Thesis (Ph. D.)--University of Texas at Austin, 1999. / Vita. Includes bibliographical references. Available also in a digital version from Dissertation Abstracts.

No presente trabalho foram estudadas as estruturas eletranicas de compostos intermetglicos pseudo-binários do tipo fases de Laves. Foi formulado um modelo para descrever o andamento do parâmetro de rede em função da concentração para estes compostos. Os resultados experimentais medidos por técnicas hiperfinas de Correlação Angular Perturbada e Espectroscopia Mõs sbauer para a série (Zr,Hf)Fe 2 foram descritos por modelos simples, que abordam a desordem destes sistemas dentro da aproximação do potencial corrente. Foram discutidas as predições dos modelos e suas aplicações para outros sistemas. / In the present work we studied the electronic structures of Laves phases pseudo binaries intermetallic compounds. A model was formulated to describe the lattice parameter as a function of the concentration in these compounds. The experimental results in the series (Zr,Hf)Fe 2, obtained by Perturbed Angular Correlations and MSssbauer Spectroscopy are described by simple models, disorder being treated using the coherent potential approximation. The model predictions were discussed, as well as their application to other systems.

The factors that determine RNA structure formation, stability, and dynamics are inexorably linked to RNA function. The Hammerhead ribozyme (HHRz) has long served as a model for studying metal-dependent folding and catalysis in RNA. The HHRz consists of three helices meeting at a common junction of conserved nucleotides that form the active site of the ribozyme. Current models of metal-dependent HHRz function involve a requirement for divalent metals to globally fold the ribozyme at low metal concentrations, followed by a second metal-dependent process which activates the HHRz for catalysis. The exact role of metal ions in activating HHRz catalysis is still a subject of investigation. We used 2-aminopurine substitutions near the active site of the ribozyme to determine if this second metal-dependent process involves a conformational rearrangement in the core of the ribozyme. We find evidence for a conformational change beyond global folding in the core of the ribozyme that not only correlates with metal activated catalysis but is also sensitive to the identity of the metal ions used for folding. Though phosphorothioate substitutions indicate that a ground-state coordination of a catalytic metal to the scissile phosphate is required for efficient catalysis, our folding studies show that this coordination event is not absolutely required for folding of the HHRz core. To investigate possible roles for metal ions in general acid-base catalysis, we tested the pH dependence of the HHRz rate using a variety of metal ions. We find the pH dependent rate profile of the ribozyme is shifted by transition metal ions, whereas other group II metals show similar profiles to Mg

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No presente trabalho foram estudadas as estruturas eletranicas de compostos intermetglicos pseudo-binários do tipo fases de Laves. Foi formulado um modelo para descrever o andamento do parâmetro de rede em função da concentração para estes compostos. Os resultados experimentais medidos por técnicas hiperfinas de Correlação Angular Perturbada e Espectroscopia Mõs sbauer para a série (Zr,Hf)Fe 2 foram descritos por modelos simples, que abordam a desordem destes sistemas dentro da aproximação do potencial corrente. Foram discutidas as predições dos modelos e suas aplicações para outros sistemas. / In the present work we studied the electronic structures of Laves phases pseudo binaries intermetallic compounds. A model was formulated to describe the lattice parameter as a function of the concentration in these compounds. The experimental results in the series (Zr,Hf)Fe 2, obtained by Perturbed Angular Correlations and MSssbauer Spectroscopy are described by simple models, disorder being treated using the coherent potential approximation. The model predictions were discussed, as well as their application to other systems.

