Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (p. 69-75).

The Galactic disk is home of many billion stars, one of which isour Sun. The stellar population of which the Sun is a member residesin the vertically thin spiral structure of the disk. There is a seconddisk population, the so-called thick disk, that has somewhat dierentspatial, kinematic and chemical properties as compared to the thindisk. It may be systematically older than the thin disk (Bernkopf et al.2001), with a star-formation hiatus separating the two. Observationsof thick-disk subgiants allow us to probe the chemical properties ofthese stars. As the subgiant evolutionary phase is short, age-datingthese stars is also possible. Are they in fact systematically older thanthe oldest thin-disk stars? This project will take rst steps towardsanswering this question based on new target selections done on DataRelease 1 of the Gaia mission. / Vintergatans disk innehåller flera miljarder stjärnor, varav en är vår Sol. Den stjärnbefolkning som Solen är medlem i ligger i den vertikalt tunna spiralstrukturen på skivan (tunna disken). Det finns en andra diskpopulation, den så kallade tjocka disken, som har något annorlunda rumsliga, kinematiska och kemiska egenskaper jämfört med den tunna disken. Den kan vara äldren än tunna disken (Bernkopf et al. 2001), med en stjärnbildningsstopp som skiljer de två. Genom att observera subjättar som är en del av den tjocka disken blir det möjligt att analysera dessa stjärnors kemiska egenskaper. Eftersom subjätte grenen är en kort evolutionär fas, åldersbestämmelse är också möjlig för dessa stjärnor. Är de faktiskt systematiskt äldre än de äldsta tunna diskens stjärnor? Detta projekt kommer att ta de första stegen mot att svara på denna fråga baserat på nya målval som gjorts på Data Release 1 från Gaia-uppdraget.

The thesis reports on fabricating alternative solid phase extraction (SPE) sorbents and colorimetric probes based on electrospun nanofibers for alkylphenols (APs). Hydroxyl methylated styrene [poly(co-styrene-CH₃OH)] and 3-oxobutanoate styrene [poly(co-styrene-OCOCH₃COCH₃)] copolymers were synthesized and fabricated into sorbent materials by electro-spinning/spraying. The fabricated morphologies consisting of bead free fibers, beaded fibers and particles were evaluated as SPE sorbents using batch experiments. Electropun fibers proved to be better sorbents as they exhibited extraction efficiency that exceeded 95% compared to 60% for beaded fibers and 40% for particles. In view to reduce sample and solvent volumes, smooth fibers were packed into pipette tips as SPE devices that yielded quantitative recoveries of APs from spiked wastewater samples. Recoveries ranged from 70% to 125% with LOD of 0.008, 0.01 and 0.1 μg mL⁻¹ for 4-tert octylphenol (4-t-OP), 4-octylphenol (4-OP) and 4-nonylphenol (4-NP) respectively, when using high performance liquid chromatography-fluorescence detector (HPLC-FLD). Furthermore, amino functionalised polydiacetylene polymers (PDAs), citrate capped gold (AuNPs) and silver nanoparticles (AgNPs) were evaluated as colorimetric probes for visual detection of APs. In colloidal studies, AuNPs probe showed a colour change from wine red to green upon introduction of analyte. UV-vis spectroscopy revealed the shifting of the surface plasmon resonance (SPR) peak from 525 nm to 729 nm induced by aggregation of AuNPs. For AgNPs probe, a colour change was observed from yellowish green to brown. Transmission electron microscopy (TEM) studies showed growth of AgNPs. A presumed oxidation of the analyte, forming an absorbing compound at 279 nm in both AgNPs and PDAs probes was also observed. For PDAs probe the colour change was from purple to pink. Concentrations as low as 30 μg mL⁻¹ were detectable in all colloidal based probes. Further colorimetric investigations were conducted with electrospun AuNPs-nylon 6 fiber mat. A colour change from purplish red to navy blue at concentrations of 1000 μg mL⁻¹ was observed. Electrospun AgNPs –nylon 6 fiber mat did not show a distinct colour change. High resolution scanning electron microscopy (HRSEM) revealed the analyte inducing the assembly of AuNPs and AgNPs as they covered the surface of the nanofiber mat. Electrospun nanofibers are a platform for analysis and thus tuning their chemistry will lead to sensitive and selective methods

No description available.

