Strategies for reducing fumigant loss to the atmosphere

A model is developed to describe transport and loss of methyl bromide (MeBr) in soil following application as a soil fumigant. The model is used to investigate the effect of soil and management factors on MeBr volatilization. Factors studied include depth of injection, soil water content, presence or absence of tarp, depth to downward barrier, and irrigation after injection. Of these factors, the most important was irrigation after injection followed by covering with the tarp, which increased the diffusive resistance of the soil and prevented early loss of MeBr. The model offers an explanation for the apparently contradictory observations of earlier field studies of MeBr volatilization from soils under different conditions. The model was also used to calculate the concentration-time index for various management alternatives, showing that the irrigation application did not make the surface soil more difficult to fumigate, except at very early times. Therefore, irrigation shows promise for reducing fumigant loss while at the same time permitting control of target organisms during fumigation.

The basel cocktail for simultaneous phenotyping of human cytochrome P450 isoforms in plasma, saliva and dried blood spots.

BACKGROUND AND OBJECTIVE Phenotyping cocktails use a combination of cytochrome P450 (CYP)-specific probe drugs to simultaneously assess the activity of different CYP isoforms. To improve the clinical applicability of CYP phenotyping, the main objectives of this study were to develop a new cocktail based on probe drugs that are widely used in clinical practice and to test whether alternative sampling methods such as collection of dried blood spots (DBS) or saliva could be used to simplify the sampling process. METHODS In a randomized crossover study, a new combination of commercially available probe drugs (the Basel cocktail) was tested for simultaneous phenotyping of CYP1A2, CYP2B6, CYP2C9, CYP2C19, CYP2D6 and CYP3A4. Sixteen subjects received low doses of caffeine, efavirenz, losartan, omeprazole, metoprolol and midazolam in different combinations. All subjects were genotyped, and full pharmacokinetic profiles of the probe drugs and their main metabolites were determined in plasma, dried blood spots and saliva samples. RESULTS The Basel cocktail was well tolerated, and bioequivalence tests showed no evidence of mutual interactions between the probe drugs. In plasma, single timepoint metabolic ratios at 2 h (for CYP2C19 and CYP3A4) or at 8 h (for the other isoforms) after dosing showed high correlations with corresponding area under the concentration-time curve (AUC) ratios (AUC0-24h parent/AUC0-24h metabolite) and are proposed as simple phenotyping metrics. Metabolic ratios in dried blood spots (for CYP1A2 and CYP2C19) or in saliva samples (for CYP1A2) were comparable to plasma ratios and offer the option of minimally invasive or non-invasive phenotyping of these isoforms. CONCLUSIONS This new combination of phenotyping probe drugs can be used without mutual interactions. The proposed sampling timepoints have the potential to facilitate clinical application of phenotyping but require further validation in conditions of altered CYP activity. The use of DBS or saliva samples seems feasible for phenotyping of the selected CYP isoforms.

Chemical composition of particulate matter and element fluxes in the eastern Norwegian Sea, NS Komsomolets wreck site area

This paper reports results of a geochemical study of suspended particulate matter and particle fluxes in the Norwegian Sea above the Bear Island slope. Concentrations of suspended particles and the main components of suspended matter were determined in the euphotic, intermediate (clean water), and bottom nepheloid layers. It was shown that biogenic components are predominant in water above the nepheloid layer, whereas suspended matter of the nepheloid layer is formed by resuspension of lithogenic components of bottom sediments. Chemical compositions of suspended matter and material collected in sediment traps are identical.

TEX86H proxy and BIT index of sediment core GeoB9528-3

Changes in the strength of Atlantic meridional overturning circulation (AMOC) are known to have profound impacts on global climate. Coupled modelling studies have suggested that, on annual to multi-decadal time scales, a slowdown of AMOC causes a deepening of the thermocline in the tropical Atlantic. However, this process has been poorly constrained by sedimentary geochemical records. Here, we reconstruct surface (UK'37 Index) and thermocline (TEXH86) water temperatures from the Guinea Plateau Margin (Eastern tropical Atlantic) over the last two glacial-interglacial cycles (~ 192 kyr). These paleotemperature records show that periods of reduced AMOC, as indicated by the d13 C benthic foraminiferal record from the same core, coincide with a reduction in the near-surface vertical temperature gradient, demonstrating for the first time that AMOC-induced tropical Atlantic thermocline adjustment exists on longer, millennial time scales. Modelling results support the interpretation of the geochemical records and show that thermocline adjustment is particularly pronounced in the eastern tropical Atlantic. Thus, variations in AMOC strength appear to be an important driver of the thermocline structure in the tropical Atlantic from annual to multi-millennial time scales.

