Em nossa dissertação, estudamos o manual retórico de Sulpício Vítor, Institutiones Oratoriae. Nossa pesquisa é dividida em quatro partes. Na primeira, comentamos a bibliografia especializada que nos antecede, abordando questões importantes, como datação, ocorrência de alguns elementos retóricos e semelhança com outros manuais. Na segunda, comparamos os exemplos fornecidos por nosso autor com exercícios declamatórios, sobretudo os de Sêneca pai, mas também os de Calpúrnio Flaco e de Pseudo-Quintiliano. Na terceira, analisamos e explicamos a teoria dos estados de causa de Sulpício Vítor, comparando, sempre que possível, suas lições com as de outros textos. Na última, apresentamos uma tradução anotada para o português. / In our dissertation, we study Sulpitius Victors rhetoric handbook, Institutiones Oratoriae. Our research is divided into four parts. The first consists of a commentary to the specialized bibliography that precedes us, addressing important issues, such as dating, occurrence of some rhetorical elements and similarities with other handbooks. The second aims to compare examples given by our author with declamation exercises, especially those ones of Seneca the Elder, but also the ones of Calpurnius Flaccus and of Ps. Quintilian. The third is dedicated to the analysis and elucidation of Sulpitius Victors issue-theory, as we compare, whenever possible, his lessons with the ones of other texts. The last includes an annotated Portuguese translation.

Le potentiel rédox et la conductivitée du fluide d'un panache de contamination sont deux paramètres clefs pour la surveillance des sites contaminées. L'objectif de ce travail de thèse est de montrer que les méthodes de résistivité et de potentiel spontané apportent des informations spatialisées sur ces deux paramètres. Ces méthodes permettent ainsi de minimiser et d'optimiser l'implantation de piézomètres de contrôle. L'application de la méthode de résistivité électrique sur le site d'Entressen en Provence (C.E.T. de Classe 2) a permis d'obtenir une carte de la conductivité du fluide de l'aquifère, définissant ainsi l'extension du panache de contamination. Les signaux de potentiel spontané mesurés sur les sites contaminés sont associés à l'écoulement de l'eau dans le sous-sol (phénomène d'électrofiltration) et à la présence de contaminants organiques (phénomène que nous appelons "électro-rédox"). Les études antérieures avaient mis en évidence l'existence d'anomalies de potentiel spontané aux abords de sites contaminés, sans pour autant parvenir à expliquer physiquement ce phénomène. Nous avons donc développé un modèle de (bio)-géobatterie naturelle, dans lequel les bactéries jouent le rôle de transfert d'électrons entre la zone réduite du panache et la zone oxydée. Le courant électrique qui en résulte est à l'origine des anomalies de potentiel électrique mesurées à la surface du sol. Pour valider ce modèle, nous avons réalisé des expériences de terrain (Entressen en Provence et Trecate en Italie) ainsi que des expériences en cuve en présence de bactéries sulfato-réductrices. Les résultats de terrain et de laboratoire sont en accord avec le modèle, montrant un couplage linéaire entre potentiel spontané et potentiel rédox.

