Seawater carbonate chemistry and biological processes during experiments with the spider crab Hyas araneus in Kongsfjorden, Svalbard, 2009

With global climate change, ocean warming and acidification occur concomitantly. In this study, we tested the hypothesis that increasing CO2 levels affect the acid-base balance and reduce the activity capacity of the Arctic spider crab Hyas araneus, especially at the limits of thermal tolerance. Crabs were acclimated to projected oceanic CO2 levels for 12 days (today: 380, towards the year 2100: 750 and 1,120 and beyond: 3,000 ?atm) and at two temperatures (1 and 4 °C). Effects of these treatments on the righting response (RR) were determined (1) at acclimation temperatures followed by (2) righting when exposed to an additional acute (15 min) heat stress at 12 °C. Prior to (resting) and after the consecutive stresses of combined righting activity and heat exposure, acid-base status and lactate contents were measured in the haemolymph. Under resting conditions, CO2 caused a decrease in haemolymph pH and an increase in oxygen partial pressure. Despite some buffering via an accumulation of bicarbonate, the extracellular acidosis remained uncompensated at 1 °C, a trend exacerbated when animals were acclimated to 4 °C. The additional combined exposure to activity and heat had only a slight effect on blood gas and acid-base status. Righting activity in all crabs incubated at 1 and 4 °C was unaffected by elevated CO2 levels or acute heat stress but was significantly reduced when both stressors acted synergistically. This impact was much stronger in the group acclimated at 1 °C where some individuals acclimated to high CO2 levels stopped responding. Lactate only accumulated in the haemolymph after combined righting and heat stress. In the group acclimated to 1 °C, lactate content was highest under normocapnia and lowest at the highest CO2 level in line with the finding that RR was largely reduced. In crabs acclimated to 4 °C, the RR was less affected by CO2 such that activity caused lactate to increase with rising CO2 levels. In line with the concept of oxygen and capacity limited thermal tolerance, all animals exposed to temperature extremes displayed a reduction in scope for performance, a trend exacerbated by increasing CO2 levels. Additionally, the differences seen between cold- and warm-acclimated H. araneus after heat stress indicate that a small shift to higher acclimation temperatures also alleviates the response to temperature extremes, indicating a shift in the thermal tolerance window which reduces susceptibility to additional CO2 exposure.

Global Scale Impacts

Global scale impacts modify the physical or thermal state of a substantial fraction of a target asteroid. Specific effects include accretion, family formation, reshaping, mixing and layering, shock and frictional heating, fragmentation, material compaction, dilatation, stripping of mantle and crust, and seismic degradation. Deciphering the complicated record of global scale impacts, in asteroids and meteorites, will lead us to understand the original planet-forming process and its resultant populations, and their evolution in time as collisions became faster and fewer. We provide a brief overview of these ideas, and an introduction to models.

Optimization of InGaAsN(Sb)/GaAs quantum dots for optical emission at 1.55 µm with low optical degradation

Low optical degradation in GaInAsN(Sb)/GaAs quantum dots (QDs) p–i–n structures emitting up to 1.55 μm is presented in this paper. We obtain emission at different energies by means of varying N content from 1 to 4%. The samples show a low photoluminescence (PL) intensity degradation of only 1 order of magnitude when they are compared with pure InGaAs QD structures, even for an emission wavelength as large as 1.55 μm. The optimization studies of these structures for emission at 1.55 μm are reported in this work. High surface density and homogeneity in the QD layers are achieved for 50% In content by rapid decrease in the growth temperature after the formation of the nanostructures. Besides, the effect of N and Sb incorporation in the redshift and PL intensity of the samples is studied by post-growth rapid thermal annealing treatments. As a general conclusion, we observe that the addition of Sb to QD with low N mole fraction is more efficient to reach 1.55 μm and high PL intensity than using high N incorporation in the QD. Also, the growth temperature is determined to be an important parameter to obtain good emission characteristics. Finally, we report room temperature PL emission of InGaAsN(Sb)/GaAs at 1.4 μm.