TEX86H proxy and BIT index of sediment core GeoB9528-3 and reconstructed temperature data from NW Africa surface sediments

Changes in the strength of Atlantic meridional overturning circulation (AMOC) are known to have profound impacts on global climate. Coupled modelling studies have suggested that, on annual to multi-decadal time scales, a slowdown of AMOC causes a deepening of the thermocline in the tropical Atlantic. However, this process has been poorly constrained by sedimentary geochemical records. Here, we reconstruct surface (UK'37 Index) and thermocline (TEX86H) water temperatures from the Guinea Plateau Margin (Eastern tropical Atlantic) over the last two glacial-interglacial cycles (~ 192 kyr). These paleotemperature records show that periods of reduced AMOC, as indicated by the d13 C benthic foraminiferal record from the same core, coincide with a reduction in the near-surface vertical temperature gradient, demonstrating for the first time that AMOC-induced tropical Atlantic thermocline adjustment exists on longer, millennial time scales. Modelling results support the interpretation of the geochemical records and show that thermocline adjustment is particularly pronounced in the eastern tropical Atlantic. Thus, variations in AMOC strength appear to be an important driver of the thermocline structure in the tropical Atlantic from annual to multi-millennial time scales.

Assessing the dynamic behavior of wsn motes and rfid semi-passive tags for temperature monitoring.

A notorious advantage of wireless transmission is a significant reduction and simplification in wiring and harness. There are a lot of applications of wireless systems, but in many occasions sensor nodes require a specific housing to protect the electronics from hush environmental conditions. Nowadays the information is scarce and nonspecific on the dynamic behaviour of WSN and RFID. Therefore the purpose of this study is to evaluate the dynamic behaviour of the sensors. A series of trials were designed and performed covering temperature steps between cold room (5 °C), room temperature (23 °C) and heated environment (35 °C). As sensor nodes: three Crossbow motes, a surface mounted Nlaza module (with sensor Sensirion located on the motherboard), an aerial mounted Nlaza where the Sensirion sensor stayed at the end of a cable), and four tags RFID Turbo Tag (T700 model with and without housing), and 702-B (with and without housing). To assess the dynamic behaviour a first order response approach is used and fitted with dedicated optimization tools programmed in Matlab that allow extracting the time response (?) and corresponding determination coefficient (r2) with regard to experimental data. The shorter response time (20.9 s) is found for the uncoated T 700 tag which encapsulated version provides a significantly higher response (107.2 s). The highest ? corresponds to the Crossbow modules (144.4 s), followed by the surface mounted Nlaza module (288.1 s), while the module with aerial mounted sensor gives a response certainly close above to the T700 without coating (42.8 s). As a conclusion, the dynamic response of temperature sensors within wireless and RFID nodes is dramatically influenced by the way they are housed (to protect them from the environment) as well as by the heat released by the node electronics itself; its characterization is basic to allow monitoring of high rate temperature changes and to certify the cold chain. Besides the time to rise and to recover is significantly different being mostly higher for the latter than for the former.

