough when using analytic equations, a Monte Carlo Ray Trace model has been developed. The developed code is designed specifically for linear Fresnel collectors, which has reduced the computing time by several orders of magnitude compared to a wider commercial software. This justifies the development of the new code. The model has been first used to compare radiation flux intensities and efficiencies of linear Fresnel collectors, both multitube receiver and secondary reflector receiver technologies, with parabolic trough collectors. Finally, the results obtained in the analytic study together with the numeric model have used in order to optimize the solar field for different orientations –North-South and East-West–, different locations –Almería and Aswan–, different tilts of the field towards the Tropic –from 0 deg to 32 deg– and different flux intensity minimum requirements –10 kW/m2 and 25 kW/m2. This thesis work has led to several important findings that should be considered in the design of Fresnel solar fields. First, flat mirrors should not be used in any case, as cylindrical and parabolic mirrors lead to higher flux intensities and efficiencies. Second, it has been concluded that, in locations relatively far from the Tropics such as Almería, East-West embodiments are more efficient, while in Aswan North- South orientation leads to a higher annual efficiency. It must be noted that East-West oriented solar fields require approximately half the number of mirrors than NS oriented fields, can be tilted towards the Equator in order to increase the efficiency and attain similar values of flux intensity at the receiver every day at midday. On the other hand, in NS embodiments the flux intensity is more even during each single day. Finally, it has been proved that the use of analytic designs with variable shift between mirrors and variable width of mirrors across the field can lead to improvements in the electricity generated per reflecting surface square meter up to 6%. The annual optical efficiency of parabolic troughs has been found to be 23% higher than the efficiency of Fresnel fields in Almería, but it is only around 9% higher in Aswan. This implies that, in order to attain the same levelized cost of electricity than parabolic troughs, the required reduction of installation costs per mirror square meter is in the range of 10-25%. Also, it is concluded that linear Fresnel collectors are more suitable for low latitude areas. As a consequence of the studies carried out in this thesis, an innovative storage system has been patented. This system takes into account the variation of the flux intensity along the day, especially for East-West oriented solar fields. As a result, the invention would allow to exploit the impinging radiation along longer time every day, increasing appreciably the optical and thermal efficiencies.

High sensitivity biosensors based on shear mode AIN resonators for in liquid operation

