No description available.

No description available.

Mammalian thioredoxin reductase (TR) contains the rare amino acid selenocysteine (Sec), which is essential for the enzyme’s catalytic activity. Substitution of the catalytic Sec residue for a cysteine (Cys) residue, results in a drop in kcat of 100- fold. Homologous high molecular weight TRs from other eukaryotes such as D. melanogaster and C. elegans, have naturally evolved a Sec to Cys substitution in their active sites and these enzymes function with high catalytic activity without the need for a Sec residue. Thus, various TRs can catalyze an identical reaction with either a Cys or Sec residue. A natural assumption in the field has always been that the lower nucleophilicity of a Cys thiol, relative to the selenol of Sec, is the reason for the much lower activity of the mammalian Cys-containing mutant. However, here I provide an alternative explanation. High Mr TRs contain either a Cys-Cys or Cys-Sec dyad that forms an eight-membered ring in the oxidized state during the redox cycle of the enzyme. These eight-membered ring structures are rare in protein structures, presumably due to the strain induced in the intervening peptide bond between the Cys residues. Here I take a “chemical approach” to studying the enzyme mechanism of TR by breaking it into two pieces. This approach is possible because of TR’s structural and mechanistic similarity to glutathione reductase (GR). In comparison to GR, TR contains an additional thiol-disulfide exchange step resulting from the presence of a sixteen amino acid C-terminal extension containing either a vicinal disulfide bond or vicinal selenylsulfide bond. This additional thiol-disulfide exchange step is in the form of the reduction and opening of the eight-membered ring motif. I have constructed a truncated version of the enzyme lacking the amino acid sequence possessing the ring motif so that I could isolate this ring-opening step from the rest of the catalytic cycle by using peptide disulfides/selenylsulfides as substrates. The results of this study using peptide substrates show that the ring opening step is the step of the catalytic cycle that is most effected by Sec to Cys substitution because the higher pKa of the Cys thiolate in comparison to the Sec selenolate means that the Cys residue must be protonated in this step.

Made available in DSpace on 2014-06-12T17:38:11Z (GMT). No. of bitstreams: 2 arquivo2438_1.pdf: 4322682 bytes, checksum: c12fd82b22dbedcb244655d5d415eb32 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2009 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / O processo de fragmentação observado em metrópoles brasileiras fragiliza os bairros periféricos pois limita o acesso da população residente nestas regiões às oportunidades urbanas ainda concentradas no Centro tradicional. Tal limitação está ligada à altos custos de transporte e ainda, em alguns casos à necessidade de vencer barreiras naturais para acesso à área central como nos casos de São Paulo, Belo Horizonte e Natal. Esta realidade cultiva no cidadão ―isolado‖ o desejo de constituição de uma rede que o coloque em contato maior e mais denso com o ―vizinho‖ na luta por um destino comum (Carlos, 2001). Com o aumento da oferta de infraestrutra de serviços públicos como saúde, educação e abastecimento para atendimento às populações periféricas em conjunto com o desenvolvimento de subcentros nestas áreas, o bairro adquire um certo grau de autosuficiência em relação ao Centro tradicional, configurando-se como ‖autarquias‖ urbanas. Aumenta-se, desta forma, o percentual de deslocamentos intrabairros. À pauta de mobilidade radial a que estavam restringidas as populações periféricas é acrescido um percentual significativo de deslocamentos vicinais de modo a viabilizar a implantação de subredes vicinais de atendimento a atual mobilidade. A pesquisa domiciliar de origem-destino realizada em 2007 em Natal, revela que o percentual de viagens internas à esta zona realizadas por transporte público coletivo chega a 32,48%. Este percentual é ainda maior quando considerados os modos individuais e não-motorizadas, chegando a 72,46% do total de viagens originadas na zona. Este trabalho discorre sobre o fortalecimento da pauta de mobilidade vicinal nas cidades brasileiras e pretende verificar a viabilidade da implantação de um sistema de transporte público composto por subrede vicinal na zona norte de Natal

No description available.

Two applications of second harmonic generation (SHG), a nonlinear optical technique, are studied. First, Fresnel factors are used with a bond model to describe SHG from vicinal silicon at five incidence angles: 7.5°, 22°, 30°, 45°, and 52°. Second, a prototype apparatus for applying SHG to enhance imaging capabilities of optical coherence tomography, a microscopy technique used in many biological fields, is briefly described. / text