Thermal diffusion profile by NRA of Deuterium implanted in solid breeder blanket materials

This paper studies the relationship between aging, physical changes and the results of non-destructive testing of plywood. 176 pieces of plywood were tested to analyze their actual and estimated density using non-destructive methods (screw withdrawal force and ultrasound wave velocity) during a laboratory aging test. From the results of statistical analysis it can be concluded that there is a strong relationship between the non-destructive measurements carried out, and the decline in the physical properties of the panels due to aging. The authors propose several models to estimate board density. The best results are obtained with ultrasound. A reliable prediction of the degree of deterioration (aging) of board is presented. Breeder blanket materials have to produce tritium from lithium while fulfilling several strict conditions. In particular, when dealing with materials to be applied in fusion reactors, one of the key questions is the study of light ions retention, which can be produced by transmutation reactions and/or introduced by interaction with the plasma. In ceramic breeders the understanding of the hydrogen isotopes behaviour and specially the diffusion of tritium to the surface is crucial. Moreover the evolution of the microstructure during irradiation with energetic ions, neutrons and electrons is complex because of the interaction of a high number of processes.

Thermal effects in Ni/Au and Mo/Au gate metallization AlGaN/GaN HEMT's reliability

AlGaN/GaN high electron mobility transistors (HEMT) are key devices for the next generation of high-power, high-frequency and high-temperature electronics applications. Although significant progress has been recently achieved [1], stability and reliability are still some of the main issues under investigation, particularly at high temperatures [2-3]. Taking into account that the gate contact metallization is one of the weakest points in AlGaN/GaN HEMTs, the reliability of Ni, Mo, Pt and refractory metal gates is crucial [4-6]. This work has been focused on the thermal stress and reliability assessment of AlGaN/GaN HEMTs. After an unbiased storage at 350 o C for 2000 hours, devices with Ni/Au gates exhibited detrimental IDS-VDS degradation in pulsed mode. In contrast, devices with Mo/Au gates showed no degradation after similar storage conditions. Further capacitance-voltage characterization as a function of temperature and frequency revealed two distinct trap-related effects in both kinds of devices. At low frequency (< 1MHz), increased capacitance near the threshold voltage was present at high temperatures and more pronounced for the Ni/Au gate HEMT and as the frequency is lower. Such an anomalous “bump” has been previously related to H-related surface polar charges [7]. This anomalous behavior in the C-V characteristics was also observed in Mo/Au gate HEMTs after 1000 h at a calculated channel temperatures of around from 250 o C (T2) up to 320 ºC (T4), under a DC bias (VDS= 25 V, IDS= 420 mA/mm) (DC-life test). The devices showed a higher “bump” as the channel temperature is higher (Fig. 1). At 1 MHz, the higher C-V curve slope of the Ni/Au gated HEMTs indicated higher trap density than Mo/Au metallization (Fig. 2). These results highlight that temperature is an acceleration factor in the device degradation, in good agreement with [3]. Interface state density analysis is being performed in order to estimate the trap density and activation energy.

On-Chip Thermal Monitoring: Design, Placement and Interconnection of Temperature Sensors