A series of bis [e] and [a] fused dibenzannulenes/cyclophanes have been synthesized for the first time using benzyne-like intermediates (annulynes). These include the dibenzannulene trans-2,9-di-t-butyl-14c, 14d-dihydro-14c-14d-dimethyldibenzo[fg,op]naphthacene 82b, and the metacyclophanedienes anti-[1,2;9,10]- dibenzo-5, 13-di-t-butyl-8,16-dimethyl[2.2]metacyclophane 82a, and anti-[1,2-b; 9,10-b]- dinaphtho-5,13-di-t-butyl-8,16-dimethyl[2.2]metacyclophane 85a. From these compounds several metal complexes including trans-{μ- [( 1,2,3,4,4a, 14b-η:8a,9,10,11,12,12a-η)-12c, 12d-dihydro-12c-12d-dimethylbenzo[ rst]pentaphene]]hexacarbonyldichromium 100, have been synthesized. Among the bis [e] fused compounds, pairs 82a/82b and 95a/95b show reversible and repeatable photo-switching properties both in solution and in the solid state. The pyrene forms 82b and 95b are characterized at low temperature and they thermally return to their cyclophane forms 82a and 95a at room temperature. A polystyrene based film of 82 shows a much better bistability required for photo-switching units. These properties make them potential candidates for optical memory units. For the similar naphtho[e] fused compound 95a, no pyrene isomer 95b was detected upon irradiation with UV light. Based on the NMR data, relative bond fixing abilities (RBFA) of several species are measured. The order is: [special characters omitted] > Benzene > Oxanorbomadiene > lU Norbomadiene The reduced species, oxanorbomene and norbomene, do not induce any significant bond localization on the [14] annulene ring. / Graduate

No presente trabalho foram estudadas as estruturas eletranicas de compostos intermetglicos pseudo-binários do tipo fases de Laves. Foi formulado um modelo para descrever o andamento do parâmetro de rede em função da concentração para estes compostos. Os resultados experimentais medidos por técnicas hiperfinas de Correlação Angular Perturbada e Espectroscopia Mõs sbauer para a série (Zr,Hf)Fe 2 foram descritos por modelos simples, que abordam a desordem destes sistemas dentro da aproximação do potencial corrente. Foram discutidas as predições dos modelos e suas aplicações para outros sistemas. / In the present work we studied the electronic structures of Laves phases pseudo binaries intermetallic compounds. A model was formulated to describe the lattice parameter as a function of the concentration in these compounds. The experimental results in the series (Zr,Hf)Fe 2, obtained by Perturbed Angular Correlations and MSssbauer Spectroscopy are described by simple models, disorder being treated using the coherent potential approximation. The model predictions were discussed, as well as their application to other systems.

Foram medidas distribuições angulares e funções de excitação do espalhamento de íons de ANTPOT. 16 O e ANTPOT. 18 O por ANTPOT. 92 Zr a energias Incidentes em torno da barreira Coulombiana, visando estudar a interferência nuclear-Coulombiana na excitação inelástica dos estados 2+ (0.934 MeV), 2 IND. 2+ (1.847 MeV) e 3- (2.340 MeV) do ANTPOT. 92 Zr, bem como na excitação do estado 2+ (1.962 MeV) do ANTPOT. 16 O, Além do espalhamento elástico e dos inelásticos, foram também observadas as reações (ANTPOT. 16 O, ANTPOT. 15 N) e ( ANTPOT. 16 O, ANTPOT. 17 O), com Intensidades comparáveis as das transições inelásticas. Foram obtidas distribuições angulares e funções de excitação também para estas reações. Os resultados experimentais foram analisados com cálculos utilizando a aproximação de Born com ondas distorcidas (DWBA) e com o formalismo de canais acoplados. A análise das distribuições angulares mostra que o padrão da interferência nuclear-Coulombiana na excitação do estado 2+ do ANTPOT. 92 zr, tanto por ANTPOT. 16 O como por ANTPOT. 18 O, somente pôde ser reproduzida introduzindo um forte termo de reorientação nuclear, e ao mesmo tempo uma intensidade de transição nuclear multo maior do que o que seria esperado dos valores de B(E2). A Introdução de reorientação no estado 3- também permitiu melhor ajuste a distribuição angular deste estado. A análise da função de excitação do estado 2+ do ANTPOT. 92 Zr mostra que, para ajustar a região da Interferência nuclear-Coulombiana, é necessário Introduzir um termo de acoplamento dependente da energia incidente. Para as reações de transferência, foi obtido um ajuste multo bom, com DWBA, para a reação (ANTPOT. 16 O, ANTPOT. 15 N). Para a reação (ANTPOT. 18 O, ANTPOT. 17 O), entretanto, encontrou-se grande discrepância entre os calculas DWBA e os dados experimentais são discutidas as possíveis origens de tais comportamentos fora dos \"padrões tradicionais\". / Angular distributions and excitation functions for the elastic and inelastic scattering of 16,18 O by 92 Zr were measured at energies in the vicinity of the Coulomb barrier, in order to study the Coulomb-nuclear Interference in the excitation of the 2+ (0.93\"1 MeV), 2 2+ (1.847 MeV) and 3- (2.340 MeV) states of 92 Zr, as well as In the excitation of the 2+ (1.982 MeV) state of 18 O. Besides the elastic and inelastic scattering, the transfer reactions ( 16O, 15N) and (18O, 17O) were also observed, with Intensities comparable to the Inelastic excitations. Angular distributions and excitation functions were thus obtained for these reactions as well. The experimental results were analyzed with DWBA and coupled channels calculations. The results from the analysis of the angular distributions show that the Coulomb-nuclear interference pattern in the 92 Zr (2+) excitation, both by 16 O and 18 O, could only be reproduced by Introducing a strong nuclear reorientation term, and at the same time a nuclear transition coupling much stronger than what would be expected from the B(E2) values. The Introduction of a nuclear reorientation term In the 3- excitation also lended to a better fit in the 3- angular distribution. The results of the analysis of the Zr(2+) excitation function shows that It is necessary to introduce an energy dependent coupling term In order to fit the Coulomb-nuclear Interference pattern. For the transfer reactions It was seen that DWBA can describe very well the ( 16O, 15N) angular distribution. For the (18O,17O) reaction, however, great discrepancies were found between the DWBA calculations and the experimental data. The possible origins of such \"uncommon\" behavior are discussed.

