This thesis primarily focuses on the systematic understanding of structure – reactivity relationships in two representative systems: bixbyite and related structures as well as indium doped CeO2. Topotactic reaction routes have gained significant attention over the past two decades due to their potential to access kinetically controlled metastable materials. This has contributed substantially to the understanding of solid state reaction pathways and provided first insights into mechanisms. Contrary to the widely used ex-situ methods, in – situ techniques including powder x-ray diffraction and thermogravimetric – differential thermal analysis have been employed extensively throughout this work in order to follow the reaction pathways in real time. Detailed analysis of the AVO3 (A = In, Sc) bixbyite reactivity under oxidative conditions has been carried out and a variety of novel metastable oxygen defect phases have been identified and characterized. The novel metastable materials have oxygen deficient fluorite structures and consequently are potential ion conductors. Structural aspects of the topotactic vs. reconstructive transformations are illustrated with this model system. The structure – reactivity study of AVO3 phases was extended to AVO3 perovskite family. Based on the research methodologies and results from AVO3 bixbyite reactivity studies a generalized mechanistic oxidation pathway has been established with a non-vanadium phase, ScTiO3 bixbyite. However, there is stark contrast in terms of structural stability and features beyond this stability limit during AVO3 and ScTiO3 bixbyite reaction pathways. A series of complex reaction sequences including phase separation and phase transitions were identified during the investigation of ScTiO3 reactivity. The two-step formation pathway for the fluorite – type oxide ion conductor Ce1-xInxO2-δ (0 ≤ x ≤ 0.3) is being reported. The formation of the BaCe1-xInxO3-δ perovskites and the subsequent CO2-capture reaction with the formation of Ce1-xInxO2-δ (0 ≤ x ≤ 0.3) has been investigated in detail. The two-step formation pathway is contrasted with the unsuccessful direct method. The stability and the extent of In – doping for the CeO2 fluorite phases that can be achieved through this CO2 – capture method are reported. The necessity and strategies for the selection of appropriate intermediate precursors for the preparation of doped CeO2 are also reported.

The daughters of women with a history of depression are at heightened risk for a range of mental health problems. The present study investigated emotion regulation, cortisol reactivity to stress, and interpersonal competence as potential indicators of risk in adolescent girls at high versus low risk for depression. Participants were a community sample of 47 girls and their mothers (27 high risk and 20 low risk). Mothers and daughters had been interviewed to assess diagnostic history as part of a previous longitudinal study. In the current study, daughters completed the Trier Social Stress Test for Children (TSST-C) and cortisol samples were collected before and after exposure to this psychosocial stressor. Both mothers and daughters completed self-report questionnaires and daughters were re-assessed using the Depressive Disorders module of the Kiddie Schedule for Affective Disorders and Schizophrenia. High risk mothers were also interviewed to assess the timing and chronicity of their depressive episodes during their daughters’ lifetime. High and low risk girls had equivalent ratings of self-reported stress following the TSST-C, but different physiological responses. Girls at high risk for depression showed a blunted cortisol response to the TSST-C whereas low risk girls showed a normal cortisol response. High risk status for depression predicted a blunted cortisol response to stress, which predicted difficulties with emotion regulation; difficulties with emotion regulation in turn predicted a greater number of self-reported depressive symptoms. These results suggest that maternal depression may act as a stressor that compromises stress-response system functioning in daughters and produces related difficulties with emotion regulation.

To exemplify how theoretical chemistry can be applied to understand ground and excited state reactivity, four different chemical reactions have been modeled. The ground state chemical reactions are the simplest models in chemistry. To begin, a route to break down halomethanes through reactions with ground state cyano radical has been selected. Efficient explorations of the potential energy surfaces for these reactions have been carried out using the artificial force induced reaction algorithm. The large number of feasible pathways for reactions of this type, up to eleven, shows that these seemingly simple reactions can be quite complex. This exploration is followed by accurate quantum dynamics with reduced dimensionality for the reaction between Cl− and PH2Cl. The dynamics indicate that increasing the dimensionality of the model to at least two dimensions is a crucial step for an accurate calculation of the rate constant. After considering multiple pathways on a single potential energy surface, various feasible pathways on multiple surfaces have been investigated. As a prototype of these reactions, the thermal decomposition of a four-membered ring peroxide compound, called 1,2-dioxetane, which is the simplest model of chemi- and bioluminescence, has been studied. A detailed description of this model at the molecular level can give rise to a unified understanding of more complex chemiluminescence mechanisms. The results provide further details on the mechanisms and allow to rationalize the high ratio of triplet to singlet dissociation products. Finally, a thermal decomposition of another dioxetane-like compound, called Dewar dioxetane, has been investigated. This study allows to understand the effect of conjugated double bonds adjacent to the dioxetane moiety in the chemiluminescence mechanism of dioxetane. Our studies illustrate that no matter how complex a system is, theoretical chemistry can give a level of insight into chemical processes that cannot be obtained from other methods.