La temperatura es una preocupación que juega un papel protagonista en el diseño de circuitos integrados modernos. El importante aumento de las densidades de potencia que conllevan las últimas generaciones tecnológicas ha producido la aparición de gradientes térmicos y puntos calientes durante el funcionamiento normal de los chips. La temperatura tiene un impacto negativo en varios parámetros del circuito integrado como el retardo de las puertas, los gastos de disipación de calor, la fiabilidad, el consumo de energía, etc. Con el fin de luchar contra estos efectos nocivos, la técnicas de gestión dinámica de la temperatura (DTM) adaptan el comportamiento del chip en función en la información que proporciona un sistema de monitorización que mide en tiempo de ejecución la información térmica de la superficie del dado. El campo de la monitorización de la temperatura en el chip ha llamado la atención de la comunidad científica en los últimos años y es el objeto de estudio de esta tesis. Esta tesis aborda la temática de control de la temperatura en el chip desde diferentes perspectivas y niveles, ofreciendo soluciones a algunos de los temas más importantes. Los niveles físico y circuital se cubren con el diseño y la caracterización de dos nuevos sensores de temperatura especialmente diseñados para los propósitos de las técnicas DTM. El primer sensor está basado en un mecanismo que obtiene un pulso de anchura variable dependiente de la relación de las corrientes de fuga con la temperatura. De manera resumida, se carga un nodo del circuito y posteriormente se deja flotando de tal manera que se descarga a través de las corrientes de fugas de un transistor; el tiempo de descarga del nodo es la anchura del pulso. Dado que la anchura del pulso muestra una dependencia exponencial con la temperatura, la conversión a una palabra digital se realiza por medio de un contador logarítmico que realiza tanto la conversión tiempo a digital como la linealización de la salida. La estructura resultante de esta combinación de elementos se implementa en una tecnología de 0,35 _m. El sensor ocupa un área muy reducida, 10.250 nm2, y consume muy poca energía, 1.05-65.5nW a 5 muestras/s, estas cifras superaron todos los trabajos previos en el momento en que se publicó por primera vez y en el momento de la publicación de esta tesis, superan a todas las implementaciones anteriores fabricadas en el mismo nodo tecnológico. En cuanto a la precisión, el sensor ofrece una buena linealidad, incluso sin calibrar; se obtiene un error 3_ de 1,97oC, adecuado para tratar con las aplicaciones de DTM. Como se ha explicado, el sensor es completamente compatible con los procesos de fabricación CMOS, este hecho, junto con sus valores reducidos de área y consumo, lo hacen especialmente adecuado para la integración en un sistema de monitorización de DTM con un conjunto de monitores empotrados distribuidos a través del chip. Las crecientes incertidumbres de proceso asociadas a los últimos nodos tecnológicos comprometen las características de linealidad de nuestra primera propuesta de sensor. Con el objetivo de superar estos problemas, proponemos una nueva técnica para obtener la temperatura. La nueva técnica también está basada en las dependencias térmicas de las corrientes de fuga que se utilizan para descargar un nodo flotante. La novedad es que ahora la medida viene dada por el cociente de dos medidas diferentes, en una de las cuales se altera una característica del transistor de descarga |la tensión de puerta. Este cociente resulta ser muy robusto frente a variaciones de proceso y, además, la linealidad obtenida cumple ampliamente los requisitos impuestos por las políticas DTM |error 3_ de 1,17oC considerando variaciones del proceso y calibrando en dos puntos. La implementación de la parte sensora de esta nueva técnica implica varias consideraciones de diseño, tales como la generación de una referencia de tensión independiente de variaciones de proceso, que se analizan en profundidad en la tesis. Para la conversión tiempo-a-digital, se emplea la misma estructura de digitalización que en el primer sensor. Para la implementación física de la parte de digitalización, se ha construido una biblioteca de células estándar completamente nueva orientada a la reducción de área y consumo. El sensor resultante de la unión de todos los bloques se caracteriza por una energía por muestra ultra baja (48-640 pJ) y un área diminuta de 0,0016 mm2, esta cifra mejora todos los trabajos previos. Para probar esta afirmación, se realiza una comparación exhaustiva con más de 40 propuestas de sensores en la literatura científica. Subiendo el nivel de abstracción al sistema, la tercera contribución se centra en el modelado de un sistema de monitorización que consiste de un conjunto de sensores distribuidos por la superficie del chip. Todos los trabajos anteriores de la literatura tienen como objetivo maximizar la precisión del sistema con el mínimo número de monitores. Como novedad, en nuestra propuesta se introducen nuevos parámetros de calidad aparte del número de sensores, también se considera el consumo de energía, la frecuencia de muestreo, los costes de interconexión y la posibilidad de elegir diferentes tipos de monitores. El modelo se introduce en un algoritmo de recocido simulado que recibe la información térmica de un sistema, sus propiedades físicas, limitaciones de área, potencia e interconexión y una colección de tipos de monitor; el algoritmo proporciona el tipo seleccionado de monitor, el número de monitores, su posición y la velocidad de muestreo _optima. Para probar la validez del algoritmo, se presentan varios casos de estudio para el procesador Alpha 21364 considerando distintas restricciones. En comparación con otros trabajos previos en la literatura, el modelo que aquí se presenta es el más completo. Finalmente, la última contribución se dirige al nivel de red, partiendo de un conjunto de monitores de temperatura de posiciones conocidas, nos concentramos en resolver el problema de la conexión de los sensores de una forma eficiente en área y consumo. Nuestra primera propuesta en este campo es la introducción de un nuevo nivel en la jerarquía de interconexión, el nivel de trillado (o threshing en inglés), entre los monitores y los buses tradicionales de periféricos. En este nuevo nivel se aplica selectividad de datos para reducir la cantidad de información que se envía al controlador central. La idea detrás de este nuevo nivel es que en este tipo de redes la mayoría de los datos es inútil, porque desde el punto de vista del controlador sólo una pequeña cantidad de datos |normalmente sólo los valores extremos| es de interés. Para cubrir el nuevo nivel, proponemos una red de monitorización mono-conexión que se basa en un esquema de señalización en el dominio de tiempo. Este esquema reduce significativamente tanto la actividad de conmutación sobre la conexión como el consumo de energía de la red. Otra ventaja de este esquema es que los datos de los monitores llegan