No description available.

Made available in DSpace on 2017-07-21T20:42:35Z (GMT). No. of bitstreams: 1 rodrigoric.pdf: 9183178 bytes, checksum: 1d5fba078a589cbc1810eea245d1e019 (MD5) Previous issue date: 2006-10-31 / Mechanical alloying is a powder processing technique involving cold welding, fracturing mechanisms and rewelding of powder particles in a ball mill. The present work applied this technique with the purpose of processing titanium, niobium and tin alloys, through planetary ball mill and attritor mill. The atomic percentages of these elements were varied in six differents ways. The niobium hydrate was used on production of some alloys in study, with the purpose to observe the effects during the milling and on the alloys obtained after sintering. Differences between processing in planetary ball mill and attritor mill, as well the cold welding influences on the kinetic parameters of milling process were approached. The use of niobium hydrate result in a decrease of powders average crystallite size, and an increase of micro hardness of sintered alloys. This work obtained beta titanium alloys and alpha-beta titanium alloys in namometric sizes. The average crystallite size, for milled powders, was 7,6 nm. / Mecano-síntese é uma técnica de processamento em pó que envolve a soldagem a frio, mecanismos de fratura e a resoldagem das partículas de pós, em moinhos de bolas. O presente trabalho utilizou esta técnica com o propósito de processar ligas de titânio, nióbio e estanho, através de moinhos de bolas planetário e de atrito. As porcentagens atômicas destes elementos foram variadas de seis maneiras diferentes. O hidreto de nióbio foi utilizado na produção de algumas ligas em estudo, com o propósito de se observar os efeitos durante a moagem e na liga obtida após a sinterização. Diferenças entre o processamento em moinho de bolas planetário e o moinho de atrito, assim como as influências da soldagem a frio nos parâmetros cinéticos do processo de moagem, foram abordadas. O uso do hidreto de nióbio resultou na diminuição do tamanho médio de cristalito dos pós, e em um acréscimo na microdureza das ligas sinterizadas. Neste trabalho foram obtidas ligas de titânio beta e de titânio alfa-beta, em tamanhos nanométricos. O tamanho médio do cristalito, para os pós moídos, foi de 7,6 nm.

Approximately one third of the genes for the completely sequenced bacterial genomes have an unknown, uncertain, or incorrect functional annotation. Approximately 11,000 putative proteins identified from the fully-sequenced microbial genomes are members of the catalytically diverse Amidohydrolase Superfamily. Members of the Amidohydrolase Superfamily separate into 24 Clusters of Orthologous Groups (cogs). Cog3653 includes proteins annotated as N-acyl-D-amino acid deacetylases (DAAs), and proteins within cog2355 are homologues to the human renal dipeptidase. The substrate profiles of three DAAs (Bb3285, Gox1177 and Sco4986) and six microbial dipeptidase (Sco3058, Gox2272, Cc2746, LmoDP, Rsp0802 and Bh2271) were examined with N-acyl-L-, N-acyl-D-, L-Xaa-L-Xaa, L-Xaa-D-Xaa and D-Xaa-L-Xaa substrate libraries. The rates of hydrolysis of the library components were determined by separating the amino acids by HPLC and quantitating the products. Gox1177 and Sco4986 hydrolyzed several N-acyl-D-amino acids, especially those where the amino acid was a hydrophobic residue. Gox1177 hydrolyzed L-Xaa-D-Xaa and N-acetyl-D-amino acids with similar catalytic efficiencies (~10⁴ M⁻¹s⁻¹). The best substrates identified for Gox1177 and Sco4986 were N-acetyl-D-Trp and N-acetyl-D-Phe, respectively. Conversely, Bb3285 hydrolyzed N-acyl-D-Glu substrates (kcat/Km ⁹́⁸ 5 x 10⁶M⁻¹s⁻¹) and, to a lesser extent, L-Xaa-D-Glu dipeptides. The structure of a DAA from A. faecalis did not help explain the substrate specificity of Bb3285. N-methylphosphonate derivatives of D-amino acids were inhibitors of the DAAs examined. The structure of Bb3285 was solved in complex with the N-methylphosphonate derivative of D-Glu or acetate/formate. The specificity of Bb3285 was due to an arginine located on a loop which varied in conformation from the A. faecalis enzyme. In a similar manner, six microbial renal dipeptidase-like proteins were screened with 55 dipeptide libraries. These enzymes hydrolyzed many dipeptides but favored L-D dipeptides. Respectable substrates were identified for proteins Bh2271 (L-Leu-D-Ala, kcat/Km = 7.4 x 10⁴ M⁻¹s⁻¹), Sco3058 (L-Arg-D-Asp, kcat/Km = 7.6 x 10⁵ M⁻¹s⁻¹), Gox2272 (L-Asn-D-Glu, kcat/Km = 4.7 x 10⁵ M⁻¹s⁻¹), Cc2746 (L-Met-D-Leu, kcat/Km = 4.6 x 10⁵ M⁻¹s⁻¹), LmoDP (L-Leu-D-Ala, kcat/Km = 1.1 x 10⁵ M⁻¹s⁻¹), Rsp0802 (L-Met-D-Leu, kcat/Km = 1.1 x 10⁵ M⁻¹s⁻¹). Phosphinate mimics of dipeptides were inhibitors of the dipeptidases. The structures of Sco3058, LmoDP and Rsp0802 were solved in complex with the pseudodipeptide mimics of L-Ala-D-Asp, L-Leu-D-Ala and L-Ala-D-Ala, respectively. The structures were used to assist in the identification of the structural determinants of substrate specificity.

