Nuclear-based hydrogen generation is a promising way to supply hydrogen for this large market in the future. This thesis focuses on one of the most promising methods, a thermochemical Cu-Cl cycle, which is currently under development by UOIT, Atomic Energy of Canada Limited (AECL) and the Argonne National Laboratory (ANL). The safety issues of the Cu-Cl cycle are addressed in this thesis. An investigation of major accident scenarios shows that potential tragedies can be avoided with effective risk analysis and safety management programs. As a powerful and systematic tool, fault tree analysis (FTA) is adapted to the particular needs of the Cu-Cl system. This thesis develops a new method that combines FTA with a reliability analysis tool, multi-state system (MSS), to improve the accuracy of FTA and also improve system reliability. / UOIT

X-ray absorption spectroscopy and computational chemistry have been used to probe the structure of biomolecules involved in cellular copper homeostasis. X-ray absorption spectroscopy shows that copper chaperones involved in cytochrome c oxidase assembly bind Cu(I) with trigonal coordination environments in poly-copper thiolate clusters, but the number of coppers in these clusters remains unclear. X-ray absorption spectroscopy of the metal-sensing transcription factor-1 from Drosophila melanogaster and metallothionein from Saccharomyces cerevisiae with stoichiometries of four or less shows a tetracopper cluster in an all-or-none manner in these molecules. These results suggest that cooperative binding of copper to form tetracopper clusters may be a common mechanism employed by copper control molecules. The active site structure of the novel copper-sensitive repressor CsoR in Mycobacterium tuberculosis binds copper in a trigonal coordination geometry with two sulfur and one nitrogen donors according to X-ray absorption spectroscopy results. Molecular dynamics simulations of both apo- and Cu-bound CsoR reveal local conformational changes in CsoR upon copper binding, which suggests multiple possible mechanisms of Cu-dependent transcriptional regulation by CsoR. Finally, X-ray absorption spectroscopy and X-ray fluorescence imaging have been used to understand the molecular basis of a promisng new treatment for Wilsons disease (a genetic disorder of Cu homeostasis) using tetrathiomolybdate. Overall, the results presented provide an essential structural basis for understanding copper homeostasis in living cells.

X-ray absorption spectroscopy and computational chemistry have been used to probe the structure of biomolecules involved in cellular copper homeostasis. X-ray absorption spectroscopy shows that copper chaperones involved in cytochrome c oxidase assembly bind Cu(I) with trigonal coordination environments in poly-copper thiolate clusters, but the number of coppers in these clusters remains unclear. X-ray absorption spectroscopy of the metal-sensing transcription factor-1 from Drosophila melanogaster and metallothionein from Saccharomyces cerevisiae with stoichiometries of four or less shows a tetracopper cluster in an all-or-none manner in these molecules. These results suggest that cooperative binding of copper to form tetracopper clusters may be a common mechanism employed by copper control molecules. The active site structure of the novel copper-sensitive repressor CsoR in Mycobacterium tuberculosis binds copper in a trigonal coordination geometry with two sulfur and one nitrogen donors according to X-ray absorption spectroscopy results. Molecular dynamics simulations of both apo- and Cu-bound CsoR reveal local conformational changes in CsoR upon copper binding, which suggests multiple possible mechanisms of Cu-dependent transcriptional regulation by CsoR. Finally, X-ray absorption spectroscopy and X-ray fluorescence imaging have been used to understand the molecular basis of a promisng new treatment for Wilsons disease (a genetic disorder of Cu homeostasis) using tetrathiomolybdate. Overall, the results presented provide an essential structural basis for understanding copper homeostasis in living cells.

This research deals with the synthesis and characterization (transmission electron microscopy and optical spectroscopy) of composite nanocondensates produced by pulse laser ablation (PLA) on Zn, Zn-Cu and Cu-Au targets in liquid or vacuum. First, wurtzite-type (W)-ZnO and