Statistical models for short-term wind power ramp forecasting

La predicción de energía eólica ha desempeñado en la última década un papel fundamental en el aprovechamiento de este recurso renovable, ya que permite reducir el impacto que tiene la naturaleza fluctuante del viento en la actividad de diversos agentes implicados en su integración, tales como el operador del sistema o los agentes del mercado eléctrico. Los altos niveles de penetración eólica alcanzados recientemente por algunos países han puesto de manifiesto la necesidad de mejorar las predicciones durante eventos en los que se experimenta una variación importante de la potencia generada por un parque o un conjunto de ellos en un tiempo relativamente corto (del orden de unas pocas horas). Estos eventos, conocidos como rampas, no tienen una única causa, ya que pueden estar motivados por procesos meteorológicos que se dan en muy diferentes escalas espacio-temporales, desde el paso de grandes frentes en la macroescala a procesos convectivos locales como tormentas. Además, el propio proceso de conversión del viento en energía eléctrica juega un papel relevante en la ocurrencia de rampas debido, entre otros factores, a la relación no lineal que impone la curva de potencia del aerogenerador, la desalineación de la máquina con respecto al viento y la interacción aerodinámica entre aerogeneradores. En este trabajo se aborda la aplicación de modelos estadísticos a la predicción de rampas a muy corto plazo. Además, se investiga la relación de este tipo de eventos con procesos atmosféricos en la macroescala. Los modelos se emplean para generar predicciones de punto a partir del modelado estocástico de una serie temporal de potencia generada por un parque eólico. Los horizontes de predicción considerados van de una a seis horas. Como primer paso, se ha elaborado una metodología para caracterizar rampas en series temporales. La denominada función-rampa está basada en la transformada wavelet y proporciona un índice en cada paso temporal. Este índice caracteriza la intensidad de rampa en base a los gradientes de potencia experimentados en un rango determinado de escalas temporales. Se han implementado tres tipos de modelos predictivos de cara a evaluar el papel que juega la complejidad de un modelo en su desempeño: modelos lineales autorregresivos (AR), modelos de coeficientes variables (VCMs) y modelos basado en redes neuronales (ANNs). Los modelos se han entrenado en base a la minimización del error cuadrático medio y la configuración de cada uno de ellos se ha determinado mediante validación cruzada. De cara a analizar la contribución del estado macroescalar de la atmósfera en la predicción de rampas, se ha propuesto una metodología que permite extraer, a partir de las salidas de modelos meteorológicos, información relevante para explicar la ocurrencia de estos eventos. La metodología se basa en el análisis de componentes principales (PCA) para la síntesis de la datos de la atmósfera y en el uso de la información mutua (MI) para estimar la dependencia no lineal entre dos señales. Esta metodología se ha aplicado a datos de reanálisis generados con un modelo de circulación general (GCM) de cara a generar variables exógenas que posteriormente se han introducido en los modelos predictivos. Los casos de estudio considerados corresponden a dos parques eólicos ubicados en España. Los resultados muestran que el modelado de la serie de potencias permitió una mejora notable con respecto al modelo predictivo de referencia (la persistencia) y que al añadir información de la macroescala se obtuvieron mejoras adicionales del mismo orden. Estas mejoras resultaron mayores para el caso de rampas de bajada. Los resultados también indican distintos grados de conexión entre la macroescala y la ocurrencia de rampas en los dos parques considerados. Abstract One of the main drawbacks of wind energy is that it exhibits intermittent generation greatly depending on environmental conditions. Wind power forecasting has proven to be an effective tool for facilitating wind power integration from both the technical and the economical perspective. Indeed, system operators and energy traders benefit from the use of forecasting techniques, because the reduction of the inherent uncertainty of wind power allows them the adoption of optimal decisions. Wind power integration imposes new challenges as higher wind penetration levels are attained. Wind power ramp forecasting is an example of such a recent topic of interest. The term ramp makes reference to a large and rapid variation (1-4 hours) observed in the wind power output of a wind farm or portfolio. Ramp events can be motivated by a broad number of meteorological processes that occur at different time/spatial scales, from the passage of large-scale frontal systems to local processes such as thunderstorms and thermally-driven flows. Ramp events may also be conditioned by features related to the wind-to-power conversion process, such as yaw misalignment, the wind turbine shut-down and the aerodynamic interaction between wind turbines of a wind farm (wake effect). This work is devoted to wind power ramp forecasting, with special focus on the connection between the global scale and ramp events observed at the wind farm level. The framework of this study is the point-forecasting approach. Time series based models were implemented for very short-term prediction, this being characterised by prediction horizons up to six hours ahead. As a first step, a methodology to characterise ramps within a wind power time series was proposed. The so-called ramp function is based on the wavelet transform and it provides a continuous index related to the ramp intensity at each time step. The underlying idea is that ramps are characterised by high power output gradients evaluated under different time scales. A number of state-of-the-art time series based models were considered, namely linear autoregressive (AR) models, varying-coefficient models (VCMs) and artificial neural networks (ANNs). This allowed us to gain insights into how the complexity of the model contributes to the accuracy of the wind power time series modelling. The models were trained in base of a mean squared error criterion and the final set-up of each model was determined through cross-validation techniques. In order to investigate the contribution of the global scale into wind power ramp forecasting, a methodological proposal to identify features in atmospheric raw data that are relevant for explaining wind power ramp events was presented. The proposed methodology is based on two techniques: principal component analysis (PCA) for atmospheric data compression and mutual information (MI) for assessing non-linear dependence between variables. The methodology was applied to reanalysis data generated with a general circulation model (GCM). This allowed for the elaboration of explanatory variables meaningful for ramp forecasting that were utilized as exogenous variables by the forecasting models. The study covered two wind farms located in Spain. All the models outperformed the reference model (the persistence) during both ramp and non-ramp situations. Adding atmospheric information had a noticeable impact on the forecasting performance, specially during ramp-down events. Results also suggested different levels of connection between the ramp occurrence at the wind farm level and the global scale.