Les systèmes nanostructurés composés de nanoparticules déposées à la surface d’oxyde présentent à la fois un intérêt fondamental et technologique. Les propriétés finales de tels systèmes dépendent principalement de la forme et de la taille des nanoparticules déposées ainsi que de leur organisation sur la surface. Dans ce contexte général, l’utilisation de surfaces vicinales apparaît comme un moyen intéressant pour réaliser des substrats gabarits sur lesquels des particules pourront être déposées. Ce travail est consacré à l’étude de la nanostructuration bidimensionnelle (2D) de surfaces vicinales de saphir obtenue dans certaines conditions expérimentales (orientation de la surface vicinale et paramètres du traitement thermique). Les principaux objectifs de cette étude sont de décrire la morphologie de surface de ces échantillons présentant une mise en ordre 2D mais aussi de proposer un mécanisme concernant le passage de l’organisation monodimensionnelle (1D) à l’organisation 2D. La morphologie des surfaces vicinales d’alumine α, traitées à 1250 °C sous atmosphère d’oxygène pur pendant des durées allant jusqu’à 380 h, a été étudiée par des techniques expérimentales complémentaires : la microscopie à force atomique (AFM), la diffusion centrale des rayons X sous incidence rasante (GISAXS) et la diffraction de surface (GIXD). Les différents résultats ainsi obtenus nous ont permis de montrer que la surface présentant une organisation 2D pouvait être décrite par une assemblée de pyramides, dont la base est un triangle isocèle, décorant un réseau rectangulaire centré. Nous avons déterminé de façon très précise la forme de ce tétraèdre irrégulier qui a été décrit selon les caractéristiques cristallographiques du saphir. Il a de plus été montré qu’un phénomène de méandrage des bords de marches est probablement à l’origine de la transition entre les réseaux 1D et 2D qui n’est observée que lorsque les bords de marches initiaux sont rectilignes. / Nanostructured systems based on nanoparticles deposited onto oxide surfaces have both a fundamental and technological interests. Final properties of such systems depend mostly on the shape and size of the nanoparticles and also on their spatial organization on the surface. In this general context, the use of vicinal surfaces appears to be an interesting way of producing templates for ordering nanoparticles. This work is devoted to the study of two-dimension (2D) nanostructuration of sapphire vicinal surfaces obtained under specific experimental conditions (vicinal surface orientation and thermal treatment parameters). The main objectives of this study were to describe the surface morphology of the samples having the 2D ordering and also to propose a mechanism regarding the transition from the 1D to the 2D ordering.Morphology of sapphire vicinal surfaces, annealed at 1250 °C under pure oxygen atmosphere during various durations up to 380 h, was studied by complementary technics: atomic force microscopy (AFM), grazing-incidence small-angle X-rays scattering (GISAXS), and grazing-incidence X-rays diffraction (GIXD). Results allowed us to describe the 2D ordered surface by being an assembly of pyramids with an isosceles triangle base decorating a rectangular centered lattice. The shape of those irregular tetrahedrons has been precisely determined with the crystallographic characteristics of sapphire. It has also been shown that a meandering step-edge phenomenon is probably the starting point of the transition between 1D and 2D lattices obtained when initial step-edges are straight.

Marine ascidian metabolite perophoramidine has since its isolation in 2002 attracted the interest of several research groups. The complex polycyclic structure with vicinal quaternary carbon stereocenters and two amidine functionalities constitutes a formidable synthetic challenge. In this project a new synthetic approach to dehalogenated perophoramidine has been investigated. The vicinal quaternary carbon stereocenters were introduced via a samarium mediated reductive dialkylation, in which the stereochemistry was determined by the metal chelate that formed, as outlined below. Several of the steps suggested in the synthetic approach have been successfully evaluated. Future work is needed to assess the remaining steps of the suggested route to dehalogenated perophoramidine.

The body of information concerning carbon-carbon spin-spin coupling constants now includes a large number of coupling constants, the establishment of a dihedral angular dependence on 3JCC, and the application of 3JCC to conformational analysis. This study adds another dimension to the growing wealth of information associated with 13 C-NMR: the influence of some non-bonded interactions on 3JCC Four types of non-bonded interactions that could influence vicinal carbon-carbon NMR coupling constants were investigated. To facilitate the NMR studies, a variety of 13C-labeled compounds were synthesized.

<p>The heteroepitaxial growth of InAs self-assembled quantum wires on vicinal substrates is investigated. InGaAlAs lattice-matched to InP was first deposited onto an InP(001) substrate with and without a 0.9 degree off-cut toward the (110) direction, followed by the deposition of a strained layer of InAs. Dense InAs quantum wires were successfully grown on both nominally flat and vicinal substrates in order to observe the effect of the presence of atomic steps. The off-cut angle was chosen based on the wire spacing on a flat substrate to serve as a template for their nucleation and improve their size distribution for use as 1.55 um wavelength lasers required by the telecommunications industry. The results have shown a modest but statistically significant improvement in the width of their size distribution. In addition, a kinetic Monte Carlo simulation including full strain calculations was developed to further understand the nucleation process. The model developed here disproves the idea that InAs quantum wires are aligned towards the (-110) direction due to diffusion anisotropy. The simulation of the formation of quantum wires similar to those observed experimentally has been achieved and the Stranski-Krastanow growth mode is demonstrated.</p> / Master of Materials Science and Engineering (MMatSE)