El diagnóstico y detección temprana de enfermedades son clave para reducir la tasa de mortalidad, las hospitalizaciones de larga duración y el desaprovechamiento de recursos. En los últimos años se ha impulsado, mediante un aumento de la financiación, el desarrollo de nuevos biosensores de bajo coste capaces de detectar y cuantificar cantidades muy pequeñas de especies biológicas de una forma barata y sencilla. El trabajo presentado en esta Tesis Doctoral describe la investigación llevada a cabo en el desarrollo de sensores gravimétricos basados en resonadores de ondas acústicas de volumen (BAW) de estructura maciza (SMR). Los dispositivos emplean películas delgadas de A1N como material piezoeléctrico y operan en modo de cizalladura, para así poder detectar especies biológicas en medio líquido. El principio de funcionamiento de estos sensores se basa en la variación que experimenta la frecuencia de resonancia al quedar una pequeña masa adherida a su superficie. Necesitan operar en modo de cizalladura para que su resonancia no se atenúe al trabajar en medio líquido, así como ofrecer una superficie capaz de ser funcionalizada específicamente para la especie biológica a detectar. El reto planteado en esta tesis requiere un acercamiento pluridisciplinar al problema que incluye el estudio de los diferentes materiales que constituyen la estructura multicapa que forma un SMR, el diseño y fabricación del dispositivo y del sistema de fluídica, la funcionalización bioquímica de la superficie del sensor, la demostración de la capacidad de detección de especies biológicas y finalmente el diseño y fabricación de la electrónica asociada para la detección de la señal eléctrica. Todas esas tareas han sido abordadas en las distintas etapas del desarrollo de esta tesis y las contribuciones más relevantes se describen en el documento. En el campo de desarrollo de los materiales, se propone un proceso en dos etapas para la pulverización reactiva de capas de A1N que contengan microcristales inclinados capaces de excitar el modo de cizalladura. Se caracteriza la velocidad acústica del modo de cizalladura en todos los materiales que componen la estructura, con el fin de poder obtener un diseño más adecuado del reflector acústico. Se propone un nuevo tipo de material aislante de alta impedancia acústica consistente en capas de W03 pulverizadas que presenta ciertas ventajas tecnológicas frente a las capas convencionales de Ta205. Respecto del diseño del transductor, se estudia la influencia que tienen los con tactos eléctricos extendidos del resonador necesarios para poder adaptar el sistema de fluídica a la estructura. Los resultados indican que es necesario trabajar sobre sustratos aislantes (tanto el soporte como el espejo acústico) para evitar efectos parásitos asociados al uso de capas metálicas bajo los electrodos del resonador que dañan su resonancia. Se analiza la influencia de las diferentes capas del dispositivo en el coeficiente de temperatura de la frecuencia (TCF) del resonador llegando a la conclusión de que las dos últimas capas del reflector acústico afectan significativamente al TCF del SMR, pudiendo reducirse ajusfando adecuadamente sus espesores. De acuerdo con los resultados de estos estudios, se han diseñado finalmente resonadores SMR operando a f .3 GHz en modo de cizalladura, con un área activa de 65000 /xm2, contactos eléctricos que se extienden f .7 mm y factores de calidad en líquido de f 50. Las extensiones eléctricas permiten adaptar el resonador a un sistema de fluídica de metacrilato. Para la detección de especies biológicas se realiza un montaje experimental que permite circular 800 ¡A por la superficie del sensor a través de un circuito cerrado que trabaja a volumen constante. La circulación de soluciones iónicas sobre el sensor descubierto pone de manifiesto que las altas frecuencias de operación previenen los cortocircuitos y por tanto el aislamiento de los electrodos es prescindible. Se desarrolla un protocolo ad-hoc de funcionalización basado en el proceso estándar APTESGlutaraldehído. Se proponen dos alternativas novedosas para la funcionalización de las áreas activas del sensor basadas en el uso de capas de oxidación de Ir02 y su activación a través de un plasma de oxígeno que no daña al dispositivo. Ambos procesos contribuyen a simplificar notablemente la funcionalización de los sensores gravimétricos. Se utilizan anticuerpos y aptámeros como receptores para detectar trombina, anticuerpo monoclonal IgG de ratón y bacteria sonicadas. Una calibración preliminar del sensor con depósitos de capas finas de Si02 de densidad y espesor conocidos permite obtener una sensibilidad de 1800 kHz/pg-cm2 y un límite de detección of 4.2 pg. Finalmente se propone el prototipo de un circuito electrónico de excitación y lectura de bajo coste diseñado empleando teoría de circuitos de microondas. Aunque su diseño y funcionamiento admite mejoras, constituye la última etapa de un sistema completo de bajo coste para el diagnóstico de especies biológicas basado en resonadores SMR de A1N. ABSTRACT Early diagnosis and detection of diseases are essential for reducing mortality rate and preventing long-term hospitalization and waste of resources. These requirements have boosted the efforts and funding on the research of accurate and reliable means for detection and quantification of biological species, also known as biosensors. The work presented in this thesis describes the development and fabrication of gravimetric biosensors based on piezoelectric AlN bulk acoustic wave (BAW) solidly mounted resonators (SMRs) for detection of biological species in liquid media. These type of devices base their sensing principles in the variation that their resonant frequency suffers when a mass is attached to their surface. They need to operate in the shear mode to maintain a strong resonance in liquid and an adequate functionalisation of their sensing area to guarantee that only the targeted molecules cause the shift. The challenges that need to be overcome to achieve piezoelectric BAW resonators for high sensitivity detection in fluids require a multidisciplinary approach, that include the study of the materials involved, the design of the device and the fluidic system, the biochemical functionalisation of the active area, the experimental proof-of-concept with different target species and the design of an electronic readout circuit. All this tasks have been tackled at different stages of the thesis and the relevant contributions are described in the document. In the field of materials, a two-stage sputtering deposition process has been developed to obtain good-quality AlN films with uniformly tilted grains required to excite the shear mode. The shear acoustic velocities of the materials composing the acoustic reflector have been accurately studied to ensure an optimum design of the reflector stack. WO3 sputtered films have been proposed as high acoustic impedance material for insulating acoustic reflectors. They display several technological advantages for the processing of the resonators. Regarding the design, a study of the influence of the electrical extensions necessary to fit a fluidic system on the performance of the devices has been performed. The results indicate that high resistivity substrates and insulating reflectors are necessary to avoid the hindering of the resonance due to the parasitic effects induced by the extensions. The influence of the different layers of the stack on the resultant TCF of the SMRs has also been investigated. The two layers of the reflector closer to the piezoelectric layer have a significant influence on the TCF, which can be reduced by modifying their thicknesses accordingly. The data provided by these studies has led to the final design of the devices, which operate at 1.3 GHz in the shear mode and display an active area of 65000 /xm2 and electrical extensions of 1.7 mm while keeping a Qahear=150 in liquid. The extensions enable to fit a custom-made fluidic system made of methacrylate. To perform the biosensing experiments, an experimental setup with a liquid closed circuit operating at constant flow has been developed. Buffers of ionic characteristics have been tested on non-isolated devices, revealing that high operation frequencies prevent the risk of short circuit. An ad-hoc functionalisation protocol based on the standard APTES - Glutaraldehyde process has been developed. It includes two new processes that simplify the fabrication of the transducers: the use of IrO2 as oxidation layer and its functionalisation through an O2 plasma treatment that does not damage the resonators. Both antibodies and aptamers are used as receptors. In liquid sensing proof-of-concept experiments with thrombin, IgG mouse monoclonal antibody and sonicated bacteria have been displayed. A preliminary calibration of the devices using SiO2 layers reveals a sensitivity of 1800 kHz/pg-cm2 and a limit of detection of 4.2 pg. Finally, a first prototype of a low-cost electronic readout circuit designed using a standard microwave approach has been developed. Although its performance can be significantly improved, it is an effective first approach to the final stage of a portable low-cost diagnostic system based on shear mode AlN SMRs.