This thesis is concerned with structure-reactivity relationships in metallocene chemistry. In particular new ansa-metallocenes of Groups 5-7 have been prepared. The structure and reactivity of these ansa-metallocenes is compared to the corresponding nonbridged metallocenes.

Antibodies play an important role in the natural immune response to invading pathogens. The strong and specific binding to their antigens also make them indispensable tools for research, diagnostics and therapy. This thesis describes the development of methods for characterization of an- tibody specificity and the use of these methods to investigate the polyclonal antibody response after immunization. Paper I describes the development of an epitope-specific serum fractionation technique based on epitope map- ping using overlapping peptides followed by chromatographic separation of polyclonal serum. This technique together with another epitope mapping technique based on bacterial display of protein fragments were then used to generate antibody sandwich pairs (Paper I), investigate epitope variations of repeated immunizations (Paper II) and to determine the ratio of antibodies targeting linear and conformational epitopes of polyclonal antibodies (Paper III). Paper IV describes the optimization of in situ-synthesized high-density peptide arrays for epitope mapping and how different peptide lengths influ- ence epitope detection and resolution. In Paper V we show the development of planar peptide arrays covering the entire human proteome and how these arrays can be used for epitope mapping and off-target binding analysis. In Paper VI we show how polyclonal antibodies targeting linear epitopes can be used for peptide enrichment in a rapid, absolute protein quantification protocol based on mass spectrometry. Altogether these investigations demonstrate the usefulness of peptide arrays for fast and straightforward characterization of antibody specificity. The work also contributes to a deeper understanding of the polyclonal anti- body response obtained after immunization with recombinant protein frag- ments. / <p>QC 20141111</p>

Systemic hypoxia frequently occurs in patients with cardiopulmonary diseases. Maintenance of vascular reactivity and endothelial viability is essential to preserving oxygen delivery in these patients. The role of matrix metalloproteinase-2 (MMP-2) and heme oxygenase-2 (HO-2) in the vascular response to hypoxia were investigated. In the first part of the thesis, the role of MMP-2 in regulating systemic arterial contraction after prolonged hypoxia was investigated. MMP-2 inhibition with cyclic peptide CTTHWGFTLC (CTT) reduced phenylephrine (PE)-induced contraction in aortae and mesenteric arteries harvested from rats exposed to hypoxia for 7 d. Responses to PE were reduced in MMP-2-/- mice exposed to hypoxia for 7 d compared to wild-type controls. CTT reduced contraction induced by big endothelin-1 (big ET-1) in aortae harvested from rats exposed to hypoxia. Increased contraction to big ET-1 after hypoxia was observed in wild-type controls, but not MMP-2-/- mice. Rat aortic MMP-2 and MT1-MMP protein levels and MMP activity were increased after 7 d of hypoxia. Rat aortic MMP-2 and MT1-MMP mRNA levels were increased in the deep medial vascular smooth muscle. These results suggest that hypoxic induction of MMP-2 activity potentiates contraction in systemic conduit and resistance arteries through proteolytic activation of big ET-1. The second part of the thesis investigated oxygen regulation of HO-2 protein and whether it plays a role in preserving endothelial cell viability during hypoxia. HO-2, but not HO-1, protein level was maintained during hypoxia in human endothelial cells through enhanced translation of HO-2 transcripts. Inhibition of HO-2 expression increased the production of reactive oxygen species, decreased mitochondrial membrane potential, and enhanced apoptotic cell death and activated caspases during hypoxia, but not during normoxia. These data indicate that HO-2 is translationally regulated and important in maintaining endothelial viability and function during hypoxia. In summary, the thesis demonstrates the importance of MMP-2 and HO-2 in preserving vascular function during prolonged systemic hypoxia. These enzymatic pathways may, therefore, represent novel therapeutic targets that may be exploited to ameliorate the effects of hypoxia in patients with cardiopulmonary disease.