directamente ordenados al controlador. Si este tipo de señalización se aplica a sensores que realizan conversión tiempo-a-digital, se puede obtener compartición de recursos de digitalización tanto en tiempo como en espacio, lo que supone un importante ahorro de área y consumo. Finalmente, se presentan dos prototipos de sistemas de monitorización completos que de manera significativa superan la características de trabajos anteriores en términos de área y, especialmente, consumo de energía. Abstract Temperature is a first class design concern in modern integrated circuits. The important increase in power densities associated to recent technology evolutions has lead to the apparition of thermal gradients and hot spots during run time operation. Temperature impacts several circuit parameters such as speed, cooling budgets, reliability, power consumption, etc. In order to fight against these negative effects, dynamic thermal management (DTM) techniques adapt the behavior of the chip relying on the information of a monitoring system that provides run-time thermal information of the die surface. The field of on-chip temperature monitoring has drawn the attention of the scientific community in the recent years and is the object of study of this thesis. This thesis approaches the matter of on-chip temperature monitoring from different perspectives and levels, providing solutions to some of the most important issues. The physical and circuital levels are covered with the design and characterization of two novel temperature sensors specially tailored for DTM purposes. The first sensor is based upon a mechanism that obtains a pulse with a varying width based on the variations of the leakage currents on the temperature. In a nutshell, a circuit node is charged and subsequently left floating so that it discharges away through the subthreshold currents of a transistor; the time the node takes to discharge is the width of the pulse. Since the width of the pulse displays an exponential dependence on the temperature, the conversion into a digital word is realized by means of a logarithmic counter that performs both the timeto- digital conversion and the linearization of the output. The structure resulting from this combination of elements is implemented in a 0.35_m technology and is characterized by very reduced area, 10250 nm2, and power consumption, 1.05-65.5 nW at 5 samples/s, these figures outperformed all previous works by the time it was first published and still, by the time of the publication of this thesis, they outnumber all previous implementations in the same technology node. Concerning the accuracy, the sensor exhibits good linearity, even without calibration it displays a 3_ error of 1.97oC, appropriate to deal with DTM applications. As explained, the sensor is completely compatible with standard CMOS processes, this fact, along with its tiny area and power overhead, makes it specially suitable for the integration in a DTM monitoring system with a collection of on-chip monitors distributed across the chip. The exacerbated process fluctuations carried along with recent technology nodes jeop-ardize the linearity characteristics of the first sensor. In order to overcome these problems, a new temperature inferring technique is proposed. In this case, we also rely on the thermal dependencies of leakage currents that are used to discharge a floating node, but now, the result comes from the ratio of two different measures, in one of which we alter a characteristic of the discharging transistor |the gate voltage. This ratio proves to be very robust against process variations and displays a more than suficient linearity on the temperature |1.17oC 3_ error considering process variations and performing two-point calibration. The implementation of the sensing part based on this new technique implies several issues, such as the generation of process variations independent voltage reference, that are analyzed in depth in the thesis. In order to perform the time-to-digital conversion, we employ the same digitization structure the former sensor used. A completely new standard cell library targeting low area and power overhead is built from scratch to implement the digitization part. Putting all the pieces together, we achieve a complete sensor system that is characterized by ultra low energy per conversion of 48-640pJ and area of 0.0016mm2, this figure outperforms all previous works. To prove this statement, we perform a thorough comparison with over 40 works from the scientific literature. Moving up to the system level, the third contribution is centered on the modeling of a monitoring system consisting of set of thermal sensors distributed across the chip. All previous works from the literature target maximizing the accuracy of the system with the minimum number of monitors. In contrast, we introduce new metrics of quality apart form just the number of sensors; we consider the power consumption, the sampling frequency, the possibility to consider different types of monitors and the interconnection costs. The model is introduced in a simulated annealing algorithm that receives the thermal information of a system, its physical properties, area, power and interconnection constraints and a collection of monitor types; the algorithm yields the selected type of monitor, the number of monitors, their position and the optimum sampling rate. We test the algorithm with the Alpha 21364 processor under several constraint configurations to prove its validity. When compared to other previous works in the literature, the modeling presented here is the most complete. Finally, the last contribution targets the networking level, given an allocated set of temperature monitors, we focused on solving the problem of connecting them in an efficient way from the area and power perspectives. Our first proposal in this area is the introduction of a new interconnection hierarchy level, the threshing level, in between the monitors and the traditional peripheral buses that applies data selectivity to reduce the amount of information that is sent to the central controller. The idea behind this new level is that in this kind of networks most data are useless because from the controller viewpoint just a small amount of data |normally extreme values| is of interest. To cover the new interconnection level, we propose a single-wire monitoring network based on a time-domain signaling scheme that significantly reduces both the switching activity over the wire and the power consumption of the network. This scheme codes the information in the time domain and allows a straightforward obtention of an ordered list of values from the maximum to the minimum. If the scheme is applied to monitors that employ TDC, digitization resource sharing is achieved, producing an important saving in area and power consumption. Two prototypes of complete monitoring systems are presented, they significantly overcome previous works in terms of area and, specially, power consumption.