Pantothenate synthetase (PS), which catalyzes the last step in the pantothenate (vitamin B5) biosynthesis, is a dimeric enzyme present in bacteria, fungi and plants. The enzymatic properties of PS from Escherichia Coli, Mycobacterium tuberculosi, Fusarium Oxysporum, Lotus japonicus, Oryza sativum, Brassica napus and Arabidopsis thaliana have been characterized. The chemical reaction and the proposed mechanism of reaction are identical for PS, irrespective of the source. However, from an enzyme mechanistic point of view, plant PS’s are dissimilar to their bacterial counterparts, in that they exhibit “allosteric behavior”, a property that has not been observed in the bacterial enzyme. The behavior is quite remarkable when one takes into consideration the fact that plant PS’s share a high degree of sequence identity (~ 40%) with the bacterial enzymes. Even more intriguing is the structural mechanism proposed to explain the observed differences in structure between the PS’s from E.Coli and M.tb, which share a 42% sequence identity. Till date there is no structural information available on the plant PS’s and of the substrate bound conformation of E.coli PS. This thesis aims to provide an understanding on some aspects of the structure – function relationship of this physiologically important enzyme. Specifically, the solution properties of E. coli PS have been examined using high-resolution multinuclear, multidimensional NMR methods. Given the large size of the full-length protein (~ 63 KDa), the structurally distinct N and C-terminal domains were cloned and expressed as individual proteins and their properties investigated. Towards this end, the tertiary fold of the 40 kDa dimeric amino-terminal domain of E. coli pantothenate synthetase has been determined using multidimensional multinuclear nuclear magnetic resonance (NMR) methods (PDB entry 2k6c). Sequence specific resonance assignments for backbone HN, 15N, 13Cα, 13C', sidechain 13Cβ and aliphatic 13CH3 (of isoleucine, leucine and valine residues) were obtained using perdeuterated ILV-methyl protonated samples (BMRB entry 6940). Secondary structure of nPS was determined from 13C secondary chemical shifts and from short and medium range NOEs. Global fold of the 40 kDa homo-dimeric nPS has been determined using a total of 1012 NOEs, 696 dihedral angles, 260 RDCs, 155 hydrogen bonds, radius of gyration potential, non-crystallographic symmetry potential and database derived potential based upon the Ramachandran map. The calculated structures, which show that the N-terminal domain forms a homo-dimer in solution, is of high stereochemical quality as judged by the Ramachandran statistics (70% of the residues have backbone dihedral angles in the allowed region, 25.5% in the additionally allowed region, 4.0% in generously allowed region, and only 0.5% in disallowed region). Dynamics of nPS, which has rotational correlation time τc of 17.3 ns, was investigated by 15N relaxometry measurements. Results of these studies indicate that the E. coli protein exhibits dynamic nature at the dimer interface. These structural and dynamic features of the protein were found to be of interest when correlated with NMR based substrate binding studies. Interaction of homo-dimeric amino-terminal domain (nPS) of E. coli pantothenate synthetase (PS; encoded by the gene panC; E.C. 6.3.2.1) with the substrates pantoate, β-alanine, ATP and the product pantothenate has been studied using isotopically edited solution NMR methods. Addition of pantoate prior to ATP has led to the interesting observation that pantoate binds each monomer of nPS at two sites. ATP displaces a molecule of pantoate from the ATP binding site. β-alanine and pantothenate do not bind the protein under the condition studied. Binding of pantoate and ATP also manifests as changes in residual dipolar couplings (RDCs) of backbone 1H-15N pairs in nPS when compared to the free form of the protein. Structures of homo-dimeric nPS bound to two molecules of pantoate (PDB entry 2k6e) as well as to pantoate + ATP (PDB entry 2k6f) were calculated by inclusion of hydrogen bonds between the ligands and backbone 1H-15N pairs of nPS in addition to other NMR derived restraints. The ligand bound structures have been compared to the similar forms of the M. tb PS. Structure of each monomer of nPS bound to pantoate and ATP shows the substrates in a favorable orientation for the intermediate pantoyl adenylate to form. Moreover, at all stages of substrate binding the symmetry of the dimer was preserved. A single set of resonances was observed for all protein-ligand complexes implying symmetric binding with full-occupancy of the ligands bound to the protein. In an effort to understand the structural basis of the observed enzymatic properties of plant PS’s, a structural model of the Arabidopsis PS was constructed. The results of these structural and substrate binding studies strongly suggest that 1 Substrate binding to PS occurs only at the active site. 2 There are no additional substrate binding sites which could potentially participate as regulatory sites. 3 Pantoate does not bind at the dimer interface to induce the observed homotropic effects. 4 The structural results presented on the substrate bound forms of nPS have direct implication for the development of novel antibacterial and herbicidal agents. Recently a great deal of interest has been evinced on the effects of molecular crowding on protein folding / unfolding pathways. Nuclear magnetic resonance is the only method by which high resolution structural information can be obtained on partially denatured states of a protein under equilibrium condition. Recent methodological advances have enabled the determination of high resolution structures using information embedded in the residual dipolar couplings. Molecular crowding using confinement may thus reveal important details about chaperone mediated protein folding. We have attempted to develop a protocol to study the effects of molecular confinement by sequestering proteins in poly-acrylamide gels and then subjecting these protein molecules to denaturation and then characterize these states by nuclear magnetic resonance. The preliminary results of these studies are described here.

