No description available.

An acetonitrile based protein extraction method was developed that demonstrated high efficient and effective removal of high abundant proteins from both human and murine serum. The protein content of the extract was characterised using gel electrophoresis, the Bradford assay and liquid chromatography tandem mass spectrometry (LC-MS/MS) with database searching. Selected reaction monitoring (SRM) analysis was used to quantify the levels of high abundant serum proteins to further validate the extraction methodology. The ACN depletion method, in combination with artificial neural networks (ANNs) data mining software, was applied to a murine growth hormone (GH) gene doping study with the aim of identifying biomarker ions capable of detecting gene doping. The LC-MS and ANNs analysis approach failed to conclusively identify a biomarker to gene doping in the mouse model. However, the application of the same technique to serum from a rhGH administration study in humans, returned models capable of discriminating between rhGH treated placebo states. The ion identified as being the most discriminatory was characterised using mass spectrometry, and was derived from the protein leucine-rich a-2-glycoprotein (LRG). Multiple LRG related tryptic peptides were identified as being up-regulated upon dosing with recombinant human GH (rhGH). A high throughput LC-MS/MS and SRM approach was developed to quantify proteins in human serum. The approach was validated by comparison of LC-MS/MS derived APO A1 concentrations with those obtained using established clinical analyser technologies. The LC-MS/MS methodology was applied to a large cohort of 257 serum samples from two rhGH administration studies performed at Royal Free Hospital . The two administrations included serum samples from 15 individuals who had been dosed daily with rhGH. Serum concentrations of the established rhGH biomarker insulin-like growth factor-I (IGF-I) were quantified by LC-MS/MS and compared well with those determined using two different immunoassay-based methodologies. Serum concentrations of the LRG protein were measured simultaneously with IGF-I and appeared to increase in 14 of the 15 rhGH dosed individuals. Combining the LRG and IGF-I data further increased the separation of rhGH treated and placebo states within each individual, and the application of ANNs analysis showed that the combination of the two proteins increased the discrimination characteristics over using IGF-I alone. The murine equivalent of the LRG protein was identified and SRM transitions for a tryptically derived peptide were developed, along with transitions for monitoring a peptide from the murine IGF-I protein. These transitions were used to quantify the two proteins in the remaining aliquots from a murine GH gene doping experiment, however neither protein appeared to increase in the GH +ve plasmid samples that were analysed.

No description available.

This thesis is concerned with furthering our understanding of the basis of visible region photocatalytic activity exhibited by doped TiO2-based materials. A range of experimental techniques including high resolution X-ray photoemission spectroscopy and diffuse reflectance spectroscopy are used to investigate electronic structure and an attempt is made to link these results to the observed photocatalytic activity. Both anionic (N) and cationic (Rh and Sn) dopants are investigated. [See pdf file for full abstract].