Sustainability of irrigated farming systems in a Tunisian region: A recursive stochastic programming analysis

The aim of this study was to evaluate the sustainability of farm irrigation systems in the Cébalat district in northern Tunisia. It addressed the challenging topic of sustainable agriculture through a bio-economic approach linking a biophysical model to an economic optimisation model. A crop growth simulation model (CropSyst) was used to build a database to determine the relationships between agricultural practices, crop yields and environmental effects (salt accumulation in soil and leaching of nitrates) in a context of high climatic variability. The database was then fed into a recursive stochastic model set for a 10-year plan that allowed analysing the effects of cropping patterns on farm income, salt accumulation and nitrate leaching. We assumed that the long-term sustainability of soil productivity might be in conflict with farm profitability in the short-term. Assuming a discount rate of 10% (for the base scenario), the model closely reproduced the current system and allowed to predict the degradation of soil quality due to long-term salt accumulation. The results showed that there was more accumulation of salt in the soil for the base scenario than for the alternative scenario (discount rate of 0%). This result was induced by applying a higher quantity of water per hectare for the alternative as compared to a base scenario. The results also showed that nitrogen leaching is very low for the two discount rates and all climate scenarios. In conclusion, the results show that the difference in farm income between the alternative and base scenarios increases over time to attain 45% after 10 years.