Inestabilidad de pórticos planos metálicos de edificación con inclusión de la flexibilidad de las uniones y elementos no prismáticos : un enfoque para la optimización

En esta tesis se aborda el problema de la modelización, análisis y optimización de pórticos metálicos planos de edificación frente a los estados límites último y de servicio. El objetivo general es presentar una técnica secuencial ordenada de optimización discreta para obtener el coste mínimo de pórticos metálicos planos de edificación, teniendo en cuenta las especificaciones del EC-3, incorporando las uniones semirrígidas y elementos no prismáticos en el proceso de diseño. Asimismo se persigue valorar su grado de influencia sobre el diseño final. El horizonte es extraer conclusiones prácticas que puedan ser de utilidad y aplicación simple para el proyecto de estructuras metálicas. La cantidad de publicaciones técnicas y científicas sobre la respuesta estructural de entramados metálicos es inmensa; por ello se ha hecho un esfuerzo intenso en recopilar el estado actual del conocimiento, sobre las líneas y necesidades actuales de investigación. Se ha recabado información sobre los métodos modernos de cálculo y diseño, sobre los factores que influyen sobre la respuesta estructural, sobre técnicas de modelización y de optimización, al amparo de las indicaciones que algunas normativas actuales ofrecen sobre el tema. En esta tesis se ha desarrollado un procedimiento de modelización apoyado en el método de los elementos finitos implementado en el entorno MatLab; se han incluido aspectos claves tales como el comportamiento de segundo orden, la comprobación ante inestabilidad y la búsqueda del óptimo del coste de la estructura frente a estados límites, teniendo en cuenta las especificaciones del EC-3. También se ha modelizado la flexibilidad de las uniones y se ha analizado su influencia en la respuesta de la estructura y en el peso y coste final de la misma. Se han ejecutado algunos ejemplos de aplicación y se ha contrastado la validez del modelo con resultados de algunas estructuras ya analizadas en referencias técnicas conocidas. Se han extraído conclusiones sobre el proceso de modelización y de análisis, sobre la repercusión de la flexibilidad de las uniones en la respuesta de la estructura. El propósito es extraer conclusiones útiles para la etapa de proyecto. Una de las principales aportaciones del trabajo en su enfoque de optimización es la incorporación de una formulación de elementos no prismáticos con uniones semirrígidas en sus extremos. Se ha deducido una matriz de rigidez elástica para dichos elementos. Se ha comprobado su validez para abordar el análisis no lineal; para ello se han comparado los resultados con otros obtenidos tras aplicar otra matriz deducida analíticamente existente en la literatura y también mediante el software comercial SAP2000. Otra de las aportaciones de esta tesis es el desarrollo de un método de optimización del coste de pórticos metálicos planos de edificación en el que se tienen en cuenta aspectos tales como las imperfecciones, la posibilidad de incorporar elementos no prismáticos y la caracterización de las uniones semirrígidas, valorando la influencia de su flexibilidad sobre la respuesta de la estructura. Así, se han realizado estudios paramétricos para valorar la sensibilidad y estabilidad de las soluciones obtenidas, así como rangos de validez de las conclusiones obtenidas. This thesis deals with the problems of modelling, analysis and optimization of plane steel frames with regard to ultimate and serviceability limit states. The objective of this work is to present an organized sequential technique of discrete optimization for achieving the minimum cost of plane steel frames, taking into consideration the EC-3 specifications as well as including effects of the semi-rigid joints and non-prismatic elements in the design process. Likewise, an estimate of their influence on the final design is an aim of this work. The final objective is to draw practical conclusions which can be handful and easily applicable for a steel-structure project. An enormous amount of technical and scientific publications regarding steel frames is currently available, thus making the achievement of a comprehensive and updated knowledge a considerably hard task. In this work, a large variety of information has been gathered and classified, especially that related to current research lines and needs. Thus, the literature collected encompasses references related to state-of-the-art design methods, factors influencing the structural response, modelling and optimization techniques, as well as calculation and updated guidelines of some steel Design Codes about the subject. In this work a modelling procedure based on the finite element implemented within the MatLab programming environment has been performed. Several keys aspects have been included, such as second order behaviour, the safety assessment against structural instability and the search for an optimal cost considering the limit states according to EC-3 specifications. The flexibility of joints has been taken into account in the procedure hereby presented; its effects on the structural response, on the optimum weight and on the final cost have also been analysed. In order to confirm the validity and adequacy of this procedure, some application examples have been carried out. The results obtained were compared with those available from other authors. Several conclusions about the procedure that comprises modelling, analysis and design stages, as well as the effect of the flexibility of connections on the structural response have been drawn. The purpose is to point out some guidelines for the early stages of a project. One of the contributions of this thesis is an attempt for optimizing plane steel frames in which both non-prismatic beam-column-type elements and semi-rigid connections have been considered. Thus, an elastic stiffness matrix has been derived. Its validity has been tested through comparing its accuracy with other analytically-obtained matrices available in the literature, and with results obtained by the commercial software SAP2000. Another achievement of this work is the development of a method for cost optimization of plane steel building frames in which some relevant aspects have been taken in consideration. These encompass geometric imperfections, non-prismatic beam elements and the numerical characterization of semi-rigid connections, evaluating the effect of its flexibility on the structural response. Hence, some parametric analyses have been performed in order to assess the sensitivity, the stability of the outcomes and their range of applicability as well.

