High-conversion-efficiency and broadband tunable femtosecond noncollinear optical parametric amplifier

We build a compact high-conversion-efficiency and broadband tunable noncollinear optical parametric amplifier (OPA) in the infra-red (IR) pumped by a femtosecond Ti:sapphire CPA laser. The OPA consists of an internal seed of white-light continuum generator (WLG) and two noncollinear optical parametric amplifiers. The tunable wavelength range is from 1.2 mu m to 2.4 mu m for both signal and idle pulses. The total OPA efficiency in the last OPA stage reaches about 40% in a wider tunable spectral range (from 1.3 mu m to 1.7 mu m for signal pulse, from 1.5 mu m to 2.0 mu m for idle pulse respectively).

Catalytic conversion of nitrogen to ammonia by an iron model complex

Threefold symmetric Fe phosphine complexes have been used to model the structural and functional aspects of biological N₂ fixation by nitrogenases. Low-valent bridging Fe-S-Fe complexes in the formal oxidation states Fe(II)Fe(II), Fe(II)/Fe(I), and Fe(I)/Fe(I) have been synthesized which display rich spectroscopic and magnetic behavior. A series of cationic tris-phosphine borane (TPB) ligated Fe complexes have been synthesized and been shown to bind a variety of nitrogenous ligands including N₂H₄, NH₃, and NH₂-. These complexes are all high spin S = 3/2 and display EPR and magnetic characteristics typical of this spin state. Furthermore, a sequential protonation and reduction sequence of a terminal amide results in loss of NH₃ and uptake of N₂. These stoichiometric transformations represent the final steps in potential N₂ fixation schemes.

Treatment of an anionic FeN₂ complex with excess acid also results in the formation of some NH₃, suggesting the possibility of a catalytic cycle for the conversion of N₂ to NH₃ mediated by Fe. Indeed, use of excess acid and reductant results in the formation of seven equivalents of NH₃ per Fe center, demonstrating Fe mediated catalytic N₂ fixation with acids and protons for the first time. Numerous control experiments indicate that this catalysis is likely being mediated by a molecular species.

A number of other phosphine ligated Fe complexes have also been tested for catalysis and suggest that a hemi-labile Fe-B interaction may be critical for catalysis. Additionally, various conditions for the catalysis have been investigated. These studies further support the assignment of a molecular species and delineate some of the conditions required for catalysis.

Finally, combined spectroscopic studies have been performed on a putative intermediate for catalysis. These studies converge on an assignment of this new species as a hydrazido(2-) complex. Such species have been known on group 6 metals for some time, but this represents the first characterization of this ligand on Fe. Further spectroscopic studies suggest that this species is present in catalytic mixtures, which suggests that the first steps of a distal mechanism for N₂ fixation are feasible in this system.

Nanostructured tungsten trioxide photoanodes for solar energy conversion

Nanostructured tungsten trioxide (WO₃) photoelectrodes are potential candidates for the anodic portion of an integrated solar water-splitting device that generates hydrogen fuel and oxygen from water. These nanostructured materials can potentially offer improved performance in photooxidation reactions compared to unstructured materials because of enhancements in light scattering, increases in surface area, and their decoupling of the directions of light absorption and carrier collection. To evaluate the presence of these effects and their contributions toward energy conversion efficiency, a variety of nanostructured WO₃ photoanodes were synthesized by electrodeposition within nanoporous templates and by anodization of tungsten foils. A robust fabrication process was developed for the creation of oriented WO₃ nanorod arrays, which allows for control nanorod diameter and length. Films of nanostructured WO₃ platelets were grown via anodization, the morphology of the films was controlled by the anodization conditions, and the current-voltage performance and spectral response properties of these films were studied. The observed photocurrents were consistent with the apparent morphologies of the nanostructured arrays. Measurements of electrochemically active surface area and other physical characteristics were correlated with observed differences in absorbance, external quantum yield, and photocurrent density for the anodized arrays. The capability to quantify these characteristics and relate them to photoanode performance metrics can allow for selection of appropriate structural parameters when designing photoanodes for solar energy conversion.

Coherent enhancement of broadband frequency up-conversion in BBO crystal by shaping femtosecond laser pulses

An optimal feedback control of broadband frequency up-conversion in BBO crystal is experimentally demonstrated by shaping femto-second laser pulses based on genetic algorithm, and the frequency up-conversion efficiency can be enhanced by similar to 16%. SPIDER results show that the optimal laser pulses have shorter pulse-width with the little negative chirp than the original pulse with the little positive chirp. By modulating the fundamental spectral phase with periodic square distribution on SLM-256, the frequency up-conversion can be effectively controlled by the factor of about 17%. The experimental results indicate that the broadband frequency up-conversion efficiency is related to both of second harmonic generation (SHG) and sum frequency generation (SFG), where the former depends on the fundamental pulse intensity, and the latter depends on not only the fundamental pulse intensity but also the fundamental pulse spectral phase. (c) 2006 Elsevier B.V. All rights reserved.