This dissertation presents a study of the molecular mechanism underlying the highly efficient solar energy conversion processes that occur in the Photosystem I (PS I) reaction centers in plants and bacteria. The primary electron donor P700 is at the heart of solar energy conversion process in PS I and the aim is to obtain a better understanding of the electronic and structural organization of P700 in the ground and excited states. Static Fourier Transform Infra-Red (FTIR) difference spectroscopy (DS) in combination with site directed mutagenesis and Density Functional Theory (DFT) based vibrational frequency simulations were used to investigate how protein interactions such as histidine ligation and hydrogen bonding modulate this organization. (P700+-P700) FTIR DS at 77K were obtained from a series of mutants from the cyanobacterium Synechocystis sp. 6803 (S. 6803) where the amino acid residues near the C=O groups of the two chlorophylls of P700 where specifically changed. (P700+-P700) FTIR DS was also obtained for a set of mutants from C. reinhardtii where the axial ligand to A0-, the primary electron acceptor in PS I was modified. The FTIR DS obtained from these mutants provides information on the axial ligands, the hydrogen bonding status as well as the polarity of the environment of specific functional groups that are part of the chlorophyll molecules that constitute P700. Assignment of the FTIR bands to vibrational modes in specific types of environment is very difficult. In order to assist the assignment of the difference bands in experimental spectra DFT based vibrational mode frequency calculations were undertaken for Chl-a and Chl-a+ model molecular systems under different set of conditions; in the gas phase, in solvents using the Polarizable Continuum Model (PCM), in the presence of explicit solvent molecules using QM/MM methods, and in the presence of axial ligands and hydrogen bonds. DFT methods were also used to calculate the charge, spin and redox properties of Chl-a/Chl-a’ dimer models that are representative of P700, the primary electron donor in PS I.

Mon travail a consisté essentiellement à proposer une traduction moderne et scientifique de l'herbier du Ps.-Apulée, un texte du IVe siècle qui contient des recettes médicales associées à diverses plantes médicinales. Cet ouvrage a connu un grand succès au Moyen Âge et il en existe de nombreux manuscrits. Néanmoins, il a longtemps été méprisé et considéré comme une simple compilation d'ouvrages grecs. L'édition commentée la plus récente est celle d'Ackermann en 1788 et il n'y a pas de traduction française qui tienne compte l'édition d'E. Howald et H. Sigerist en 1927 et des progrès accomplis depuis dans la connaissance de ce texte. Nous avons donc essayé de traduire le texte de l'Herbier édité par ces deux savants tout en expliquant, critiquant et parfois contestant certains de leurs choix. Nous avons aussi cherché dans l'introduction et dans les notes à situer l'oeuvre dans la tradition médicale en travaillant à la fois sur les sources de l'oeuvre et sur sa postérité et nous avons joint à la traduction en annexes un certain nombre de nos outils de travail. Nous espérons que ce travail permettra de mieux comprendre ce que représentaient les plantes médicinales, " les simples ", dans l'Antiquité tardive.

The self-assembly of polystyrene-stabilized cadmium sulfide nanoparticles (PS-CdS) with amphiphilic stabilizing chains of polystyrene-block-poly(acrylic acid) (PS-b-PAA) into colloidal quantum dot compound micelles (QDCMs) is studied on two-phase gas-liquid segmented microfluidic reactors. The resulting particle sizes are found to arise from the interplay of shear-induced coalescence and particle breakup, depending on a combination of chemical and flow conditions. Variation of water content, gas-to-liquid ratio, and total flow rate, enable control of QDCM sizes in the range of 140 – 40 nm. The flow-variable shear effect on similar microfluidic reactors is then applied to direct the solution self-assembly of a PS-b-PAA block copolymer into various micelle morphologies. The difference between off-chip and on-chip morphologies under identical chemical conditions is explained by a mechanism of shear-induced coalescence enabled by strong and localized on-chip shear fields, followed by intraparticle chain rearrangements to minimize local free energies. Time-dependent studies of these nanostructures reveal that on-chip kinetic structures will relax to global equilibrium given sufficient time off-chip. Further investigations into the effect of chemical variables on on-chip shear-induced morphologies reveal a combination of thermodynamic and kinetic effects, opening avenues for morphology control via combined chemical (bottom-up) and shear (top-down) forces. An equilibrium phase diagram of off-chip micelle morphologies is constructed and used in conjunction with kinetic considerations to rationalize on-chip mechanisms and morphologies, including cylinders and vesicles, under different chemical conditions. Finally, we extend our strategy of two-phase microfluidic self-assembly of PS-b-PAA to the loading of fluorescent hydrophobic probes (pyrene and naphthalene) with different affinities for the PS core. The on-chip loading approach provides a fast alternate to the slow off-chip method, with implications for the potential development for point-of-care devices for drug loading. On-chip loading results indicate that loading efficiencies are dependent on water content and, to a lesser extent, on flow rate; the results also suggest that the on-chip morphologies of the PS-b-PAA micelles are an important factor in the loading efficiencies. / Graduate