Abstract Isopropyl alcohol¡]IPA¡^and toluene are extensively used in industry as solvents. They are all highly toxic to animals and humans. Accordingly, IPA and toluene are strongly associated with problems of VOCs. In first step catalytic incineration was adopted to decompose IPA and toluene in laboratory, and the second step for a pilot-scale regenerative catalytic oxidizer ¡]RCO¡^were adopted to decompose mixture VOCs in real soil herein. The screening test of catalytic activity and the influences of the operational parameters on IPA and toluene removal efficiencies were widely discussed through catalytic incinerations of IPA and toluene in laboratory. The more effective and cheaper catalysts through above discussions of catalytic incineration were selected. And they were utilized in an pilot scale RCO as follows to investigate their performance in VOCs oxidation and RCO operations in THC removal of contamination soils. The achievements of this study are summarized as follows: ¡]1¡^Cu/Mn and Cu/Co gravel catalytic incinerations of isopropyl alcohol The results demonstrated that 10 wt% Cu0.6Co0.4 catalyst was the most effective because the CO2 yield reached 95 % under the following operating conditions; a temperature of 425oC, an inlet IPA concentration of 2500 ppm, an oxygen concentration of 21%, and a space velocity of 13500 hr-1. Additionally, the stability test results indicated that the 10 wt% Cu0.6Co0.4 catalyst exhibited excellent stability at both low and high conversion of IPA. ¡]2¡^20% Cu/Mn aluminum oxide catalytic incinerations of toluene The conversion for toluene reached 95% when the Cu/Mn catalyst was used with a metal ratio of 1:1 and 20% loading at 350¢XC, an influent toluene concentration of 1000 ppm, oxygen concentration of 21%, a space velocity of 12000 hr-1, and relative humidity of 26%. The long-term test was proceeded for seven days at a constant influent toluene concentration of 1000 ppm, constant oxygen concentration of 21%, constant space velocity of 12000 hr-1 and constant relative humidity of 26%. The SEM results indicated the Cu/Mn catalyst was quite stable at 350¢J. ¡]3¡^RCO testing for a copper/manganese catalyst of gaseous toluene The Cu/Mn (20wt%) catalyst was selected as the best one, because it converted 95% of the toluene at 400¢J. The results also indicating that the Cu/Mn catalyst was quite stable at 400¢J. (4) RTO treatment of VOCs with SVE system The conversion for VOCs reached 80% at 900¢XC, an influent VOCs concentration of 450-2000 ppm and a gas flow rate of 0.5 m3/min.The Thermal Recovery Efficiency¡]TRE¡^was approximately 86-90% in a RTO operated at 800-900¢J. (5)RCO treatment of VOCs with SVE system¡]10 wt% Cu0.6Co0.4 gravel catalyst¡^ The 10 wt% Cu0.6Co0.4 gravel catalyst was the poverty active, because it converted 65% of the VOCs by SVE system operated at 650¢J. (6)RCO treatment of VOCs with SVE system¡]20% Cu/Mn aluminum oxide catalytst¡^ The 20% Cu/Mn aluminum oxide catalytic was the best choice, because it converted 95% of the VOCs at 650¢J, an influent VOCs concentration of 450-10000 ppm and a gas flow rate of 0.5-1.5 m3/min. The SEM results indicated that the conversion of VOCs decay did not clearly vary at 650¢J, also indicating that the Cu/Mn catalyst selected was quite stable. The TRE was approximately 90% in a RCO¡]20% Cu/Mn aluminum oxide catalytic¡^operated at 650¢J. (7)RCO treatment of VOCs with SVE system¡]20% Cu/Mn gravel catalytst¡^ The 20% Cu/Mn gravel catalytst was the best selection , because it converted 95% of the VOCs at 600¢J, an influent VOCs concentration of 450-10000 ppm and a gas flow rate of 0.5-1.5 m3/min. The SEM results indicated that the conversion of VOCs decay did not clearly vary at 600¢J, also indicating that the Cu/Mn catalyst selected was quite stable. The TRE was approximately 90% in a RCO¡]20% Cu/Mn gravel catalytic¡^operated at 600¢J.

Copper is an integral component of key metabolic enzymes. Numerous physiological processes depend on a fine balance between the biosynthetic incorporation of copper into proteins and the export of excess copper from the cell. The homeostatic control of copper requires the activity of the copper transporting ATPases (Cu-ATPases). In Wilson disease the disruption in the function of the Cu-ATPase ATP7B results in the accumulation of excess copper and a marked deficiency of copper-dependent enzymes. In this work, the structure of ATP7B has been modeled by homology using the Ca-ATPase X-ray structure, enabling a mechanism of copper transport by ATP7B to be proposed. The fourth transmembrane helix (TM4) of Ca-ATPase contains conserved residues critical to cation binding and is predicted to correspond to TM6 of the ATP7B homology model, containing the highly conserved CXXCPC motif. The interaction with Cu(I) and the importance of the 3 cysteines in TM6 of ATP7B has been shown using model peptides. ATP7B has a large cytoplasmic N-terminus comprised of six copper-binding domains (WCBD1-6), each capable of binding one Cu(I). Protein-protein interactions between WCBDs and the copper chaperone Atox1 has been shown, contrary to previous reports, to occur even in the absence of copper. 15N relaxation measurements on the apo and Cu(I)-bound WCBD4-6 show that there is minimal change in the dynamic properties and the relative orientation of the domains in the two states. The domain 4-5 linker remains flexible, and domain 5-6 is not a rigid dimer, with flexibility between the domains. Copper transfer to and between WCBD1-6 likely occurs via protein interactions facilitated by the flexibility of the domains with respect to each other. The flexible linkers connecting the domains are important in giving the domains motional freedom to interact with Atox1, to transfer copper to other domains, and finally to transfer copper to the transmembrane site for transport across the membrane.