Degradation in seawater of structural adhesives for hybrid fibre-metal laminated materials

The adhesives used for applications in marine environments are subject to particular chemical conditions, which are mainly characterised by an elevated chlorine ion content and intermittent wetting/drying cycles, among others.These conditions can limit the use of adhesives due to the degradation processes that they experience. In this work, the chemical degradation of two different polymers, polyurethane and vinylester, was studied in natural seawater under immersion for different periods of time.The diffusion coefficients and concentration profiles of water throughout the thickness of the adhesiveswere obtained.Microstructural changes in the polymer due to the action of water were observed by SEM, and the chemical degradation of the polymer was monitored with the Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The degradation of the mechanical properties of the adhesive was determined by creep tests withMixed Cantilever Beam (MCB) specimens at different temperatures. After 180 days of immersion of the specimens, it was concluded that the J-integral value (depending on the strain) implies a loss of stiffness of 51% and a decrease in the failure load of 59% for the adhesive tested.

Tuning the properties of carbon fiber-reinforced poly (phenylene sulphide) laminates via incorporation of inorganic fullerene-like WS2 nanoparticles

Novel carbon fiber (CF)-reinforced poly(phenylene sulphide) (PPS) laminates incorporating inorganic fullerene-like tungsten disulfide (IF-WS2) nanoparticles were prepared via melt-blending and hot-press processing. The influence of the IF-WS2 on the morphology, thermal, mechanical and tribological properties of PPS/CF composites was investigated. Efficient nanoparticle dispersion within the matrix was attained without using surfactants. A progressive rise in thermal stability was found with increasing IF-WS2 loading, as revealed by thermogravimetric analysis. The addition of low nanoparticle contents retarded the crystallization of the matrix, whereas concentrations equal or higher than 1.0 wt% increased both the crystallization temperature and degree of crystallinity compared to those of PPS/CF. Mechanical tests indicated that with only 1.0 wt% IF-WS2 the flexural modulus and strength of PPS/CF improved by 17 and 14%, respectively, without loss in toughness, ascribed to a synergistic effect between the two fillers. A significant enhancement in the storage modulus and glass transition temperature was also observed. Moreover, the wear rate and coefficient of friction strongly decreased, attributed to the lubricant role of the IF-WS2 combined with their reinforcing effect. These inorganic nanoparticles show great potential to improve the mechanical and tribological properties of conventional thermoplastic/CF composites for structural applications.

Highly conductive coatings of carbon black/silica composites obtained by a sol-gel process

Conductive submicronic coatings of carbon black (CB)/silica composites have been prepared by a sol-gel process and deposited by spray-coating on glazed porcelain tiles. Stable CB dispersions with surfactant were rheologically characterized to determine the optimum CB-surfactant ratio. The composites were analyzed by Differential Thermal and Thermogravimetric Analysis and Hg-Porosimetry. Thin coatings were thermally treated in the temperature range of 300-500degC in air atmosphere. The microstructure of the coatings was determined by scanning electron microscopy and the structure evaluated by confocal Raman spectroscopy. The electrical characterization of the samples was carried out using dc intensity-voltage curves. The coatings exhibit good adhesion, high density and homogeneous distribution of the conductive filler (CB) in the insulate matrix (silica) that protects against the thermal degradation of the CB nanoparticles during the sintering process. As consequence, the composite coatings show the lowest resistivity values for CB-based films reported in the literature, with values of ~7times10 -5Omegam.

Thermal and mechanical effects of different excitation modes based on low frequency laser modulation in optical hyperthermia

The low frequency modulation of the laser source (menor que30KHz) allows the generation of a pulsed signal that intermittently excites the gold nanorods. The temperature curves obtained for different frequencies and duty cycles of modulation but with equal average power and identical laser parameters, show that the thermal behavior in continuous wave and modulation modes is the same. However, the cell death experiments suggest that the percentage of death is higher in the cases of modulation. This observation allows us to conclude that there are other effects in addition to temperature that contribute to the cellular death. The mechanical effects like sound or pressure waves are expected to be generated from thermal expansion of gold nanorods. In order to study the behavior and magnitude of these processes we have developed a measure device based on ultrasound piezoelectric receivers (25KHz) and a lock-in amplifier that is able to detect the sound waves generated in samples of gold nanorods during laser irradiation providing us a voltage result proportional to the pressure signal. The first results show that the pressure measurements are directly proportional to the concentration of gold nanorods and the laser power, therefore, our present work is focused on determine the real influence of these effects in the cell death process.

