Im Wasser-oxidierenden Cluster („oxygen-evolving complex“, OEC) des Photosystem II findet sich die primäre Quelle der Sauerstoffproduktion der Erde. Der OEC katalysiert in grünen Pflanzen unter Absorption von Sonnenlicht die Vierelektronen-Oxidation von Wasser zu Sauerstoff in einer zyklischen Sequenz von Oxidationszuständen (Kok-Zyklus). In dieser Arbeit wurden Strukturen, Spindichteverteilungen sowie EPR-Parameter ein-, zwei- und vierkerniger Mangankomplexe, die in Bezug auf den OEC modelliert wurden, mit Hilfe der Dichtefunktionaltheorie (DFT) berechnet. Hauptziel war das Verständnis der molekularen und elektronischen Struktur des vierkernigen Manganclusters des OEC durch direkten Vergleich mit experimentellen EPR-Daten. / Photosynthesis is the most fundamental process of life on earth. The biological production of oxygen in plant photosynthesis occurs in photosystem II (PSII). Here two water molecules are coupled in a four-electron oxidation to one O2 molecule, catalyzed by a tetranuclear manganese complex, known as the oxygen-evolving complex (OEC). In this thesis, density-functional theory (DFT) methods were validated and subsequently employed to study structures, spin-density distributions and EPR parameters of mono-, di-, and tetranuclear complexes with regard to the OEC. The goal was to draw conclusions on the molecular and electronic structure of the OEC.

In this thesis I will discuss the development, construction and testing of a sub-Kelvin Q-band electron paramagnetic resonance (EPR) spectrometer and optically detected magnetic resonance (ODMR) of wide bandgap semiconductors at Q-band. The sub-Kelvin EPR spectrometer was developed to be integrated into a standard commercial system. Characterisation of the cryogenics and microwave components of the spectrometer will be discussed as well as the design and adaptations made to enable EPR experiments to be performed below 1 K. A waveguide thermal break design, previously only used in detectors for the cosmic microwave background radiation, was optimised using ANSYS High frequency structure simulator (HFSS) to operate at Q-band and was built and tested in this spectrometer. The sub-Kelvin EPR spectra of Cr3+ in Al2O3 and [Cr12O9(OH)3(O2CCMe3)15] were obtained. The resonant cavity of the spectrometer was also successfully tested at room temperature, with a pulsed microwave bridge, paving the way for further development of the system to enable sub-Kelvin pulsed EPR. A home-built Q-band ODMR spectrometer was used to investigate the wide band gap semiconductors ZnO and InGaN/GaN multiple quantum wells (MQWs). The ZnO was a natural crystal, and used to characterise the spectrometer. ODMR from a green c-plane InGaN/GaN MQW was studied to probe the method of carrier localisation in the QW. It was shown qualitatively that the ODMR results support current theories for carrier localisation mechanisms, but the noise on these measurements needs to be reduced to provide quantitative support.

A 3.5 jours de développement (J3.5), l'embryon de souris est constitué d'un épithélium externe, le trophectoderme, et d'une masse cellulaire interne (MCI). La MCI est hétérogène, constituée des précurseurs de l'épiblaste (Epi) et de l'endoderme primitif (EPr), représentée par l'expression exclusive de Nanog et de Gata6 respectivement. Lors de l'implantation à E4.5, l'EPr forme un épithélium à la surface de la MCI, en regard de la cavité blastocoelique. L'Epi donnera tous les tissus du nouveau-né. L'EPr permet les premiers échanges nutritionnels entre l'embryon et la mère. Je m'intéresse au rôle de Nanog et de Gata6 dans la détermination et la différenciation de l'Epi et de l'EPr. De plus, je m'intéresse à l'implication de la signalisation RTK dans l'expression de ces deux gènes. Enfin, je cherche à comprendre les interrelations entre Gata6 et Nanog. A l'aide des modèles de souris KO, des modèles in vitro ainsi que des techniques innovantes développées au sein du laboratoire, nous avons mis en évidence que la modulation de l'expression de Nanog, Gata6, Fgf4 et Fgfr2 semble suffisante pour l'engagement des cellules vers un devenir Epi ou EPr. De plus, ces résultats permettent de proposer un nouveau modèle expliquant le rôle de Gata6 et de Nanog dans la spécification des cellules Epi et EPr. / At 3.5 days of development (E3.5), the mouse embryo consists of an outer epithelium, the trophectoderm, and an inner cell mass (ICM). The ICM is heterogeneous, composed of the precursors of the epiblast (Epi) and the primitive endoderm (PrE), expressing either Nanog or Gata6 respectively. Upon implantation at E4.5 the EPr forms an epithelium on the surface of the ICM, facing the blastocoelic cavity. The Epi give rise all tissues of the newborn. The PrE allows the first nutritional exchanges between the embryo and the mother. I focus on the role of Nanog and Gata6 in the determination and differentiation of Epi and PrE. In addition I am interested in the involvement of RTK signaling in the expression of both genes. Finally, I seek to understand the relationships between Gata6 and Nanog. Using the transgenic mouse models, in vitro models as well as innovative techniques developed in the laboratory, we have demonstrated that modulating the expression of Nanog, Gata6, FGF4 and FGFR2 seems sufficient for commitment of cells to become an Epi or EPr. Furthermore, these results allow proposing a new model explaining the role of Gata6 and Nanog in the determination and differentiation of Epi and PrE cells.