Copper is an integral component of key metabolic enzymes. Numerous physiological processes depend on a fine balance between the biosynthetic incorporation of copper into proteins and the export of excess copper from the cell. The homeostatic control of copper requires the activity of the copper transporting ATPases (Cu-ATPases). In Wilson disease the disruption in the function of the Cu-ATPase ATP7B results in the accumulation of excess copper and a marked deficiency of copper-dependent enzymes. In this work, the structure of ATP7B has been modeled by homology using the Ca-ATPase X-ray structure, enabling a mechanism of copper transport by ATP7B to be proposed. The fourth transmembrane helix (TM4) of Ca-ATPase contains conserved residues critical to cation binding and is predicted to correspond to TM6 of the ATP7B homology model, containing the highly conserved CXXCPC motif. The interaction with Cu(I) and the importance of the 3 cysteines in TM6 of ATP7B has been shown using model peptides. ATP7B has a large cytoplasmic N-terminus comprised of six copper-binding domains (WCBD1-6), each capable of binding one Cu(I). Protein-protein interactions between WCBDs and the copper chaperone Atox1 has been shown, contrary to previous reports, to occur even in the absence of copper. 15N relaxation measurements on the apo and Cu(I)-bound WCBD4-6 show that there is minimal change in the dynamic properties and the relative orientation of the domains in the two states. The domain 4-5 linker remains flexible, and domain 5-6 is not a rigid dimer, with flexibility between the domains. Copper transfer to and between WCBD1-6 likely occurs via protein interactions facilitated by the flexibility of the domains with respect to each other. The flexible linkers connecting the domains are important in giving the domains motional freedom to interact with Atox1, to transfer copper to other domains, and finally to transfer copper to the transmembrane site for transport across the membrane.

Submitted by Viviane Lima da Cunha (viviane@biblioteca.ufpb.br) on 2016-07-27T14:58:46Z No. of bitstreams: 1 arquivototal.pdf: 2690635 bytes, checksum: 755347a9fe593fec9ee6de7af48d4375 (MD5) / Made available in DSpace on 2016-07-27T14:58:46Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 2690635 bytes, checksum: 755347a9fe593fec9ee6de7af48d4375 (MD5) Previous issue date: 2015-07-16 / Shape memory alloys are widely used to produce mechanical actuators which operate in a temperature range that are responsible for the shape recovery of the sensor element. Such applications are numerous engineering. In this case, the main aspect responsible for a good performance of the system is the stability of the characteristics temperature of the alloy, i.e., the start and finish temperatures of the austenitic and martensitic transformations. Cu-Al-Be alloys are very attractive from the commercial point of view and have low transformation temperatures, thus, attractive for various applications. However, the stability of the phases is still the subject of various investigations. In this work, a device for conducting thermal cycling experiments was constructed which is able to cycling the samples up to 10,000 times, enabling the investigation of the thermal stability of Cu-Al-Be alloy containing Cr, as grain refining element. Experimental results have shown that the thermal cycling over extended periods of times increases the temperatures of the martensitic phase reversion - stabilizing the martensite phase. On the other hand tests carried out during the aging heat treatments did not significantly alter these temperatures. It was concluded that the main mechanism for stabilization of the martensitic phase is related to the immobilization of the interface due to defects introduced during the thermocycling. / Ligas passíveis do efeito memória de forma são muito usadas para confecção de atuadores mecânicos os quais trabalham em uma faixa de temperatura as quais são responsáveis pela recuperação de forma do elemento sensor. Este tipo de aplicação é numeroso na engenharia. Neste caso, o principal aspecto responsável para um bom desempenho do sistema reside na estabilidade das temperaturas características da liga, ou seja, nas temperaturas de início e fim das transformações austenítica e martensítica. Ligas Cu-Al-Be são bastante atrativas do ponto de vista comercial e possuem temperaturas de transformação baixas, sendo assim, atrativas para diversas aplicações. Entretanto, a estabilidade das fases é ainda tema de diversas investigações. Nesse trabalho, foi construído um dispositivo para realização de ciclagem térmica por longos períodos, até 10.000 ciclos, de modo a possibilitar a investigação da estabilidade térmica de ligas Cu-Al-Be contendo Cr como elemento refinador de grão. Os resultados experimentais demonstraram que a ciclagem durante longos períodos aumenta as temperaturas de reversão da fase martensítica - estabilização da fase martensítica. Por outro lado, os testes realizados durante os tratamentos térmicos de envelhecimento não alteram de modo significativo estas temperaturas. Foi concluído que o principal mecanismo para estabilização da fase martensítica está relacionado com a imobilização da interfase devido à introdução de defeitos durante a ciclagem térmica.