ΔPhe an analogue of a coded amino acid phenylalanine (Phe) residue but with double bond between Cα and Cβ atoms, is one of the well studied residue among all the dehydro amino acids, as a conformation constraining amino acid. Due to the presence of double bond Cα=Cβ, and consequent conjugation of ΔPhe ring electrons with Cα=Cβ double bond, ΔPhe gains conformation restricting (constraining) characteristics compared to coded amino acid Phe. ΔPhe which assumes an achiral residue has all its atoms restricted to an approximate plane. Apart from the conformation constraining property, the designer friendly ΔPhe residue has its ability to i) engage in side chain aromatic interactions ii) act as nuclei for C-HLO/N-HLπ weak interactions involving the side chain and/ or backbone atoms, and iii) acquire ambidextrous conformation as observed in many model peptides. It is these properties, which makes ΔPhe, a residue of intense research in the field of de novo protein secondary and super secondary design. Analysis of solid state and solution state structures of containing ΔPhe residues suggests that ΔPhe, in general induces β-bend in short peptides and 310-helical conformation in longer peptides (>4).

Thesis (Ph. D.)--University of Oklahoma. / Bibliography: leaves 182-199.

A bifunctional imidazolium linker was used for the production of highly crosslinked element organic frameworks by Suzuki-coupling with tetrafunctional boronic acids. The resulting porous materials are good heterogeneous organocatalysts in the N-heterocyclic carbene-catalyzed conjugated umpolung of α,β-unsaturated cinnamaldehyde. / Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG-geförderten) Allianz- bzw. Nationallizenz frei zugänglich.

Les cellules cancéreuses se multiplient de manière incontrôlée, se propagent dans le corps et constituent une menace significative à la santé publique, mettant en évidence la nécessité de traitements universels. Parmi les modalités thérapeutiques complémentaires, la radiothérapie est une des plus couramment utilisée pour éliminer ces cellules. L’introduction récente de la Radiothérapie par Émetteurs Alpha Diffusants (Alpha DaRT), une thérapie innovante contre le cancer, utilise des sources radioactives contenant des atomes de Ra-224 pour améliorer l'efficacité du traitement en exploitant les propriétés radiobiologiques des particules alpha. L'objectif de cette étude est de caractériser le spectre énergétique d’une source Alpha DaRT en distinguant les particules alpha et bêta, et d'évaluer les activités du Ra-224 et de ses descendants à l’aide d’un compteur à scintillation liquide moderne. Grâce à l'utilisation du compteur à scintillation liquide Hidex 600 SLe, équipé de trois PMT, et de la séparation alpha/bêta 2D/3D, il est possible de déterminer les activités absolues des radionucléides. La séparation alpha/bêta 2D/3D surmonte les limitations des études précédentes et offre une représentation visuelle unique des spectres, améliorant ainsi la caractérisation des sources Alpha DaRT. Le suivi sur plusieurs mois d’une source Alpha DaRT, avec la décroissance progressive de son activité, et la mesure par scintillation liquide de son facteur d’efficacité en excluant les traces de contamination au Th-228, supportent la faisabilité d’utiliser cette méthode de mesure sur une longue période. Pour ce faire, le compte des particules alpha et bêta a été séparés par le compteur et classifié en fonction de l’énergie émise des particules. Un programme maison en Python a été développé pour extraire les activités de chaque fille dans la chaîne de désintégration du Ra-224. Un résultat intéressant est qu’en raison de la décroissance rapide (demi-vie de 0,3 μs) du Po-212 (une descendante du Ra-224), une partie de l'activité alpha totale n’est pas mesurée par le compteur. Ce phénomène doit être pris en compte lors de l'évaluation des efficacités de la scintillation liquide pour les mesures quantitatives des sources Alpha DaRT. Les résultats ont ensuite été comparés à aux valeurs attendues de la littérature et des calculs numériques. / Cancer cells multiply uncontrollably, spread throughout the body, and pose a significant public health threat, requiring the need for universal treatments. Among the complementary therapeutic modalities, radiotherapy is one of the most commonly used to eliminate these cells. The recent introduction of Alpha DaRT (Diffusing Alpha-emitters Radiation Therapy), an innovative cancer therapy, involves the use of radioactive sources containing Ra-224 atoms to enhance treatment efficacy by exploiting the radiobiological properties of alpha particles. The aim of this study is to characterize an Alpha DaRT source by distinguishing alpha and beta particles, and to evaluate the activities of Ra-224 and its descendants using a modern liquid scintillation counter. With the use of the Hidex 600 SLe liquid scintillation counter, equipped with three PMTs, and the 2D/3D alpha/beta separation method, it is possible to determine the absolute activities of the radionuclides. The 2D/3D alpha/beta separation method overcomes the limitations of previous studies and provides a unique visual representation of spectra, thereby improving the characterization of Alpha DaRT sources. Monitoring an Alpha DaRT source over several months, with its progressively decaying activity, and measuring its efficiency excluding traces of Th-228 contamination, confirm the feasibility of using this method of measurement over a long period. Counts from alpha and beta particles were separated by the counter and binned according to their emitted energies. An in-house Python program was developed to extract the activities of each daughter in the Ra-224 decay chain. An interesting finding is due to the fast (0.3 μs half-life) decay of Po-212 (Ra-224 daughter), part of the alpha activity is missed by the counter. This phenomenon should be considered when assessing the efficiency of liquid scintillation for quantitative measurements of Alpha DaRT sources. These results were then compared to expected values from literature and numerical calculations.