As a novel high temperature fuel cell, the direct carbon fuel cell (DCFC) is drawing ever-increasing attention due to its significant high conversion efficiency, diversified fuel resources and low pollution compared with conventional coal-fired power plants. Despite the advantages of the DCFC technology, there are a number of fundamental and technological challenges which need to be overcome for its further development and commercialization. One of the major hurdles in current study of the DCFC is that the efficacy of carbon fuels is still unclear. Meanwhile, the effects of impurities in the carbon fuels on the performance and lifetime of the DCFC are still up for debate. Furthermore, the molecular-level study on the mechanism of electrochemical oxidation of carbon fuels in the DCFC is limited by the lack of techniques to detect the reaction intermediates at high temperature. Finally, how to scale up the DCFC system with suitable hardware materials and optimum structural designs needs further investigation. Based on successfully developing a DCFC system with a stirring molten carbonate electrolyte, various commercial and self-made carbon fuels including activated carbons, carbon blacks, graphitic carbons, coals and carbon nanofibers (CNFs) are systematically characterized and evaluated in this thesis. It is found that the nature of carbon fuels plays an important role in the anodic performance of the DCFC. A higher surface area and a smaller particle size of carbon fuel can effectively improve its electrochemical reactivity by increasing the interaction between the carbon particles and the molten carbonate electrolyte. On the contrary, a higher graphitic degree of carbon fuel results in a lower electrochemical reactivity in the DCFC due to the less reactive sites such as edges and defects on carbon surface. Furthermore, the order of the electrochemical reactivities for carbon fuels is in good agreement with the concentration of oxygen-containing functional groups on their surface, which is believed to play a key role in the electrochemical oxidation of carbons in the DCFC. In order to better understand the relationship between the surface chemistry of carbons and their electrochemical performance in the DCFC, various pre-treatment techniques including acid washing, air-plasma treatment, air oxidation, pyrolysis and the pre-electrochemical oxidation (in molten alkali carbonate electrolytes) have been conducted on the carbon fuels. It is shown that both the HNO3 washing and pre-electrochemical oxidation are much more effective to improve the electrochemical reactivities of carbon fuels compared to other pre-treatment techniques, which is attributed to the significant changes in the microstructure of carbon fuels and more surface oxygen functional groups produced during the pre-treatments. In contrast, the pyrolysis treatment results in a sharp decrease of electrochemical reactivity of carbon fuels due to the decreases in oxygen-containing surface groups and surface areas, and the increase of their graphitic degrees. For the sake of the optimum operational conditions for the DCFC system, the influences of stirring rates, the carbon fuel loadings and fuel cell temperatures on the anodic performance of the DCFC are investigated. It has been shown that the carbon discharge rates can be significantly boosted by effective stirring and high carbon fuel concentrations due to an improved mass transport. A higher operation temperature can also increase the current density and open circuit voltage of the DCFC. However, the complete electrochemical oxidation of carbon into CO2 can be only achieved at the low operation temperature of 600-700 ºC, while the partially electrochemical oxidation of carbon into CO occurs at 800 ºC, which will significantly decrease the carbon efficiency to less than 10% at 800 ºC. In the study of self-made CNFs as fuels for the DCFC, both microstructure and electrochemical reactivity of CNFs are highly dependent on their synthesis conditions. Compared with Ni-Al2O3 catalyst, the coprecipitated Ni-Cu-Al2O3 catalyst produced more CNFs with higher electrochemically reactivity. Over the same catalyst, the CNFs synthesized at lower temperature typically have higher surface areas, more surface oxygen functional groups and lower graphitic degrees, thereby leading to a higher electrochemical reactivity in the DCFC tests. In an effort to study the catalytic effects of mineral impurities on the electrochemical performance of the DCFC, Al2O3 and SiO2 present passivation effects in the anodic reaction. In contrast, the CaO, MgO and Fe2O3 show catalytic effects in the carbon electrochemical oxidation, which is demonstrated by the increases of current densities at low over-potentials in the polarization curves.

No description available.