Neste trabalho são apresentados estudos em três diferentes sistemas utilizando-se as técnicas de Ressonância Paramagnética Eletrônica (RPE) e absorção eletrônica. No primeiro estudou-se a formação dos possíveis complexos entre o aminoácido aliina, extraído do alho, e o íon cobre (II). Os dados de RPE e absorção eletronica no visível (400-1100 nm) foram utilizados para caracterizar os diferentes complexos obtidos. No segundo utilizou-se o monocristal do complexo dicloro bis (benzil difenil fosfinóxido) Cobre (II) e efetuaram-se medidas de RPE variando-se a direção de aplicação do campo magnético no monocristal. Os auto-valores encontrados para as componentes do tensor g&#175 foram: g1= 2,0891; g2= 2,4554 e g3= 2,0767. Com base nos dados de RPE e cristalográficos e usando a teoria de campo cristalino foi proposto dxy como estado fundamental para o íon cobre (II) neste complexo. Fez-se também um estudo preliminar observando-se as variações no centro ativo de hemoproteínas moduladas pelo grau de hidratação. Metahemoglobina bovina e metamioglobina eqüina liofilizadas foram usadas e o sinal de RPE do íon ferro (III) monitorado. Dos espectros de RPE das duas proteínas são observadas pelo menos duas simetrias para o íon ferro (III), uma axial caracterizada por um valor de g próximo de 6 e outra caracterizada por g= 4,3 correspondendo a simetria rômbica. A intensidade dos sinais mostrou-se muito sensíveis ao grau de hidratação. Metahemoglobina e metamioglobina apresentaram comportamentos distintos dos sinais de RPE e sugeriu-se serem eles devido as diferenças estruturais entre as duas proteínas / In this work studies in three different systems using Electron Paramagnetic Resonance (EPR) and eletronic absorption techniques are presented. The formation of possible complexes between the amino acid aliin, extracted of garlic, and the copper (II) íon was studied in the first work. EPR and visible eletronic absorption (400-1100 nm) data were utilized to characterize the different complexes obtained. In the second work a crystal of the complex dichloro bis (benzyl diphenyl phosphinoxide) copper (II) was used and the EPR measures were made for different directions of application of the magnetic field in the crystal. The eigenvalues obtained for the g&#175 tensor components were: g1= 2,0891; g2= 2,4554 and g3= 2,0767. Using EPR and crystallographic data and crystal field theory dxy was proposed as the ground state of the copper (II) íon in this complex. A preliminary study was also made observing changes at the active Center of the hemeproteins modulated by the hydration degree. Lyophilized bovine methemoglobin ande quine metmyoglobin were used and the EPR signal of the iron (III) íon monitored. Or both proteins the EPR spectra corresponding to at least two iron symmetries were observed, one axial characterized by a g value near 6.0 and another characterized by g= 4,3 corresponding to rhombic symmetry. The intensity of these signals were very sensitive to the hydration degree. Metmyoglobin and methemoglobin showed distint behaviors of the EPR signals and it was suggested that they were due to structural differences between the two proteins