In this thesis, the structural, optical, and electrical properties of wurtzite MgxZn1-xO:Al and MgxZn1-xO:Ga thin films have been investigated in dependence on Mg and dopant concentration. Among the transparent conductive oxides (TCOs), ZnO based compounds have gained renewed interest as a transparent electrode for large scale applications such as defroster windows, at panel displays, touch screens, and thin film solar cells due to low material and processing cost, non-toxicity, and suitable physical properties. In general, these applications require transparent electrodes with lowest possible resistivity of rho < 10^-3 Ohmcm and lower [1]. Recently, it has been reported that Ga and Al doped ZnO thin films can be deposited with respective resistivity of 5x10^-5 Ohmcm [2] and 3 x10^-5 Ohmcm [3] which are similar to the data obtained for other practical TCOs, i.e. the resistivity of about 4x 10^-5 Ohmcm for Sn doped In2O3 (ITO) thin films [4]. Moreover, the bandgap of ZnO can be increased by alloying with Mg offering band alignment between transparent electrode and active (or buffer) layer of the device, e.g. Cu(In,Ga)Se2 solar cells [5]. The tunable bandgap of these transparent electrodes can further increase the efficiency of the devices by avoiding energy losses in the interface region of the layers. From this point of view, this work has been aimed to investigate the doping efficiency and limits in transparent conductive (Mg,Zn)O alloys. For this purpose, the samples investigated in this work have been grown by pulsed-laser deposition (PLD) using a novel, continuous composition spread method (CCS). In general, this method allows to grow thin films with lateral composition gradient(s) [6, 7]. All MgxZn1-xO:Al and MgxZn1-xO:Ga thin films have been deposited on 2-inch in diameter glass, c- or r-plane sapphire substrates using threefold segmented PLD targets in order to grow thin films with two perpendicular, lateral composition gradients, i.e. the Mg composition is varied in one direction whereas the Al/Ga concentration is varied in a perpendicular direction [7, 8]. In order to investigate the influence of the temperature, samples grown at different substrate temperatures in the range of 25 to 600 C were investigated. The optical and electrical measurements have been carried out on (5x 5)mm^2 samples that were cut from the CCS wafers along the respective composition gradients, i.e. Mg and Al/Ga contents. Subsequently, physical properties of thin films have been analyzed for a large range of Al/Ga content between 0.5 and 7 at.%, which corresponds to doping concentrations between 2x 10^20 and 3x 10^21 cm^-3, for different Mg contents x(Mg) ranging from 0.01 to 0.1. It has been found that practically the limiting the dopant concentrations is about 2 x10^21 cm^-3. Further, the electrical data suggests, that the compensating intrinsic defect is doubly chargeable hinting to the zinc vacancy (V_Zn) as microscopic origin. Increasing the dopant concentration above 2 x10^21 cm^-3 leads to a degradation of electrical and structural properties [8]. Further, the influence of growth and annealing temperatures on structural, electrical and optical properties of the films has been studied. For that purpose, Al and Ga doped (2.5 at.% = 1x10^21 cm^-3) Mg0.05Zn0.95O thin films have been chosen from CCS samples grown at T_g = (25 - 600) C . For both doping series, the samples grown at higher temperatures exhibit better crystalline quality compared to the samples grown at lower growth temperatures. As a result, samples grown at higher temperatures reveal higher Hall mobility. For the Al-doping series, the highest free charge carrier density of n = 8.2x 10^20 cm^-3 was obtained for an Mg0.05Zn0.95O:Al thin film grown at 200 C, with corresponding Hall mobility of mu = 13.3 cm^2/Vs, a resistivity of rho = 5.7x10^-4 Ohmcm, and optical bandgap of E_g = 3.8 eV. Interestingly, the free charge carrier density of n = (5 - 8) x 10^20 cm^-3 for samples grown with T_g > 300 C is clearly higher than the value of n = 1.25 x 10^20 cm^-3 that was obtained for the high temperature grown sample, i.e. at T_g = 600 C. Furthermore, for all T_g, Al-doped films have a higher doping efficiency than the Ga-doped counterparts. In order to look deeper into the microscopic origin of this behavior, the samples were post-annealed in vacuum at 400 C. Experimental results showed that the free charge carrier density of Al-doped samples first decreased and saturated afterward with increasing annealing time. On the other hand, the free charge carrier density of the Ga-doped samples first slightly increased and saturated with increasing annealing time. For both doping series, the saturation value of n ~ 1 x 10^20 cm^-3 was very close to the data that has been observed for (i) high temperature grown samples and (ii) the solubility limit of Al in ZnO of 0.3 at.% = 1.2x 10^20 cm^-3, that has been determined by Shirouzu et al. for high temperature grown (T_g > 600 C) Al-doped ZnO [9]. Correspondingly, the optical bandgap also changed, i.e. increased (decreased) for Al- (Ga-) doping series, and approached a constant value of 3.5 0 +- 0.1 eV which is explained by generation of acceptor-like compensating defects, and the solubility limit of the dopants. From XRD data, no secondary phases were found for as-grown and post-annealed films. However, the slight improvement of crystalline quality has been observed on post-annealed samples. Further, it has been shown that the growth and annealing temperatures are important as they strongly affect the metastable state of the solid solution that samples grown at low temperature represent. The low solubility limit of the dopants, i.e. 0.3 at.% for Al in ZnO under equilibrium condition, can be increased by preparing samples by non-equilibrium growth techniques [10]. This is also consistent with experimental results of this work that Al- as well as Ga-doped metastable ZnO and (Mg,Zn)O thin films can be prepared with highest possible doping efficiency for the dopant concentration up to 2.5 at.% when growth or annealing temperatures below 400 C are used.