A estrutura nuclear do primeiro estado excitado do ANTPOT.64 Zn (J POT.= 2 POT.+, E IND.X = 0.992 MeV) foi estudada através de medidas do efeito de reorientação neste núcleo, e de distribuições angulares e funções de excitação do espalhamento de ANTPOT.16 O e ANTPOT.18 O por ANTPOT.64 Zn na região de interferência nuclear-coulombiana. Foram investigados os processos de interação do núcleo ANTPOT.64 Zn com os íons ANTPOT.16 O e ANTPOT.18 O no espalhamento inelástico sem e com excitação do projétil. O efeito de reorientação na excitação coulombiana observado através do retroespalhamento de ANTPOT.4 He, ANTPOT.16 O e ANTPOT.18 O, permitiu a determinação precisa da probabilidade reduzida de transição B(E2; O POT.+ 2 POT.+) e do momento de quadrupolo estático Q IND.2+ do primeiro estado excitado do ANTPOT.64 Zn. As distribuições angulares e funções de excitação experimentais do espalhamento elástico de ANTPOT.16 O e ANTPOT.18 O por ANTPOT.64 Zn foram analisadas com o modelo óptico. Os resultados experimentais do espalhamento inelástico de ANTPOT.16 O e ANTPOT.18 O pelo mesmo núcleo, na região de interferência nuclear-coulombiana, foram analisados com a aproximação de Born com ondas distorcidas (DWBA) e considerando o acoplamento de canais, com fator de forma do modelo coletivo. Foram determinados os parâmetros de deformação nuclear do primeiro estado excitado 2 POT.+ do ANTPOT.64 Zn e do ANTPOT.18 O. / he nuclear structure of the first excited state of 64Zn (J=2+, Ex=0.992MeV) was studied by measuring the reorientation effect in this nucleus, the angular distributions and excitation functions of 16O and 18O scattering by 64Zn, in the Coulomb-nuclear interference region. The interaction processes between the 64Zn nucleus and the 16O and 18O ions in the inelastic scattering, with and without projectile excitation, were also investigated. The reorientation effect in Coulomb excitation, observed through backscattering of 4He, 16O and 18O ions, allowed a precise determination of the reduced transition probability B(E2; O+ 2+) and the static quadrupole moment Q2+ of the first excited state of 64Zn. Analyses of the angular distributions and excitation functions, obtained for the elastic scattering of 16O and18O by 64Zn, were performed in terms of the optical model. The experimental results fot the inelastic scattering of 16O and 18O by the same nucleus, in the Coulomb-nuclear interference region, were analysed by means of both distorted wave Born approximation (DWBA) and channel coupling with a collective form factor. Nuclear deformation parameters were thus determined for the 2+1 state of 64Zn and of 180.