The draft for a Common Consolidated Corporate Tax Base Directive in the European Union includes the suggestion for an apportionment formula which allocates taxable group profits to group member corporations. These allocated profits shall then be taxed in the respective Member States. The draft directive delegates the right to define one factor of the apportionment formula, the term "Employee" to the Member States, who are therefore free to choose a narrow or a broad definition, the latter including also atypical employment schemes. Using a game-theoretic approach the paper shows that the individually rational strategy of any Member State to define "Employee" broadly so as to maximize the volume of the apportionment factor and thus maximize the allocated share of taxable income is only the best solution when tax rate differences and differences in the volume of atypical employment schemes are disregarded. If such differentials and the corporate groups' reactions to different Member States' definitions are included in modelling the game's pay-offs a narrow definition of "Employee" yields the highest individual pay-offs to the Member States involved. This change of dominant strategies is triggered by the corporate group's shifting of the employment factor from high-tax to low-tax Member States. Our paper differs from previous research on the economic effects of the CCCTB apportionment formula as it is the first paper identifying and analysing the employment factor and its distorting effects. The paper discusses possible tax minimizing strategies for corporate groups by shifting workforce and develops a model to quantify these potential relocations. Furthermore the paper presents advice to policy makers in their "Employee" definition decision and shows how Member States could use this definition to both minimize outward factor shifting and maximize inward factor shifting.(authors' abstract) / Series: WU International Taxation Research Paper Series

Made available in DSpace on 2016-08-03T12:19:56Z (GMT). No. of bitstreams: 1 Silas Cardoso2.pdf: 1303036 bytes, checksum: 6bfbab99f1aee463f9c257e694559274 (MD5) Previous issue date: 2015-05-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The research aims the Torah as an aniconic cultic object in the postexilic, revealing its ritualistic face in the Ancient Israel worship. It is proposed that the centralization of Torah in the Second Temple Period will be an ideological and macrostructural construction i.e., an invented tradition of the post-exilic priesthood that aims to unify the nation that rebuild itself. For that analysis, three cuts related to the question are persecuted: (1) the cult materiality in its continuities and ruptures with the pre-exilic Israelite religion, from the material culture and biblical analysis of four central cultic objects presented in the Deuteronomistic History, bamah, massebah, Asherah and Ark; (2) the redactional practices that defend the Torah centralization that inspires in the other cults of Ancient Israel, especially observed in the exegetical analysis of Ps 19, one of the major Torah Psalms of the Hebrew salter; (3) the canonical texts editing that was legitimator retroprojected visions of the posterior and centralized vision of Torah, from the creation of a text materiality typology, from the exegetical analysis of the texts. With that environment we propose a model of four instances of construction of post-exilic aniconism, centralized on Torah and reaching the different layers from judahite religion. / A pesquisa trabalha a Torá como objeto de culto anicônico no pósexílio, apresentando sua face ritualística no culto do Israel Antigo. É proposto que a centralização da Torá no período do Segundo Templo seria uma construção ideológica macroestrutural i.e., uma tradição inventada do grupo sacerdotal pós-exílico em vista de unificar a nação que se reconstruía e reconfigurava. Para tal análise, observam- se três recortes distintos ligados à questão: (1) a materialidade do culto em suas continuidades e rupturas com a religião israelita pré-exílica, a partir da análise da cultura material e da análise da literatura bíblica de quatro objetos cúlticos centrais da OHD, bamah, massebah, Asherá e arca; (2) as práticas redacionais que advogavam a centralização da Torá com inspiração nos demais cultos e concepções do divino no Antigo Israel, especialmente observada na análise exegética do Sl 19, como um dos principais Salmos da Torá que teriam sido produzidos no período para promulgar a nova prática; e (3) a editoração dos diversos textos canônicos que teriam sido retroprojeções legitimadores da visão posterior centralizadora da Torá, através da criação de uma tipologia da materialidade dos textos e da Torá advinda da análise exegética de diversos textos. Com tal panorama, sob pesquisa exegética de orientação histórico-crítica, é proposto um modelo de quatro instâncias de construção do aniconismo pós-exílico, centralizado na Torá e atingindo as diferentes camadas da religião judaíta.

Different sampling devices for paper spray - mass spectrometry (PS - MS) were investigated to improve the assay’s simplicity and sensitivity over traditional approaches. In the first one, pressure-sensitive adhesive paper was used as both sampling tool to collect drug residues on surfaces and paper substrate in PS - MS analysis. This method showed a significant improvement in drug collection on surfaces leading to low nano-gram level detection limits. Other sampling device being investigated was snap-in solid-phase extraction column, which demonstrated the ability to detect trace amounts of drugs in plasma while allowed easy transportation and the use of PS - MS automated system.

This diploma thesis deals with the position of diagnostics of reinforced concrete structures in the building industry. The theoretical part deals with the research of methods for practical part of this thesis and basic imagine of procedure. The practical part deals with the survey of an existing building, quality of concrete and reinforcement of elements. The last part is the static calculation of the selected element for the intended use of the building. At the end, the results of the construction and technical survey are evaluated.