Title: Ethical, Social and Political Dimension of Doping in the Field of Sport Objectives: To work up the issue of doping, a brief overview of doping agents and methods, history of doping and antidoping (doping organization, doping control and sanctions). Assess the issue of doping in sport from the perspective of ethical, social and political. Mapping anchoring doping issues in documents or legislation of the Czech Republic and the EU, to reveal the causes and consequences of doping and the prevention and repression as an integral part of the antidoping activities and also to the education of athletes. Methods: The dissertation has a theoretic character, uses qualitative methods: compares, analyse and interprets texts from publications and sources. It draws own conclusions from these bases. Results: This dissertation clears up the issue of doping in the dimensions of ethical, social and political. Collected and interprets virtually all relevant documents, on global scale. Emphasizes the need to combine prevention and repression in the fight against doping and the importance of education in the spirit of sport and the Olympic ideas. Keywords: Antidoping documents - Doping - Ethics in Sport - Evil in Sports - Gamesmanship - Sportsmanship

Au cours de cette étude, nous avons synthétisé par chimie douce en solution aqueuse des particules de TiO2 sous forme anatase, brookite et rutile. Chaque polymorphe a été obtenu pur, avec des nanoparticules de taille et de morphologie contrôlées. Ces particules ont ensuite été calcinées à des températures comprises entre 500 et 750°C afin d'étudier le phénomène de frittage. Nous avons observé que la morphologie initiale des particules a un impact sur celle des particules frittées. Nous avons également montré que les mécanismes et les cinétiques de transition de phase anatase → rutile et brookite → rutile étaient fortement impactés par le changement morphologique des nanoparticules initiales ainsi que par la nature de l'atmosphère gazeuse et par la présence d'impuretés en surface des particules. Cette dernière propriété a été utilisée dans un second temps pour stabiliser thermiquement les particules d'anatase et de brookite par des dopages au lanthane, ce qui a permis de gagner au moins 100°C sur la température de transition et d'obtenir ainsi des surfaces spécifiques conséquentes, même à 500°C. Ces études se sont appuyées sur de nombreuses techniques de caractérisations comme l'analyse thermogravimétrique, la spectroscopie UV, les microscopies électroniques à balayage et en transmission. La diffraction des Rayons X a été abondamment utilisée afin de caractériser les tailles, les morphologies et l'évolution des différentes phases avec la température / During this study, we have synthesized TiO2 nanoparticles by soft routes in aqueous media. Anatase, brookite and rutile have been obtained in pure phases, with well-defined size and morphology. Thermal treatments were conducted at temperatures ranging from 500 to 750°C to study particles sintering. We have observed the influence of initial morphology on particles sintering. We also have shown that the anatase → rutile and brookite → rutile phase transition and kinetic were modified by initial morpholgy of particules, but also by annealing gas atmosphere and by the presence of impurities on the particles. This last result was used in a second point to thermically stabilized anatase and brookite nanoparticles by lanthanum doping. Particles have been characterized by numerous techniques, such as high resolution transmission electron microscopy, thermogravimetric analyses and differential scanning calorimetry. X-ray diffraction was widely used to characterize sizes, morphologies and phase transition during sintering