No description available.

Arising out of the EPR debate, the Bell and Wigner inequalities of quantum theory are experimentally testable relations which address the question of quantum completeness. This thesis provides feasibility results for a fermionic test of the Bell inequality, and the first known attempt to investigate the completeness question through the Wigner relation. Such a test is made possible by the production of an entangled p-p singlet at the KVI research facility in Groningen, the Netherlands, through the reactions 12C(d,2He)12B and p(d,2He)n. The p-p spin-correlations are analyzable via the KVI's 2-pi polarimeter acceptance, which eliminates loopholes common to previous experiments. The results distinguish between a hidden variables and quantum mechanical description of the universe. Also presented is a critique of the GHZ argument against the existence of local hidden variables.

Arising out of the EPR debate, the Bell and Wigner inequalities of quantum theory are experimentally testable relations which address the question of quantum completeness. This thesis provides feasibility results for a fermionic test of the Bell inequality, and the first known attempt to investigate the completeness question through the Wigner relation. Such a test is made possible by the production of an entangled p-p singlet at the KVI research facility in Groningen, the Netherlands, through the reactions 12C(d,2He)12B and p(d,2He)n. The p-p spin-correlations are analyzable via the KVI's 2-pi polarimeter acceptance, which eliminates loopholes common to previous experiments. The results distinguish between a hidden variables and quantum mechanical description of the universe. Also presented is a critique of the GHZ argument against the existence of local hidden variables.

Cu is an important trace element in living systems, including animals. It is a part of many enzymes responsible for different processes occurring in the body. However, antagonists can severely decrease the amount of Cu available to the animal, which results in numerous health issues caused by Cu deficiency. The main antagonists of the Cu are thiomolybdates whose effect is especially harsh in ruminants due to their high potential to synthesize these compounds. Thiomolybdates (the ions MoOxS4-x2- ,where x = 0-3) are formed in the rumen from molybdate and sulfide (from degradation of sulfate), both of which come from the food and water ingested by the animal.<p> The first part of the project described in this thesis was to develop reproducible preparative methods of CuTM samples in solution and solids, under conditions as biologically relevant as possible. This crucial information is missing in the literature related to Cu deficiency. The second part studied the structure of the adduct formed between Cu and two of the thiomolybdates: tetrathiomolybdate, TM4 and trithiomolybdate, TM3, as these are the most important in Cu deficiency.<p> In solution, the appropriate solution medium and the concentration of reactants were chosen to study the stoichiometry of Cu:TM in solution before precipitation occurs.<p> Conditions for preparation of solid CuTM adducts were chosen to obtain the amount of solid necessary for further studies and to eliminate the formation of unwanted side-products. In the solid phase, the stoichiometry of Cu:TM was investigated by elemental analysis. EPR spectroscopy of solid CuTM samples revealed the presence of diamagnetic species which were partially identified.<p> EXAFS studies were performed on both the Mo and Cu K edges. Spectra defined the oxidation states of both main metal atoms, Cu and Mo. Fitting of the measured EXAFS spectra of solid CuTM samples prepared at three different Cu:TM ratios determined the interatomic distances involved in these compounds. This data was used to determine the structure of the CuTM units which polymerize to form the final product. IR spectroscopy was also used to confirm the presence of some of the groups in these adducts.<p> All the results from the various spectroscopic techniques were then combined to proposed a complete reaction scheme for the two-step formation of the CuTM4 and CuTM3 adduct species.