Edad de menarquía e indicadores de adiposidad en mujeres del País Vasco (España)

[ES] El objetivo del presente trabajo es analizar la relación entre la cantidad de grasa y su patrón de distribución con la edad de menarquia, en una muestra de 641 jóvenes universitarias de la UPVEHU (18+ a 29+ años), así como en una muestra de 378 mujeres de más edad (30+ y 49+ años). Se midieron la estatura, el peso y cinco pliegues de grasa subcutánea. Se calcularon el IMC y el % de grasa (Siri, 1961). La obtención de los patrones de distribución de grasa, central vs. periférico, se realizó mediante un ACP. La edad de menarquia se ha estimado mediante el método retrospectivo y las categorías de maduración se basan en las medias y desviaciones típicas de cada muestra. En general, se comprueba que las maduradoras tempranas tienen mayor cantidad de grasa y son algo más centrales que las de maduración media y tardía. La asociación es más evidente en la muestra de mayor edad, por lo que la asociación entre maduración sexual y adiposidad depende de la etapa del ciclo vital, haciéndose más patente conforme aumenta la edad.

Part I. Efforts directed towards the total synthesis of shionone. Part II. Conversion of estrone to androst-4-EN-3-ONE: a new method for activating the C-9 and C-10 positions of estrogenic steroids for substitution

Part I: An approach to the total synthesis of the triterpene shionone is described, which proceeds through the tetracyclic ketone i. The shionone side chain has been attached to this key intermediate in 5 steps, affording the olefin 2 in 29% yield. A method for the stereo-specific introduction of the angular methyl group at C-5 of shionone has been developed on a model system. The attempted utilization of this method to convert olefin 2 into shionone is described.

Part II: A method has been developed for activating the C-9 and C-10 positions of estrogenic steroids for substitution. Estrone has been converted to 4β,5β-epoxy-10β-hydroxyestr-3-one; cleavage of this epoxyketone using an Eschenmoser procedure, and subsequent modification of the product afforded 4-seco-9-estren-3,5-dione 3-ethylene acetal. This versatile intermediate, suitable for substitution at the 9 and/or 10 position, was converted to androst-4-ene-3-one by known procedures.

Resonance cones and mode conversion in a warm magnetized bounded plasma

The warm plasma resonance cone structure of the quasistatic field produced by a gap source in a bounded magnetized slab plasma is determined theoretically. This is initially determined for a homogeneous or mildly inhomogeneous plasma with source frequency lying between the lower hybrid frequency and the plasma frequency. It is then extended to the complicated case of an inhomogeneous plasma with two internal lower hybrid layers present, which is of interest to radio frequency heating of plasmas.

In the first case, the potential is obtained as a sum of multiply reflected warm plasma resonance cones, each of which has a similar structure, but a different size, amplitude, and position. An important interference between nearby multiply-reflected resonance cones is found. The cones are seen to spread out as they move away from the source, so that this interference increases and the individual resonance cones become obscured far away from the source.

In the second case, the potential is found to be expressible as a sum of multiply-reflected, multiply-tunnelled, and mode converted resonance cones, each of which has a unique but similar structure. The effects of both collisional and collisionless damping are included and their effects on the decay of the cone structure studied. Various properties of the cones such as how they move into and out of the hybrid layers, through the evanescent region, and transform at the hybrid layers are determined. It is found that cones can tunnel through the evanescent layer if the layer is thin, and the effect of the thin evanescent layer is to subdue the secondary maxima of cone relative to the main peak, while slightly broadening the main peak and shifting it closer to the cold plasma cone line.

Energy theorems for quasistatic fields are developed and applied to determine the power flow and absorption along the individual cones. This reveals the points of concentration of the flow and the various absorption mechanisms.

A study of a new electromechanical energy conversion process using superconducting frequency modulated resonators

Experimental demonstrations and theoretical analyses of a new electromechanical energy conversion process which is made feasible only by the unique properties of superconductors are presented in this dissertation. This energy conversion process is characterized by a highly efficient direct energy transformation from microwave energy into mechanical energy or vice versa and can be achieved at high power level. It is an application of a well established physical principle known as the adiabatic theorem (Boltzmann-Ehrenfest theorem) and in this case time dependent superconducting boundaries provide the necessary interface between the microwave energy on one hand and the mechanical work on the other. The mechanism which brings about the conversion is another known phenomenon - the Doppler effect. The resonant frequency of a superconducting resonator undergoes continuous infinitesimal shifts when the resonator boundaries are adiabatically changed in time by an external mechanical mechanism. These small frequency shifts can accumulate coherently over an extended period of time to produce a macroscopic shift when the resonator remains resonantly excited throughout this process. In addition, the electromagnetic energy in s ide the resonator which is proportional to the oscillation frequency is al so accordingly changed so that a direct conversion between electromagnetic and mechanical energies takes place. The intrinsically high efficiency of this process is due to the electromechanical interactions involved in the conversion rather than a process of thermodynamic nature and therefore is not limited by the thermodynamic value.

