Memoria (licenciado en ciencias jurídicas y sociales) / No autorizada por el autor para ser publicada a texto completo / El objetivo de este trabajo es hacer un análisis para distinguir y determinar en qué consisten los principios de libertad de prestación de servicios, libre competencia, neutralidad tecnológica, compatibilidad internacional y equivalencia del soporte electrónico al soporte de papel, e identificar las instituciones y actividades en que ellos se manifiestan. Al efecto, el estudio se ordena del mismo modo que la Ley N° 19.799 enuncia los principios, y en él se determinan las propiedades, elementos, las características, funciones y los efectos jurídicos que, en virtud de ellos, producen las instituciones y actividades que incorpora el texto de la Ley. Se ha optado por tratar en forma conjunta los principios de libertad de prestación de servicios y de libre competencia en el primer Capítulo. Por otra parte, el análisis del principio de equivalencia de soportes se ha separado en dos Capítulos. Uno destinado a tratar la aplicación de este principio a los documentos electrónicos y otro destinado a tratar la firma electrónica. Cabe señalar que, para el desarrollo de este trabajo, se hizo necesario el estudio de algunas materias que exceden al ámbito de la Ley, como es el caso de la libertad en la prestación de servicios, la libre competencia, el estudio de los instrumentos públicos y privados y el de la firma manuscrita. Ello permitirá un mejor entendimiento de los incisos segundo y tercero del artículo 1 de la Ley

Nitrogen heterocycles are present in nearly 60% of all small-molecule drugs approved by the US Food and Drug Administration. New innovative methods that streamline the synthesis of such heterocycles are therefore highly desirable. The use of new or underdeveloped reactive intermediates provides an excellent opportunity to develop novel heterocyclic syntheses. For example, nitrogen-substituted isocyanates (N-isocyanates) are a class of rare amphoteric isocyanates with high, but severely underdeveloped synthetic potential. The research efforts presented in this thesis have been directed towards the use of such intermediates for the rapid construction of heterocycles using cascade reactions. Using an in situ generation approach from masked (blocked) isocyanate precursors, we were able to control the homo dimerization of these species and design several cascade reactions forming more than 10 different classes of heterocycles using appropriate nitrogen nucleophiles. Given the importance of the N-N-C=O motif in pharmaceuticals and agrochemicals, N-isocyanates provide the opportunity to synthesize highly desirable cores for different industrial applications. To illustrate the potential of this new tool in heterocyclic chemistry, more than 200 heterocycles were synthesized using this methodology. In Chapter 2, heterocycles incorporating only one atom from the N-isocyanate will be presented. More precisely, the first cascade reaction involving N-isocyanates for the rapid synthesis of saturated heterocycles will be presented. The incorporation of 2 atoms within the ring will then be discussed in Chapter 3 with the synthesis of hydantoins, imidazolones, thiazolines, pyrazoles and phthalazinones. Chapter 4 will focus on the incorporation of every atom in the heterocycle to form other bioactive cores such as azauracils, pyridazinones and azadiketopiperazines. Lastly, Chapter 5 will describe our efforts for the synthesis of acyclic molecules such as semicarbazides and aza-peptides.

Beaucoup de données infrmatiques sont structurées de manière arborescente. Dans le contexte du Web, c'est le cas en particulier des données au format XML. De par sa généricité, ce format est rapidement devenu un standard pour l'échange et la sauvegarde d'informations. A l'instar des langages de requêtes pour les bases de données relationnelles, le besoin d'avoir des langages de requêtes pour les documents XML est devenu crucial. On distingue les requêtes unaires (sélection d'un ensemble de sous-parties d'un document) des requêtes n-aires (sélection d'un ensemble de n-uplets de sous-parties d'un document). Beaucoup de formalismes logiques pour les requêtes unaires ont été étudiés, en revanche, peu d'approches logiques existent pour les requêtes n-aires. Cette thèse étudie de manière fondamentale les requêtes n-aires, en proposant et en étudiant principalement deux formalismes logiques pour requêtes n-aires: une extension du paradigme navigationnel du standard W3C XPath au cas n-aire, appelée langage de composition, et une adaptation de la logique spatiale d'arbres TQL, introduite par Cardelli et Ghelli. Les questions de pouvoir d'expressivité, de complexité d'évaluation des requêtes ainsi que leur satisfiabilité sont abordées. L'étude du problème de satisfiabilité pour la logique TQL a nécessité l'introduction de nouveaux automates d'arbres avec tests globaux, dont l'étude est réalisée de manière indépendante. / Ln computer science many data are shaped as trees. ln the context of the Web, it is the case for XML formatted data in particular. XML is a markup language that has rapidly become a standard for information storage and data exchange. As query languages for relational databases are not well-suited to XML data, the need to have query languages specific to XML documents has increased. We distinguish unary queries which select a set of subparts of a document from n-ary queries which select a set of n-tuples of subparts of a document. Many logical formalisms for unary queries have been proposed, but less work has been done on logical formalisms for n-ary queries. This thesis is a fundamental study of n-ary queries that proposes two logical formalisms for n-ary queries: an extension of the navigational paradigm of the W3C standard XPath to n-ary queries, called the composition language, and an adapation of the spatiallogie TQL introduced by Cardelli and Ghelli. The question of expressive power, the complexity of the query evaluation problem as well as the satisfiability problem are considered. ln particular, the satisfiability problem for a TQL fragment is proved to be decidable by reduction to the emptiness test of a new class of tree automata with global constraints that is studied independently.