Neste trabalho estudou-se a formação de complexos da tirosina e de seus dipeptídeos tirosil-glicina e glicil-tirosina com o íon Cu2+. Para a caracterização destes complexos foram utilizadas as técnicas espectroscópicas de Absorção ótica na região do visível (400 a 800 nm), Ressonância paramagnética eletrônica em duas temperaturas (ambiente e &#8764-150&#176C) e a técnica de fluorescência. No caso da tyr os dados experimentais obtidos pela espectroscopia de RPE sugerem a formação de pelo menos duas espécies distintas de complexos além do cobre hidratado. Os complexos propostos foram: o CuL4 (ao redor de pH 3,5) e o CuL2 (na faixa de pH 4,0 e 12,0). Já para os dipeptídeos são evidenciados três tipos diferentes de complexos. São propostos os seguintes complexos: CuL2 (ao redor de pH 4,5), CuL (H2O) (na faixa de pH 7,0 e 12,0) e CuL(OH)22- (acima de pH 12,0). Os espectros de RPE mostram claramente que com o aumento de pH, ocorre a complexação do Cu2+ com os dipeptídeos. Em pHs altos (acima de pH 10,0) surgem nestes espectros uma estrutura superhiperfina de 5 linhas típicas para a coordenação de Cu2+ com dois nitrogênios. Quanto a tirosina, o espectro de seu complexo com Cu2+, não apresenta estrutura superhiperfina, sendo o sinal obtido, típico do complexo com Cu2+. Da mesma forma que foi observado por RPE, pode-se observar pelos espectros óticos, que em pHs baixos (2,0 a 3,5) para os dipeptídeos, os espectros apresentam uma banda larga e mal-resolvida, característica do íon de Cu2+ livre em solução. Observou-se também um deslocamento do máximo das bandas para o azul, apresentando características típicas das transições d-d correspondentes às várias espécies de complexos do metal em equilíbrio. Os dados de fluorescência foram muito informativos. As titulações da tyr e dos dipeptídeos puros em função do pH permitiram a determinação dos valores de pKs dos grupos ionizáveis. O efeito de supressão de fluorescência devido ao paramagnetismo do cobre foi usado tanto para a determinação da estequiometria quanto para a determinação das constantes de associação dos complexos dos dipeptídeos com Cu2+ em dois pHs fixos (pH 7,0 e 9,0). Encontrou-se complexos com a seguinte estequiometria (ligante/metal) : 2:1 e 1:1 respectivamente para a tyr e para os dipeptídeos nestes pHs. Um modelo simples de equilíbrio foi desenvolvido e estimou-se as constantes de associação da ordem de 107M-1 para os complexos de dipeptídeos- Cu2+. / The main goal of this work was to study the formation of the complexes of tyrosine and its dipeptides tyrosil-glycil and glycil-tyrosine with the transition metal íon Cu2+. The characterization of these complexes was performed through the use of spectroscopic techniques: optical absorption, electron paramagnetic resonance at both room temperature and -150&#176C and fluorescence emission. The EPR spectroscopy suggested for tyrosine two distints species. The following complexes were proposed: CuL4 (pH 3,5) and CuL2 (in the range of pH between 4,0-12,0). Three different complexes were evidentiated for dipeptides- Cu2+: CuL2 (pH 4,5); CuL(H2O) (in the range of pH between 7,0-12,0) and CuL(OH)22- (above pH 12,0). EPR spectra shows clearly the complexation of Cu2+ to the dipeptides. Both at intermediate and high pHs and specially above pH 10,0 a superhyoerfine structure of five lines typical for coordination of copper to two nitrogens was observed. In the case of the aminoacid no superhyperfine structure is observed. EPR data suggest that in a wide pH range between 7,0 and 11,0 the complex formed by the dipeptides was CuL(H2O). Electronic optical absorption was measured at room temperature as a function of pH in the range 2,0-13,0. It was observed that at low pHs (2,0 3,5) the spectra for the dipeptides was characterized by a broad not well resolved band around 800 nm characteristic of hidrated free Cu2+ in water solution. EPR spectra are in agreement with this observation. Increase of pH leads to a blue shift in the absorption band maximum and as a consequence to typical spectra for d-d transitions of the various species of complexes of cooper in equilibrium in solution. Fluorescence data were also very informative. The pure tyr and dipeptides tritation allowed to determine pKs values of ionizable groups. The effect of fluorescence suppression due to paramagnetic copper was used both to establish the stoichiometry of the complexes and the association constants. The stoichiometry of the complexes was determined as 2:1 and 1:1 ligand:metal for tyrosine and the dipeptides respectively at pH 7,0 and pH 9,0. A simple equilibrium model was developed and the association constants for the Cu2+ dipeptides complexes at pH 7,0 and pH 9,0 were estimated to be around 107M-1.