O objetivo deste trabalho consistiu na caracterização das zeólitas Y e ZSM-5, usando a técnica de Espectroscopia de Alta resolução em sólidos por Ressonância Magnética Nuclear (RMN). Os espectros de alta resolução do 13C e 27Al foram obtidos usando, simultaneamente, as técnicas de desacoplamento em alta potência (DEC) e rotação da amostra em torno de ângulo mágico (MAS). Utilizamos os espectros de alta resolução dos núcleos de 27Al para analisarmos a coordenação e a quantificação dos alumínios estruturais e extra-estruturais em zeólitas Y e de 13C para analisarmos o posicionamento de moléculas direcionadas localizadas nos canais da ZSM-5 / The objective of this work consisted of the characterization of zeolites Y and ZSM-5, using Solid State High Resolution Nuclear Magnetic Resonance Spectrsocopy. The 13C and 27Al high resolution spectra were obtained using simultaneously, High Power Decoupling (DEC) and Magic Angle Spinning (MAS). The high resolution 27Al spectra were used to distinguish and quantify framework and non-framework aluminium in zeolites Y. The high resolution 13C spectra were used to probe the position and configuration of the guest organic molecules within the framework of the ZSM-5 zeolite

<p>We present an investigation of the magnetic field geometries and inhomogeneous distribution of chemical elements in the atmospheres of peculiar A and B stars. Our study combines high-quality spectroscopic and spectropolarimetric stellar observations with the development and application of novel techniques for theoretical interpretation of the shapes and variability of stellar line profiles. In particular, we extend the method of Doppler imaging to the analysis of spectra in the four Stokes parameters, making it possible to derive detailed and reliable stellar magnetic maps simultaneously with the imaging chemical inhomogeneities.</p><p>The magnetic Doppler imaging is applied to study of magnetic topologies and distributions of chemical elements in the peculiar stars α² CVn and 53 Cam. We found that the magnetic field geometry of 53 Cam is considerably more complex than a low-order multipolar topology, commonly assumed for magnetic A and B stars. Our Doppler imaging analysis also led to a discovery and study of spots of enhanced mercury abundance in the atmosphere of α And, a star where the presence of a global magnetic field is unlikely.</p><p>The ESO 3.6-m telescope is used to collect unique, very high spectral- and time-resolution observations of rapidly oscillating peculiar A (roAp) stars and to reveal line profile variations due to stellar pulsations. We present a detailed characterization of the spectroscopic pulsational behaviour and demonstrate a remarkable diversity of pulsations in different spectral lines. The outstanding variability of the lines of rare-earth elements is used to study propagation of pulsation waves through the stellar atmospheres and identify pulsation modes. This analysis led to a discovery of a non-axisymmetric character of pulsations in roAp stars.</p><p>Our study of chemical stratification in the atmosphere of the roAp star γ Equ provides a compelling evidence for significant variation of the chemical composition with depth. We find a combined effect of extreme chemical anomalies and a growth of pulsation amplitude in the outermost atmospheric layers to be the most likely origin of the high-amplitude pulsational variations of the lines of rare-earth elements.</p><p>Observations of cool magnetic CP stars are obtained with the ESO Very Large Telescope and are used for empirical investigation of the anomalies in the atmospheric temperature structure. We show that the core-wing anomaly of the hydrogen Balmer lines observed in some cool CP stars can be attributed to a hot layer at an intermediate atmospheric depth.</p>