New Intermediate band sulphide nanoparticles acting in the full visible light range spectra as an active photocatalyst

Nowadays one of the challenges of materials science is to find new technologies that will be able to make the most of renewable energies. An example of new proposals in this field are the intermediate-band (IB) materials, which promise higher efficiencies in photovoltaic applications (through the intermediate band solar cells), or in heterogeneous photocatalysis (using nanoparticles of them, for the light-induced degradation of pollutants or for the efficient photoevolution of hydrogen from water). An IB material consists in a semiconductor in which gap a new level is introduced [1], the intermediate band (IB), which should be partially filled by electrons and completely separated of the valence band (VB) and of the conduction band (CB). This scheme (figure 1) allows an electron from the VB to be promoted to the IB, and from the latter to the CB, upon absorption of photons with energy below the band gap Eg, so that energy can be absorbed in a wider range of the solar spectrum and a higher current can be obtained without sacrificing the photovoltage (or the chemical driving force) corresponding to the full bandgap Eg, thus increasing the overall efficiency. This concept, applied to photocatalysis, would allow using photons of a wider visible range while keeping the same redox capacity. It is important to note that this concept differs from the classic photocatalyst doping principle, which essentially tries just to decrease the bandgap. This new type of materials would keep the full bandgap potential but would use also lower energy photons. In our group several IB materials have been proposed, mainly for the photovoltaic application, based on extensively doping known semiconductors with transition metals [2], examining with DFT calculations their electronic structures. Here we refer to In2S3 and SnS2, which contain octahedral cations; when doped with Ti or V an IB is formed according to quantum calculations (see e.g. figure 2). We have used a solvotermal synthesis method to prepare in nanocrystalline form the In2S3 thiospinel and the layered compound SnS2 (which when undoped have bandgaps of 2.0 and 2.2 eV respectively) where the cation is substituted by vanadium at a ?10% level. This substitution has been studied, characterizing the materials by different physical and chemical techniques (TXRF, XRD, HR-TEM/EDS) (see e.g. figure 3) and verifying with UV spectrometry that this substitution introduces in the spectrum the sub-bandgap features predicted by the calculations (figure 4). For both sulphide type nanoparticles (doped and undoped) the photocatalytic activity was studied by following at room temperature the oxidation of formic acid in aqueous suspension, a simple reaction which is easily monitored by UV-Vis spectroscopy. The spectral response of the process is measured using a collection of band pass filters that allow only some wavelengths into the reaction system. Thanks to this method the spectral range in which the materials are active in the photodecomposition (which coincides with the band gap for the undoped samples) can be checked, proving that for the vanadium substituted samples this range is increased, making possible to cover all the visible light range. Furthermore it is checked that these new materials are more photocorrosion resistant than the toxic CdS witch is a well know compound frequently used in tests of visible light photocatalysis. These materials are thus promising not only for degradation of pollutants (or for photovoltaic cells) but also for efficient photoevolution of hydrogen from water; work in this direction is now being pursued.