Power-frequency control of hydropower plants with long penstocks in isolated systems with wind generation

In this paper the power-frequency control of hydropower plants with long penstocks is addressed. In such configuration the effects of pressure waves cannot be neglected and therefore commonly used criteria for adjustment of PID governors would not be appropriate. A second-order Π model of the turbine-penstock based on a lumped parameter approach is considered. A correction factor is introduced in order to approximate the model frequency response to the continuous case in the frequency interval of interest. Using this model, several criteria are analysed for adjusting the PI governor of a hydropower plant operating in an isolated system. Practical criteria for adjusting the PI governor are given. The results are applied to a real case of a small island where the objective is to achieve a generation 100% renewable (wind and hydro). Frequency control is supposed to be provided exclusively by the hydropower plant. It is verified that the usual criterion for tuning the PI controller of isolated hydro plants gives poor results. However, with the new proposed adjustment, the time response is considerably improved

Acoustic characterization of open cavities with the image source model

El objetivo de esta tesis es investigar las resonancias acústicas de una cavidad abierta tridimensional, de paredes rectas o inclinadas, mediante un método rápido y eficiente en el dominio del tiempo. Este método modela la respuesta temporal en cualquier punto como la convolución de la forma de onda de la fuente con la respuesta impulsiva de la cavidad, la cual se obtiene como una secuencia de impulsos retardados y atenuados procedentes de la fuente real, el primero, y de las fuentes imágenes especulares, los siguientes (Modelo Fuente Imagen, ISM). Además de las componentes directa y reflejadas en las paredes, la respuesta impulsiva también incluye las contribuciones difractadas en los bordes, obtenidas mediante la generación de las componentes difractadas de cada fuente imagen. Las frecuencias de resonancia acústica de la cavidad abierta son extraídas de los picos de la Función de Respuesta en Frecuencia (FRF), obtenida como la transformada de Fourier de la respuesta temporal correspondiente entre una fuente puntual y un punto cualquiera de la cavidad. Las frecuencias de resonancia acústicas estimadas mediante este Método de Fuentes Imagen + difracción en bordes son validadas por comparación con las que proporciona un Modelo de Elementos Finitos (FEM) y con las medidas experimentalmente, con diferencias menores que el 1.6 % y el 2.7 %, respectivamente. A modo de comparación, las frecuencias de resonancia estimadas para la misma cavidad por el método ISM, cuando no se incluye la difracción en los bordes, difieren en un 5.7 % de las obtenidas experimentalmente. ABSTRACT The goal of this thesis is to investigate the acoustic resonances of a three-dimensional open cavity, with parallel and non-parallel walls, by a fast and efficient method in the time domain. This method models the time response in any point as the convolution of the source waveform with the impulse response of the cavity, which, in turn, is obtained as a sequence of attenuated and delayed impulses coming, the first from the real, and the subsequent from the mirror imaged sources (Image Source Model). Besides direct and wall-reflected components, the impulse response includes also edge-diffracted contributions by generating first order diffraction components for each image source. The acoustic resonance frequencies of the open cavity are extracted from the peaks of the Frequency Response Function (FRF), obtained as the Fourier transform of the corresponding time response between a point source and any point in the cavity. The acoustic resonance frequencies estimated by the Image Source Model + edge diffraction are validated by comparison with those provided by a Finite Element Model (FEM) and the ones measured experimentally, differing less than 1.6 % and 2.7 %, respectively. As a comparison, resonance frequencies estimated with the pure Image Source Model differ by 5.7 % from the measured ones.

Utilización de modelos hidráulicos bidimensionales en la determinación del tiempo de concentración