Improving Optical Performance of Concentrator Cells by Means of a Deposited Nanopattern Layer

Multijunction solar cells (MJSC) use anti-reflective coatings (ARC) to minimize Fresnel reflection losses for a family of light incidence angles. These coatings adapt the refractive index of the cell to that of the surrounding medium. Patterns with sizes in the range of the light wavelength can be used to further reduce reflections through diffraction. Transparent nanopatterns with a gradual profile, called moth-eye nanostructures, can adapt the refractive index of the optical interfaces (often with n∼1.5) used to encapsulate concentrator solar cells to that of the air (n air∼1). Here we show the effect of a nanometric moth-eye ARC with a round motif deposited on commercial MJSC that achieves short-circuit current (I SC) gains greater than 2% at normal incidence and even higher in the case of tilted illumination. In this work, MJSC with different moth-eye ARC are characterized under quantum efficiency (QE) as well as under concentrated illumination I-V in order to assess their potential. Simulations based on coupled wave analysis (RCWA) are used to fit the experimental results with successful results.

Prime factors

We use Voiculescu’s free probability theory to prove the existence of prime factors, hence answering a longstanding problem in the theory of von Neumann algebras.

On representations of finite type

Representations of the (infinite) canonical anticommutation relations and the associated operator algebra, the fermion algebra, are studied. A “coupling constant” (in (0,1]) is defined for primary states of “finite type” of that algebra. Primary, faithful states of finite type with arbitrary coupling are constructed and classified. Their physical significance for quantum thermodynamical systems at high temperatures is discussed. The scope of this study is broadened to include a large class of operator algebras sharing some of the structural properties of the fermion algebra.

Fourier transform infrared spectroscopy reveals a rigid α-helical assembly for the tetrameric Streptomyces lividans K+ channel

The structure of the tetrameric K+ channel from Streptomyces lividans in a lipid bilayer environment was studied by polarized attenuated total reflection Fourier transform infrared spectroscopy. The channel displays approximately 43% α-helical and 25% β-sheet content. In addition, H/D exchange experiments show that only 43% of the backbone amide protons are exchangeable with solvent. On average, the α-helices are tilted 33° normal to the membrane surface. The results are discussed in relationship to the lactose permease of Escherichia coli, a membrane transport protein.

Mutant G protein α subunit activated by Gβγ: A model for receptor activation?

How receptors catalyze exchange of GTP for GDP bound to the Gα subunit of trimeric G proteins is not known. One proposal is that the receptor uses the G protein's βγ heterodimer as a lever, tilting it to pull open the guanine nucleotide binding pocket of Gα. To test this possibility, we designed a mutant Gα that would bind to βγ in the tilted conformation. To do so, we excised a helical turn (four residues) from the N-terminal region of αs, the α subunit of GS, the stimulatory regulator of adenylyl cyclase. In the presence, but not in the absence, of transiently expressed β1 and γ2, this mutant (αsΔ), markedly stimulated cAMP accumulation. This effect depended on the ability of the coexpressed β protein to interact normally with the lip of the nucleotide binding pocket of αsΔ. We substituted alanine for an aspartate in β1 that binds to a lysine (K206) in the lip of the α subunit's nucleotide binding pocket. Coexpressed with αsΔ and γ2, this mutant, β1-D228A, elevated cAMP much less than did β1-wild type; it did bind to αsΔ normally, however, as indicated by its unimpaired ability to target αsΔ to the plasma membrane. We conclude that βγ can activate αs and that this effect probably involves both a tilt of βγ relative to αs and interaction of β with the lip of the nucleotide binding pocket. We speculate that receptors use a similar mechanism to activate trimeric G proteins.

Quantum groups with invariant integrals

Quantum groups have been studied intensively for the last two decades from various points of view. The underlying mathematical structure is that of an algebra with a coproduct. Compact quantum groups admit Haar measures. However, if we want to have a Haar measure also in the noncompact case, we are forced to work with algebras without identity, and the notion of a coproduct has to be adapted. These considerations lead to the theory of multiplier Hopf algebras, which provides the mathematical tool for studying noncompact quantum groups with Haar measures. I will concentrate on the *-algebra case and assume positivity of the invariant integral. Doing so, I create an algebraic framework that serves as a model for the operator algebra approach to quantum groups. Indeed, the theory of locally compact quantum groups can be seen as the topological version of the theory of quantum groups as they are developed here in a purely algebraic context.