We present an investigation of the magnetic field geometries and inhomogeneous distribution of chemical elements in the atmospheres of peculiar A and B stars. Our study combines high-quality spectroscopic and spectropolarimetric stellar observations with the development and application of novel techniques for theoretical interpretation of the shapes and variability of stellar line profiles. In particular, we extend the method of Doppler imaging to the analysis of spectra in the four Stokes parameters, making it possible to derive detailed and reliable stellar magnetic maps simultaneously with the imaging chemical inhomogeneities. The magnetic Doppler imaging is applied to study of magnetic topologies and distributions of chemical elements in the peculiar stars α2 CVn and 53 Cam. We found that the magnetic field geometry of 53 Cam is considerably more complex than a low-order multipolar topology, commonly assumed for magnetic A and B stars. Our Doppler imaging analysis also led to a discovery and study of spots of enhanced mercury abundance in the atmosphere of α And, a star where the presence of a global magnetic field is unlikely. The ESO 3.6-m telescope is used to collect unique, very high spectral- and time-resolution observations of rapidly oscillating peculiar A (roAp) stars and to reveal line profile variations due to stellar pulsations. We present a detailed characterization of the spectroscopic pulsational behaviour and demonstrate a remarkable diversity of pulsations in different spectral lines. The outstanding variability of the lines of rare-earth elements is used to study propagation of pulsation waves through the stellar atmospheres and identify pulsation modes. This analysis led to a discovery of a non-axisymmetric character of pulsations in roAp stars. Our study of chemical stratification in the atmosphere of the roAp star γ Equ provides a compelling evidence for significant variation of the chemical composition with depth. We find a combined effect of extreme chemical anomalies and a growth of pulsation amplitude in the outermost atmospheric layers to be the most likely origin of the high-amplitude pulsational variations of the lines of rare-earth elements. Observations of cool magnetic CP stars are obtained with the ESO Very Large Telescope and are used for empirical investigation of the anomalies in the atmospheric temperature structure. We show that the core-wing anomaly of the hydrogen Balmer lines observed in some cool CP stars can be attributed to a hot layer at an intermediate atmospheric depth.

Graduation date: 1992

O objetivo deste trabalho consistiu na caracterização das zeólitas Y e ZSM-5, usando a técnica de Espectroscopia de Alta resolução em sólidos por Ressonância Magnética Nuclear (RMN). Os espectros de alta resolução do 13C e 27Al foram obtidos usando, simultaneamente, as técnicas de desacoplamento em alta potência (DEC) e rotação da amostra em torno de ângulo mágico (MAS). Utilizamos os espectros de alta resolução dos núcleos de 27Al para analisarmos a coordenação e a quantificação dos alumínios estruturais e extra-estruturais em zeólitas Y e de 13C para analisarmos o posicionamento de moléculas direcionadas localizadas nos canais da ZSM-5 / The objective of this work consisted of the characterization of zeolites Y and ZSM-5, using Solid State High Resolution Nuclear Magnetic Resonance Spectrsocopy. The 13C and 27Al high resolution spectra were obtained using simultaneously, High Power Decoupling (DEC) and Magic Angle Spinning (MAS). The high resolution 27Al spectra were used to distinguish and quantify framework and non-framework aluminium in zeolites Y. The high resolution 13C spectra were used to probe the position and configuration of the guest organic molecules within the framework of the ZSM-5 zeolite

Ce travail de thèse porte sur le développement d'un spectromètre laser à cascade quantique (QCL) dans le moyen infrarouge pour des applications en spectroscopie et en métrologie des fréquences. Les principaux objectifs ont été tout d'abord de lever la forte contrainte que constitue le faible domaine spectral accessible au laser à CO2 mais également d'accroître la faible puissance laser disponible pour nos expériences de spectroscopie. Ce nouvel instrument intéresse directement les expériences développées au sein du groupe Métrologie Molécules et Tests Fondamentaux : la mise en évidence de non conservation de la parité dans les molécules chirales et la détermination de la constante de Boltzmann par spectroscopie laser. Au cours de ce travail de thèse, nous avons caractérisé le bruit d'intensité, le bruit de fréquence ainsi que la largeur de raie de la source QCL libre. Les résultats obtenus comparés à la littérature montrent une grande qualité spectrale de cette source laser. L'asservissement en phase de la source QCL sur un laser à CO2 ultra-stable a permis de démontrer le transfert des propriétés spectrales du laser à CO2 à la source QCL. Le spectromètre a ensuite été utilisé pour des expériences de spectroscopie en absorption linéaire des molécules NH3 et de la molécule de Méthyltrioxorhénium, molécules d'intérêt pour les projets de mesure de la constante de Boltzmann et de recherche d'un et de la non-conservation de la parité. Le potentiel de ce spectromètre a également été démontré dans des expériences de spectroscopie à très haute résolution, en absorption saturée. / This thesis is devoted to the developpement of a laser spectrometer quantum cascade to frequency metrology and high-resolution spectroscopy. The objective of this work is to developp a new tool for projects in our group : Measuring the Boltzman constant and test of non conservation of parity. Thus the new source was characterized by measuring its spectral density noise, amplitude noise and its emission line width. The phase locking of the QCL on the CO2 laser has achived spectroscopy NH and MTO, molecules of interest for the projects of the group mentioned aboive respectively.