Contribución al estudio de sistemas de hipertermia óptica y su aplicación en muestras biológicas

Las nanopartículas de metales nobles (especialmente las de oro) tienen un gran potencial asociado al desarrollo de sistemas de terapia contra el cáncer debido principalmente a sus propiedades ópticas, ya que cuando son irradiadas con un haz de luz sintonizado en longitud de onda con su máximo de Resonancia de Plasmón Superficial, absorben de manera muy eficiente dicha luz y la disipan rápidamente al medio en forma de calor localizado. Esta característica por tanto, puede ser aprovechada para conseguir elevar la temperatura de células tumorales hasta sobrepasar umbrales a partir de los cuales se produciría la muerte celular. Partiendo de estos principios, esta tesis se centra en el desarrollo y la caracterización de una serie de prototipos de hipertermia óptica basados en la irradiación de nanopartículas de oro con un haz de luz adecuado, así como en la aplicación in vitro de la terapia sobre células cancerígenas. Además, el trabajo se orienta a identificar y comprender los procesos mecánicos y térmicos asociados a este tipo de hipertermia, y a desarrollar modelos que los describan, estudiando y planteando nuevas formas de irradiación, para, en última instancia, poder optimizar los procesos descritos y hacerlos más efectivos. Los resultados obtenidos indican que, el uso de nanopartículas de oro, y más concretamente de nanorods de oro, para llevar a cabo terapias de hipertermia óptica, permite desarrollar terapias muy efectivas para inducir muerte en células cancerígenas, especialmente en tumores superficiales, o como complemento quirúrgico en tumores internos. Sin embargo, los efectos de la toxicidad de las nanopartículas de oro, aún deben ser detalladamente estudiados, ya que este tipo de terapias sólo será viable si se consigue una completa biocompatibilidad. Por otro lado, el estudio exhaustivo de los procesos térmicos que tienen lugar durante la irradiación de las nanopartículas ha dado lugar a una serie de modelos que permiten determinar la efectividad fototérmica de las nanopartículas y además, visualizar la evolución de la temperatura tanto a escala nanométrica como a escala macrométrica, en función de los parámetros ópticos y térmicos del sistema. El planteamiento de nuevas formas de irradiación y el desarrollo de dispositivos orientados a estudiar los fenómenos mecánicos que tienen lugar durante la irradiación pulsada de baja frecuencia y baja potencia de nanopartículas de oro, ha dado lugar a la detección de ondas de presión asociadas a procesos de expansión termoelástica, abriendo la puerta al desarrollo de terapias de hipertermia que combinen la muerte celular producida por calentamiento con la muerte derivada de los fenómenos mecánicos descritos.VII Noble metal nanoparticles (especially gold ones), have a huge potential in the development of therapy systems against cancer mainly due to their optical properties, so that, when these particles are irradiated with a light that is syntonized in wavelength with their maximum of Surface Plasmon Resonance, they effectively absorb and dissipate the light to the surrounding medium as localized heat. We can take advantage of this characteristic for rising the temperature of cancer cells above the threshold at which cellular death would occur. From these principles, this thesis is oriented to the development and characterization of a series of optical hyperthermia prototypes based on the irradiation of gold nanoparticles using the suitable light, and on the in vitro application of this therapy over cancer cells, to understand the mechanical and thermal processes associated with this kind of hyperthermia, developing descriptive models, and to study and to approach new ways of irradiation in order to, ultimately, optimize the described processes and make them more effective. The obtained results show that, the use of gold nanoparticles, and more specifically, of gold nanorods, to carry out optical hyperthermia therapies, allows the development of very effective therapies in order to induce death in VIII cancer cells, especially in superficial tumors, or like surgical complement in more internal tumors. However, the toxicity effects of the gold nanoparticles still need to be studied more detail, because this kind of therapies will be feasible only if a complete biocompatibility is achieved. On the other hand, the exhaustive study of the thermal processes that take place during the irradiation of the nanoparticles resulted in a series of models that allow the determination of the photothermal efficiency of the nanoparticles and also the visualization of the temperature evolution, both at nanoscale and at macroscale, as a function of the optical and thermal parameters of the system. The proposal of new ways of irradiation and the development of devices oriented to study the mechanical effects that take place during the low frequency and low power pulsing irradiation of gold nanoparticles has led to the detection of pressure waves associated to thermoelastic expansion processes, opening the door to the development of hyperthermia therapies that combine the cellular death due to the heating with the death derived from the described mechanical phenomena.