A highly reentrant superconducting resonator resonating in the range of 90 to 160 MHz was used for demonstrating this new conversion technique. The resonant frequency was mechanically modulated at a rate of two kilohertz. Experimental results showed that the time evolution of the electromagnetic energy inside this frequency modulated (FM) superconducting resonator indeed behaved as predicted and thus demonstrated the unique features of this process. A proposed usage of FM superconducting resonators as electromechanical energy conversion devices is given along with some practical design considerations. This device seems to be very promising in producing high power (~10W/cm^3) microwave energy at 10 - 30 GHz.

Weakly coupled FM resonator system is also analytically studied for its potential applications. This system shows an interesting switching characteristic with which the spatial distribution of microwave energies can be manipulated by external means. It was found that if the modulation was properly applied, a high degree (>95%) of unidirectional energy transfer from one resonator to the other could be accomplished. Applications of this characteristic to fabricate high efficiency energy switching devices and high power microwave pulse generators are also found feasible with present superconducting technology.

Análisis comparativo de los mercados de trabajo de Francia y España

El principal objetivo de este trabajo es analizar las diferencias más significativas existentes entre los mercados de trabajo de España y Francia. Desde un punto de vista temporal, se ha actuado cronológicamente, comenzando en la década de 1960 para acabar con las consecuencias de la crisis económica de 2007 sobre los mercados de trabajo de España y Francia. Las principales variables estudiadas han sido el género, la edad, el nivel de estudios o el sector de actividad de los trabajadores así como un gran número de agregados macroeconómicos como la tasa de desempleo, la tasa de actividad o el grado de temporalidad en el empleo de ambos países. En relación a los resultados más destacados de este trabajo, se puede afirmar que tanto la economía española como su mercado de trabajo son más volátiles y pro cíclicos que los de Francia. Por otro lado, la reciente crisis económica ha afectado mucho más gravemente a Francia que a España, donde se han perdido más de 3.600.000 empleos. La existencia de estas diferencias señala claramente que las diferencias en el comportamiento del mercado de trabajo en España y en Francia no se deben exclusivamente a las diferencias en el crecimiento económico, sino a diferencias estructurales e institucionales propias de los respectivos mercados de trabajo nacionales. Idioma: Castellano

Análisis comparativo de los mercados de trabajo de Francia y España

El principal objetivo de este trabajo es analizar las diferencias más significativas existentes entre los mercados de trabajo de España y Francia. Desde un punto de vista temporal, se ha actuado cronológicamente, comenzando en la década de 1960 para acabar con las consecuencias de la crisis económica de 2007 sobre los mercados de trabajo de España y Francia. Las principales variables estudiadas han sido el género, la edad, el nivel de estudios o el sector de actividad de los trabajadores así como un gran número de agregados macroeconómicos como la tasa de desempleo, la tasa de actividad o el grado de temporalidad en el empleo de ambos países. En relación a los resultados más destacados de este trabajo, se puede afirmar que tanto la economía española como su mercado de trabajo son más volátiles y pro cíclicos que los de Francia. Por otro lado, la reciente crisis económica ha afectado mucho más gravemente a Francia que a España, donde se han perdido más de 3.600.000 empleos. La existencia de estas diferencias señala claramente que las diferencias en el comportamiento del mercado de trabajo en España y en Francia no se deben exclusivamente a las diferencias en el crecimiento económico, sino a diferencias estructurales e institucionales propias de los respectivos mercados de trabajo nacionales. Idioma: Castellano

Análisis y perspectivas del sector de automoción en España

El mercado español se encuentra en una fase de recuperación, convirtiéndose en un mercado rentable para la industria automovilística, que le ofrece ventajas fiscales y laborales. El desarrollo tecnológico y el cambio de mentalidad de la sociedad hacia una sociedad más ecológica se convierten en oportunidades claras para el sector. El sector automovilístico mantiene un potencial de crecimiento favorable con una evolución positiva de la demanda. La necesidad de adaptarse a los perfiles cambiantes de los compradores hace necesaria cambiar la gestión del cliente hacia una mayor cercanía. La alta competencia y la introducción de vehículos sustitutivos al tradicional en el mercado se han convertido en verdaderos retos para la industria. Los objetivos principales de las empresas del sector son, fundamentalmente, mejorar la competitividad a través de la diferenciación, la diversificación de la cartera de productos y la desintegración vertical de la cadena productiva para aprovecharse del bajo poder de negociación de los proveedores.