Afin d’augmenter la durabilité des PEMFC, des aérogels de dioxyde d'étain ont été étudiés pour remplacer le carbone comme support de catalyseur cathodique. SnO2 est un semi-conducteur de type n dont la conductivité électronique peut être améliorée en le dopant par des cations hypervalents tels que Nb5+, Ta5+ ou Sb5+. Pour être un support de catalyseur efficace, le matériau doit aussi posséder une surface spécifique élevée avec une morphologie mésoporeuse pour permettre à la fois la dispersion et l'activité du catalyseur (Pt). À cette fin, notre objectif était de développer des aérogels de SnO2 dopé. Dans cette étude, les aérogels ont été synthétisés par voie sol-gel en milieu acide à partir d’alcoxydes métalliques comme précurseurs. Nos matériaux présentent une morphologie aérée très intéressante avec une surface spécifique relativement élevée (80-90 m2/g). De plus, tous les aérogels SnO2 dopés au Sb ont présenté une amélioration très significative de la conductivité électronique pour atteindre une valeur d’environ 0,12 S/cm. Les nanoparticules de platine ont ensuite été déposées sur la surface de l'aérogel SnO2 dopé Sb en utilisant trois méthodes différentes. La méthode basée sur la réduction chimique par l’intermédiaire d’un polyol fournit le meilleur résultat en terme d'activité catalytique massique, mesurée en électrode à disque tournant (Is = 32 mA/mgPt). Cette valeur est, par ailleurs, encore plus élevée que celle de l'électrocatalyseur TEC10E40E (Is = 27 mA/mgPt). Les AMEs intégrant notre aérogel SnO2 dopé au Sb ont enfin montré une très bonne durabilité à des potentiels élevés. / In order to tackle the problem of low durability, tin dioxide aerogels were studied to replace carbon black as a catalyst support in proton exchange membrane fuel cells (PEMFCs). SnO2 is a well-known n-type semi-conductor whose electronic conductivity can be improved by doping with hypervalent cations such as Nb5+, Ta5+ or Sb5+. In addition, as a catalyst support, this material has to develop a high specific surface area with adequate mesoporous morphology to allow both good dispersion and activity of the catalyst (Pt). To this end, our objective was to develop doped SnO2 aerogels. In this study, SnO2 based-aerogels were successfully synthesized following an acid-catalyzed sol–gel route starting with metal alkoxides as precursors. Our materials have shown a very interesting airy morphology with among other a reasonable specific surface area (80–90 m2/g). Moreover, all Sb-doped aerogels exhibited significant improvement in electronic conductivity and reach a value of around 0.12 S/cm. Platinum nanoparticles were then deposed on the Sb doped SnO2 aerogel surface using three different methods. The method based on chemical reduction using a polyol route provided the best result in term of mass catalytic activity measured by RDE (Is = 32 mA/mgPt). This value is even higher than that of the reference electrocatalyst TEC10E40E (Is = 27 mA/mgPt). Sb doped SnO2 aerogel based MEAs have exhibited a very good durability at high potentials.

Foram realizados estudos da síntese e do crescimento de cristais de BaY2F8:TR (TR= Nd3+; Pr3+; Er3+; Tb3+; Dy3+) simplesmente dopados e codopados (Nd3+:Dy3+ ; Nd3+:Pr3+) por meio do método de fusão por zona (FZ). Os cristais crescidos foram caracterizados quanto a sua estrutura por Difração de raios-x (DRX) e Difração de nêutrons (DN) com análise pelo método de Rietveld. Foi também estudado o comportamento na fusão deste material puro e dopado com elementos terras raras trivalentes através de: microscopia eletrônica de varredura (MEV) e espectroscopia dispersiva de raios-x (EDS). A concentração final de dopantes, bem como, sua distribuição nos cristais crescidos foi estimada e, quando possível, foi ainda calculado o coeficiente de segregação de cada dopante nesta matriz. Os cristais foram também analisados por espectroscopia de absorção e emissão no caso dos materiais duplamente dopados, sendo observada evidencias de transferência de energia Nd-Pr na região UV. Foram obtidos cristais com dimensões da ordem de 40 mm x 10mm com boa qualidade óptica e estrutural adequados para estudos espectroscópicos e testes de ação laser com bombeamento por laser de diodo. Experiências preliminares de crescimento de fibras monocristalinas desta matriz pura e dopada com Tb3+, pelo método de crescimento de micro-pulling down, foram também realizadas visando uma avaliação do método aplicado a este fluoreto. Foram obtidas apenas fibras translúcidas com diâmetro constante sendo necessária maior investigação sobre o crescimento de fibras deste material puro ou dopado. / Synthesis and Growth process of single crystals of BaY2F8:TR (TR= Nd3+; Pr3+; Er3+; Tb3+;Dy3+) single-doped and co-doped (Nd3+ :Dy3+ ; Nd3+:Pr3+) were performed by Zone Melting method (ZM). The grown crystals were characterized by X-ray diffraction (XRD) and Neutron Diffraction (ND) and analyzed by the Rietveld Method. The melting behavior of this pure and trivalent rare earth doped-fluoride was investigated also by scanning electron microscopy (MEV) and X-ray energy dispersive spectroscopy (EDS). The concentration and distribution of the dopants in the grown crystals were measured, and when feasible, the segregation coefficient was estimated. The single crystals were also analyzed by absorption spectroscopy and emission spectroscopy in the case of the co-doped crystals. Evidences of the occurrence of energy transfer process in the UV for Nd-Pr were detected. From the study of the growth process single crystals of 40mm x 10mm in size, with good optical and structural quality were obtained for spectroscopy studies and tests of laser emission. Initial experiments were also performed in the growth of single crystalline fibers of this host doped with Tb3+, by the micro-pulling down method aiming a preliminary evaluation of the use of this growth process. Only semi-transparent fibers were obtained. Additional studies are necessary to improve the growth of single crystalline fibers of this fluoride.