Hoy en día, las organizaciones que no cuentan con información integrada, y por ende trabajan con las llamadas islas de información, no favorecen a las gerencias en la adecuada toma de decisiones, lo que genera en muchas ocasiones grandes pérdidas económicas a las compañias. El presente informe muestra cómo las necesidad intrínseca de la alta dirección de contar con información confiable, precisa e integrada ha hecho posible que la organización se integre a lo largo de las áreas. Por ende, se diferencia de la competencia mediante la implantación de un sistema de Planificación de los Recursos Empresariales (ERP), lo que permite otras ventajas, como la reducción de costos, el aumento de la productividad y la automatización de procesos, vital en una empresa que desea ser competitiva. La implementación del ERP Baan IV fuer realizada en el Grupo empresarial Vega, se llevó a cabo en respuesta a la problemática que tenía la organización con el uso de diferentes plataformas, arquitectura de red, lenguaje de programación y en resumidas cuentas: información diferente. Por lo tanto la implantación de un sistema integrado permitirá a la organización obtener una ventaja competitiva o en su defecto contribuir a alinearse comparativamente con sus competidores. De esta forma, se encontró en la organización la disponibilidad de una respuesta adecuada de información (a la medida de las necesidades), y una solución que permitiría la integración total de todas las operaciones con el fin de gestionar adecuadamente cada una de las áreas de la empresa.

Cu is an important trace element in living systems, including animals. It is a part of many enzymes responsible for different processes occurring in the body. However, antagonists can severely decrease the amount of Cu available to the animal, which results in numerous health issues caused by Cu deficiency. The main antagonists of the Cu are thiomolybdates whose effect is especially harsh in ruminants due to their high potential to synthesize these compounds. Thiomolybdates (the ions MoOxS4-x2- ,where x = 0-3) are formed in the rumen from molybdate and sulfide (from degradation of sulfate), both of which come from the food and water ingested by the animal.<p> The first part of the project described in this thesis was to develop reproducible preparative methods of CuTM samples in solution and solids, under conditions as biologically relevant as possible. This crucial information is missing in the literature related to Cu deficiency. The second part studied the structure of the adduct formed between Cu and two of the thiomolybdates: tetrathiomolybdate, TM4 and trithiomolybdate, TM3, as these are the most important in Cu deficiency.<p> In solution, the appropriate solution medium and the concentration of reactants were chosen to study the stoichiometry of Cu:TM in solution before precipitation occurs.<p> Conditions for preparation of solid CuTM adducts were chosen to obtain the amount of solid necessary for further studies and to eliminate the formation of unwanted side-products. In the solid phase, the stoichiometry of Cu:TM was investigated by elemental analysis. EPR spectroscopy of solid CuTM samples revealed the presence of diamagnetic species which were partially identified.<p> EXAFS studies were performed on both the Mo and Cu K edges. Spectra defined the oxidation states of both main metal atoms, Cu and Mo. Fitting of the measured EXAFS spectra of solid CuTM samples prepared at three different Cu:TM ratios determined the interatomic distances involved in these compounds. This data was used to determine the structure of the CuTM units which polymerize to form the final product. IR spectroscopy was also used to confirm the presence of some of the groups in these adducts.<p> All the results from the various spectroscopic techniques were then combined to proposed a complete reaction scheme for the two-step formation of the CuTM4 and CuTM3 adduct species.

This dissertation concerns the use of bicyclic guanidinate ligands to prepare new dimetal paddlewheel compounds. Specifically, Ru_2^6+, Re_2^6+, Re_2^7+, and Os_2^7+ compounds will be examined to observe any changes brought about by using bicyclic guanidinate ligands with varying ring sizes. In the Ru_2^6+ compounds, different ligand ring sizes cause a change in the electronic configuration and magnetic properties. Bicyclic guanidinate ligands allow the preparation of Re_2^7+ compounds from Re_2^6+ compounds, both of which are examined structurally and electrochemically. [Os2(hpp)4]^+ is examined to improve upon earlier studies, yielding a model of the g-tensor components with respect to the compound structure. An additional project included in the dissertation involves the study of an asymmetric trinickel extended metal atom chain. The structural effects of the asymmetry are examined to help elucidate the magnetic behavior that differs significantly from symmetric trinickel extended metal atom chains.