El tiempo de concentración de una cuenca sigue siendo relativamente desconocido para los ingenieros. El procedimiento habitual en un estudio hidrológico es calcularlo según varias fórmulas escogidas entre las existentes para después emplear el valor medio obtenido. De esta media se derivan los demás resultados hidrológicos, resultados que influirán en el futuro dimensionamiento de las infraestructuras. Este trabajo de investigación comenzó con el deseo de conseguir un método más fiable y objetivo que permitiera obtener el tiempo de concentración. Dada la imposibilidad de poner en práctica ensayos hidrológicos en una cuenca física real, ya que no resulta viable monitorizar perfectamente la precipitación ni los caudales de salida, se planteó llevar a cabo los ensayos de forma simulada, con el empleo de modelos hidráulicos bidimensionales de lluvia directa sobre malla 2D de volúmenes finitos. De entre todos los disponibles, se escogió InfoWorks ICM, por su rapidez y facilidad de uso. En una primera fase se efectuó la validación del modelo hidráulico elegido, contrastando los resultados de varias simulaciones con la formulación analítica existente. Posteriormente, se comprobaron los valores de los tiempos de concentración obtenidos con las expresiones referenciadas en la bibliografía, consiguiéndose resultados muy satisfactorios. Una vez verificado, se ejecutaron 690 simulaciones de cuencas tanto naturales como sintéticas, incorporando variaciones de área, pendiente, rugosidad, intensidad y duración de las precipitaciones, a fin de obtener sus tiempos de concentración y retardo. Esta labor se realizó con ayuda de la aceleración del cálculo vectorial que ofrece la tecnología CUDA (Arquitectura Unificada de Dispositivos de Cálculo). Basándose en el análisis dimensional, se agruparon los resultados del tiempo de concentración en monomios adimensionales. Utilizando regresión lineal múltiple, se obtuvo una nueva formulación para el tiempo de concentración. La nueva expresión se contrastó con las formulaciones clásicas, habiéndose obtenido resultados equivalentes. Con la exposición de esta nueva metodología se pretende ayudar al ingeniero en la realización de estudios hidrológicos. Primero porque proporciona datos de manera sencilla y objetiva que se pueden emplear en modelos globales como HEC-HMS. Y segundo porque en sí misma se ha comprobado como una alternativa realmente válida a la metodología hidrológica habitual. Time of concentration remains still fairly imprecise to engineers. A normal hydrological study goes through several formulae, obtaining concentration time as the median value. Most of the remaining hydrologic results will be derived from this value. Those results will determine how future infrastructures will be designed. This research began with the aim to acquire a more reliable and objective method to estimate concentration times. Given the impossibility of carrying out hydrological tests in a real watershed, due to the difficulties related to accurate monitoring of rainfall and derived outflows, a model-based approach was proposed using bidimensional hydraulic simulations of direct rainfall over a 2D finite-volume mesh. Amongst all of the available software packages, InfoWorks ICM was chosen for its speed and ease of use. As a preliminary phase, the selected hydraulic model was validated, checking the outcomes of several simulations over existing analytical formulae. Next, concentration time values were compared to those resulting from expressions referenced in the technical literature. They proved highly satisfactory. Once the model was properly verified, 690 simulations of both natural and synthetic basins were performed, incorporating variations of area, slope, roughness, intensity and duration of rainfall, in order to obtain their concentration and lag times. This job was carried out in a reasonable time lapse with the aid of the parallel computing platform technology CUDA (Compute Unified Device Architecture). Performing dimensional analysis, concentration time results were isolated in dimensionless monomials. Afterwards, a new formulation for the time of concentration was obtained using multiple linear regression. This new expression was checked against classical formulations, obtaining equivalent results. The publication of this new methodology intends to further assist the engineer while carrying out hydrological studies. It is effective to provide global parameters that will feed global models as HEC-HMS on a simple and objective way. It has also been proven as a solid alternative to usual hydrology methodology.