Foram realizados estudos da síntese e do crescimento de cristais de BaY2F8:TR (TR= Nd3+; Pr3+; Er3+; Tb3+; Dy3+) simplesmente dopados e codopados (Nd3+:Dy3+ ; Nd3+:Pr3+) por meio do método de fusão por zona (FZ). Os cristais crescidos foram caracterizados quanto a sua estrutura por Difração de raios-x (DRX) e Difração de nêutrons (DN) com análise pelo método de Rietveld. Foi também estudado o comportamento na fusão deste material puro e dopado com elementos terras raras trivalentes através de: microscopia eletrônica de varredura (MEV) e espectroscopia dispersiva de raios-x (EDS). A concentração final de dopantes, bem como, sua distribuição nos cristais crescidos foi estimada e, quando possível, foi ainda calculado o coeficiente de segregação de cada dopante nesta matriz. Os cristais foram também analisados por espectroscopia de absorção e emissão no caso dos materiais duplamente dopados, sendo observada evidencias de transferência de energia Nd-Pr na região UV. Foram obtidos cristais com dimensões da ordem de 40 mm x 10mm com boa qualidade óptica e estrutural adequados para estudos espectroscópicos e testes de ação laser com bombeamento por laser de diodo. Experiências preliminares de crescimento de fibras monocristalinas desta matriz pura e dopada com Tb3+, pelo método de crescimento de micro-pulling down, foram também realizadas visando uma avaliação do método aplicado a este fluoreto. Foram obtidas apenas fibras translúcidas com diâmetro constante sendo necessária maior investigação sobre o crescimento de fibras deste material puro ou dopado. / Synthesis and Growth process of single crystals of BaY2F8:TR (TR= Nd3+; Pr3+; Er3+; Tb3+;Dy3+) single-doped and co-doped (Nd3+ :Dy3+ ; Nd3+:Pr3+) were performed by Zone Melting method (ZM). The grown crystals were characterized by X-ray diffraction (XRD) and Neutron Diffraction (ND) and analyzed by the Rietveld Method. The melting behavior of this pure and trivalent rare earth doped-fluoride was investigated also by scanning electron microscopy (MEV) and X-ray energy dispersive spectroscopy (EDS). The concentration and distribution of the dopants in the grown crystals were measured, and when feasible, the segregation coefficient was estimated. The single crystals were also analyzed by absorption spectroscopy and emission spectroscopy in the case of the co-doped crystals. Evidences of the occurrence of energy transfer process in the UV for Nd-Pr were detected. From the study of the growth process single crystals of 40mm x 10mm in size, with good optical and structural quality were obtained for spectroscopy studies and tests of laser emission. Initial experiments were also performed in the growth of single crystalline fibers of this host doped with Tb3+, by the micro-pulling down method aiming a preliminary evaluation of the use of this growth process. Only semi-transparent fibers were obtained. Additional studies are necessary to improve the growth of single crystalline fibers of this fluoride.