Este trabalho apresenta um estudo sobre o efeito de sombreamento em detectores de nêutrons, quando estes são utilizados em medidas de reatividade com a técnica de rod drop. O sombreamento pode ser entendido como uma mudança na eciência dos detectores, quando esta é dada em nêutrons detectados/ssão ocorrida no reator, sendo mais evidente nos detectores mais próximos ao banco sendo inserido. O método de análise, fundamentalmente teórica, baseou-se em simulações do reator IPEN/MB-01 utilizando o código CITATION e o programa MCNP. Em ambos os casos, os resultados são estáticos, mostrando os uxos neutrônicos apenas em duas situações: antes da inserção do banco, e após sua inserção. A reatividade, neste caso, é obtida utilizandose a expressão derivada da técnica de source jerk. Em adição ao estudo teórico, os dados de um experimento de rod drop realizado no reator IPEN/MB-01 também foram utilizados. Neste caso, a reatividade foi obtida com o método de cinética inversa, já que os dados experimentais são constituídos de valores que variam no tempo. Em todos os casos, fatores de correção para o efeito de sombreamento são propostos. / This work presents a study on the eect of shading in neutron detectors, when used in measures of reactivity with the rod drop technique. Shading can be understood as a change in the eciency of the detectors, when it is given in detected neutrons / ssion occurred in the reactor, more evident in the detectors closest to the bank being inserted. The method of analysis was based on simulations of reactor IPEN/MB-01, using the code CITATION and MCNP program. In both cases, the results were static, showing Neutronic ows in only two situations: before insertion of the control rod and after insertion. The measure of reactivity in this case was achieved using the expression derived from the source jerk technique. In addition to theoretical study, data from a rod drop experiment conducted in the reactor IPEN/MB-01 were also used. In this case, the reactivity was obtained using inverse kinetic method, since experimental data were set of values that vary with time. In all cases, correction factors for the shadowing eect have been proposed.

Ionic liquids (ILs) are nowadays a large and widely explored class of ionic compounds that melt below 100 °C. Due to their attractive properties, ILs are now of growing interests in a variety of inorganic materials preparation. However, most studies have put much focus on the description of new synthetic strategies. The chemical reactivity of ILs in the reactions is often neglected. In this dissertation, a series of metal chalcogenides were synthesized using the decompositions of ILs. The role or chemical reactivity of ILs in the reactions was demonstrated in detail. The hierarchical desert-rose-like SrTiO3 particles have been successfully prepared based on an ethylene glycol (EG) mediated one-pot IL-assisted solvothermal synthetic route. The used basic ionic liquid tetrabutylammonium hydroxide (TBAH) serves as an alkaline source and can also replace EG as the sole solvent to synthesize polyhedral SrTiO3, showing “all-in-one” solvent and reactant. A series of metal sulfides, such as Sb2S3, Bi2S3, PbS, CuS, Ag2S, ZnS, and CdS have been obtained from a choline chloride/thioacetamide based deep eutectic solvent (DES, an IL analog solvent) by a simple and general synthetic method. The reaction mainly proceeds in two steps: i) the dispersion of metal salts in the DES and the formation of a metal-DES complex, and ii) the decomposition of the metal-DES complex and formation of the final products. In addition, the chemical reactivity of phosphonium based ILs with selenium and tellurium at above 220 °C was systematically investigated by a series of dissolution experiments, tracking the solute selenium and tellurium species by nuclear magnetic resonance (NMR). NMR results clearly indicate some common decomposition mechanisms for quaternary phosphonium ILs at a relatively high temperature in the presence of selenium or tellurium. The decomposition of the quaternary phosphonium cations should proceed by an elimination of one alkyl substituent via an SN2 reaction, forming the respective trialkylphosphane selenides or tellurides in the presence of selenium or tellurium, which is then responsible for the genuine dissolution of selenium or tellurium. However, in the case of tellurium, the dissolution behavior is much more complicated compared to that of selenium. The coupling of P and Te which indicates a P–Te bond formation is only observed in the NMR spectra when a sufficient amount of tellurium (e.g. Te : IL = 1 : 1) is provided. The existence of a parallel-competitive IL decomposition route besides the SN2 reaction is regarded as the side reaction for the dissolution of tellurium. This may at least partially explain the relatively lower solubility of tellurium in phosphonium based ILs compared to that of selenium.