Site-specific conformational determination in thermal unfolding studies of helical peptides using vibrational circular dichroism with isotopic substitution

Understanding the detailed mechanism of protein folding requires dynamic, site-specific stereochemical information. The short time response of vibrational spectroscopies allows evaluation of the distribution of populations in rapid equilibrium as the peptide unfolds. Spectral shifts associated with isotopic labels along with local stereochemical sensitivity of vibrational circular dichroism (VCD) allow determination of the segment sequence of unfolding. For a series of alanine-rich peptides that form α-helices in aqueous solution, we used isotopic labeling and VCD to demonstrate that the α-helix noncooperatively unwinds from the ends with increasing temperature. For these blocked peptides, the C-terminal is frayed at 5°C. Ab initio level theoretical simulations of the IR and VCD band shapes are used to analyze the spectra and to confirm the conformation of the labeled components. The VCD signals associated with the labeled residues are amplified by coupling to the nonlabeled parts of the molecule. Thus small labeled segments are detectable and stereochemically defined in moderately large peptides in this report of site-specific peptide VCD conformational analysis.

Induction of pheromone production in a moth by topical application of a pseudopeptide mimic of a pheromonotropic neuropeptide.

An amphiphilic analog of Locusta myotropin II (Lom-MT-II), Glu-Gly-Asp-Phe-Thr-Pro-Arg-Leu-amide, was synthesized by addition of 6-phenylhexanoic acid (6-Pha) linked through alanine to the amino terminus. This pseudopeptide, [6-Pha-Ala0]Lom-MT-II, was found to have pheromonotropic activity equivalent to pheromone biosynthesis activating neuropeptide when injected into females of Heliothis virescens. Topical application of [6-Pha-Ala0]Lom-MT-II or Helicoverpa zea-pheromone biosynthesis activating neuropeptide (PBAN), dissolved in dimethyl sulfoxide, to the descaled abdomen of females induced production of pheromone, although more Hez-PBAN than [6-Pha-Ala0]Lom-MT-II was required to obtain significant production of pheromone. Application of [6-Pha-Ala0]Lom-MT-II, dissolved in water, to the abdomen induced production of pheromone, but neither Hez-PBAN nor Lom-MT-II dissolved in water stimulated production of significant amounts of pheromone. Dose- and time-response studies indicated that application of the amphiphilic mimetic in water induced pheromone production in as little as 15 min after application and that the effects were maintained for prolonged periods. These findings show that amphiphilic pseudopeptide mimics of insect neuropeptides will penetrate the insect cuticle when applied topically in water and induce an endogenous response.