The development of cost-effective and sustainable catalytic methods for the production of enantiomerically pure chiral amines is a key challenge facing the pharmaceutical and fine chemical industries. There is an increasing demand for broadly applicable synthetic methods which deliver the desired amine product in high yield and enantiomeric excess (e.e.). Previously we have described the development of variants of monoamine oxidase from Aspergillus niger (MAO-N) which are able to mediate the complete conversion of racemic amines to the corresponding enantiomerically pure products in a single step. In this thesis we report a panel of MAO-N variants (D5, D9 and D11) developed in our laboratory, which are able to mediate the deracemisation of primary, secondary and tertiary amines with broad structural features. In particular, we have synthesized and subjected to deracemisation a broad range of tetrahydroisoquinolines and tetrahydro-β-carbolines checking enantioselectivity and enantiopreference of our biocatalysts. A relation between lipophilicity of the substituents and enantiopreference of the enzyme has been identified. We have also engineered a new MAO-N variant (D11) with a greatly increased substrate scope and enhanced tolerance for bulky substrates. Application of this engineered biocatalyst is highlighted by the asymmetric synthesis of the generic drugs Solifenacin and Levocetirizine as well as a number of important classes of biologically active alkaloid natural products. We also report a novel MAO-N mediated asymmetric oxidative Pictet-Spengler approach to the synthesis of (R)-harmicine.Another challenge facing the chemist in the new millennium is the development of cleaner and more efficient chemical processes. To this aim the combination of two or more catalytic systems to complete a series of cascade reactions is considered particularly appealing. We have reported a concurrent redox cascade for the deracemisation of pyrrolidines and tetrahydroisoquinolines using our monoamine oxidase-N with a biotinylated Ir-complex within streptavidin (SAV). To achieve the final goal it is necessary to shield the metal inside a host to avoid the mutual inactivation of the two catalysts. We have also described the combination of MAO-N with berberine bridge enzyme (BBE) for the synthesis of berbines (tetrahydroprotoberberines), which represent a sub-class of tetrahydro-isoquinoline alkaloids found in various plants. This bi-enzymatic cascade allows the synthesis of these structures achieving a theoretical 100% yield instead of the 50% given by the kinetic resolution using BBE itself.

In many series of compounds, intensity of biological activity and chemical reactivity are proportional. Generally whenever a alkyl group replaces a reactive hydrogen atom, as would be the case for an N-substituted hydroxylamine as compared to hydroxylamine, the over-all biological activity of the resulting compound is lower than that of its nonalkylated analogue. Since toxicity and physiological activity are not proportional, this comparison can only suggest possible types of derivatives to prepare and test.

The cultural and popular media landscape of the United States of America changed after the Civil-Rights movement of the 1960s. The word “Nigger” was changed during that same period of American history. There are several authors and a comic that helped change this word during the 1960s. The post Civil-Rights American has a different experience and understanding with this word than those born before 1970. This work triangulates the current cultural location of the word “Nigger,” “nigga,” and “the n-word” using linguistics, law, and two media case studies. The “Nigger” trinity is a model that adds value to the discourse that surrounds this one word in post civil-rights/post 1960s America.

Soybean [Glycine max (L.) Merr.] biomass and yield has increased over the past several decades in the midsouthern United States; therefore, a better understanding of the nutrient requirements of the crop is needed. Nutrient uptake and partitioning in soybean is fundamental to understanding the physiology of nutrient accumulation relative to crop yield. Technological advances and improved management strategies in soybean production have contributed to significant yield increases. Research was established in 2017 and 2018 in Stoneville, MS, to evaluate soybean nutrient uptake and partitioning across multiple soybean cultivars and two planting dates. Coarse- and fine-textured soils commonly cropped in Mississippi under furrow irrigation were utilized. Soybean total aboveground biomass was collected at multiple growth stages, including V4, R2, R5.5, R6.5, and R8. At reproductive stages R5.5 to R8, soybean aboveground biomass was partitioned into senesced leaves, pods, and seeds. All biomass components were analyzed for content of primary macronutrients. Two soybean cultivars for each of four herbicide-resistant technologies were selected to represent subplot treatments. The greatest yield was produced by dicamba- and glyphosate-tolerant HT, followed by glufosinate tolerant, followed by conventional HT. Soybean planted in April produced grain yield greater than May planted soybean. Averaged across four site years, field removal of total N, P2O5, and K2O partitioned into the seed at physiological maturity was approximately 175 kg N ha-1, 33 kg P2O5 ha-1, and 120 kg K2O ha-1.

No description available.

Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

Glycosylation O-linked β-N-acetylglucosamine (O-GlcNAc) is post-translational modification of proteins, regulated by β-N-acetylglucosaminyltransferase (OGT) and β-N-acetylglucosaminidase (OGA). This intracellular glycosylation differs from the other glycosylation types - it is dynamically regulated, similarly to phosphorylation, β-N-acetylglucosamine serves as a nutrient and stress sensor in cell. Chronically dysregulated O-linked glycosylation by GlcNAc is associated with pathology of various diseases, such as diabetes mellitus type II, oncological and neurodegenerative diseases. Expression of enzymes OGT and OGA is very sensitive for homeostasis of GlcNAc, which is the product of hexosamine biosynthetic pathway. Changes in expressions of these ezymes could be used as a potencial blood marker, e.g. in early stage of diabetes. The aim of this master thesis was to study changes in expression of genes encoding ezymes OGT and OGA in cohort of obese patients in comparison with healthy controls and also to compare the state before and after change of lifestyle (loosing weight). Analysed cohort comprised of 34 samples of isolated lymphocytes from peripheral blood from obese adolescent patients and 80 samples of adults patients. RNA was isolated by TriReagent, quantification of the expression of mRNA was...