Photoconductivity and Electro-Optical Properties of Wide Band Gap Metal Oxides

The PhD activity described in this Thesis was focused on the study of metal-oxide wide-bandgap materials, aiming at fabricating new optoelectronic devices such as solar-blind UV photodetectors, high power electronics, and gas sensors. Photocurrent spectroscopy and DC photocurrent time evolution were used to investigate the performance of prototypes under different atmospheres, temperatures and excitation wavelengths (or dark conditions). Cathodoluminescence, absorption spectroscopy, XRD and SEM were used to assess structural, morphologic, electrical and optical properties of materials. This thesis is divided into two main sections, each describing the work done on a different metal-oxide semiconductor. 1) MOVPE-grown Ga2O3 thin films for UV solar-blind photodetectors and high power devices The semiconducting oxides, among them Ga2O3, have been employed for several decades as transparent conducting oxide (TCO) electrodes for fabrication of solar cells, displays, electronic, and opto-electronic devices. The interest was mainly confined to such applications, as these materials tend to grow intrinsically n-type, and attempts to get an effective p-type doping has consistently failed. The key requirements of TCO electrodes are indeed high electrical conductivity and good transparency, while crystallographic perfection is a minor issue. Furthermore, for a long period no high-quality substrates and epi-layers were available, which in turn impeded the development of a truly full-oxide electronics. Recently, Ga2O3 has attracted renewed interest, as large single crystals and high-quality homo- and hetero-epitaxial layers became available, which paved the way to novel application areas. Our research group spent the last two years in developing a low temperature (500-700°C) MOVPE growth procedure to obtain thin films of Ga2O3 on different substrates (Dept. of Physics and IMEM-CNR at UNIPR). We obtained a significant result growing on oriented sapphire epitaxial films of high crystalline, undoped, pure phase -Ga2O3 (hexagonal). The crystallographic properties of this phase were investigated by XRD, in order to clarify the lattice parameters of the hexagonal cell. First design and development of solar blind UV photodetectors based on -phase was carried out and the optoelectronic performance is evaluated by means of photocurrent spectroscopy. The UV-response is adequately fast and reliable to render this unusual phase a subject of great interest for future applications. The availability of a hexagonal phase of Ga2O3 stable up to 700°C, belonging to the same space group of gallium nitride, with high crystallinity and tunable electrical properties, is intriguing in view of the development of nitride-based devices, by taking advantage of the more favorable symmetry and epitaxial relationships with respect to the monoclinic β-phase. In addition, annealing at temperatures higher than 700°C demonstrate that the hexagonal phase converts totally in the monoclinic one. 2) ZnO nano-tetrapods: charge transport mechanisms and time-response in optoelectronic devices and sensors Size and morphology of ZnO at the nanometer scale play a key role in tailoring its physical and chemical properties. Thanks to the possibility of growing zinc oxide in a variety of different nanostructures, there is a great variety of applications, among which gas sensors, light emitting diodes, transparent conducting oxides, solar cells. Even if the operation of ZnO nanostructure-based devices has been recently demonstrated, the mechanisms of charge transport in these assembly is still under debate. The candidate performed an accurate investigation by photocurrent spectroscopy and DC-photocurrent time evolution of electrical response of both single-tetrapod and tetrapod-assembly devices. During the research done for this thesis, a thermal activation energy enables the performance of samples at high temperatures (above about 300°C). The energy barrier is related to the leg-to-leg interconnection in the assembly of nanotetrapods. Percolation mechanisms are responsible for both the very slow photo-response (minutes to hours or days) and the significant persistent photocurrent. Below the bandgap energy, electronic states were investigated but their contribution to the photocurrent are two-three order of magnitude lower than the band edge. Such devices are suitable for employ in photodetectors as well as in gas sensors, provided that the mechanism by which the photo-current is generated and gas adsorption on the surface modify the conductivity of the material are known.

Modelagem e controle de posição e orientação de uma Plataforma de Stewart

Este trabalho apresenta o controle de posição e orientação de um modelo não linear de Plataforma de Stewart com seis graus de liberdade construído no ambiente de sistemas multicorpos ADAMS® desenvolvido pela Mechanical Dynamics, Inc. O modelo não linear é exportado para o ambiente SIMULINK® desenvolvido pela MathWorks, Inc., onde o controle de posição e orientação é realizado a partir da linearização do modelo e a aplicação de um sistema seguidor com realimentação de estados. Utililiza-se, também o SIMULINK® para implementar a dinâmica de um sistema servoválvula e cilindro hidráulico com um servocontrole de pressão e assim simular o comportamento dinâmico de um simulador de vôo com acionamento hidráulico. A utilização destes pacotes comerciais visa obter uma economia de tempo e esforço na modelagem de sistemas mecânicos complexos e na programação para obtenção da resposta do sistema no tempo, além de facilitar a análise de várias configurações de Plataformas de Stewart