"Mémoire présenté à la Faculté des études supérieures En vue de l'obtention du grade de LL.M. Dans le programme de maîtrise en droit" / Depuis que le commerce électronique est devenu un environnement commercial assez répandu, les réseaux de distribution (nouveaux et préexistants) composés de fournisseurs et de distributeurs essayent de développer une réelle activité commerciale sur la toile. Cet enjeu a bouleversé l'organisation de la revente des produits en se posant en concurrent et en complément des réseaux traditionnels de distribution. Notre travail porte sur l'analyse juridique de l'incidence d'Internet sur les relations entre distributeurs et fournisseurs, plus particulièrement sur le contrat cadre qui lie ces deux parties. Nous avons articulé notre travail autour de la comparaison des systèmes juridiques européen et nord-américain. Nous examinons la coexistence et la compatibilité entre ces réseaux de distribution et la vente virtuelle, pour ensuite, proposer certaines pistes pour le développement des réseaux existant via Internet. / Ever since ecommerce has become a widespread commerciai environment, the distribution networks (new and preexistent), composed of suppliers and distributors, have tried to develop a real commercial activity on the web. This objective upsets the organization of the resale of the products by becoming competitor and complement of the traditional networks of distribution. Our work deals with the legal analysis of the incidence of Internet on the relations between distributors and suppliers, more particularly on the contract which bind these two parties. We articulated our work around the comparison of the European and North-American legal systems. We examine the coexistence and compatibility between of these distribution networks and the virtual merchandising, with the goal of proposing certain avenues for the future development of the existing networks through the Internet.

Challenges encountered in pathogen identification and detection include the genetic heterogeneity of strains within species of some foodborne pathogens, isolation of injured cells, mixed strains or mixed species contamination of foods, and differentiation between viable and dead cells. The first objective of this research was to evaluate an isolation medium that was based on time-delayed release (5 to 6 h) of selective agents in tablet format to a modified Listeria recovery enrichment broth (mLRB) medium for enhanced and rapid recovery of injured Listeria. The second objective involved the use of Fourier transform infrared (FT-IR) spectroscopy and chemometric analysis for the differentiation of: Listeria monocytogenes epidemic clones (ECs); viable versus heat-killed populations; different mixed strains and mixed species of Listeria; and different injury treatments and repair in Listeria populations. Nitrite- or acid-injured Listeria at approximately 10 CFU/ml were recovered in mLRB medium, and cell populations enumerated at various times (12 to 48 h) of incubation at 37oC. Analysis of variance revealed that acid-injured Listeria populations in mLRBS6 (mLRB plus the selective agents at 6 h) were significantly higher (P < 0.05) than those in mLRBS0 (mLRB plus the selective agents at 0 h) at 24 h; however, the differences in populations on these two media were not significant for nitrite-injured Listeria. Cell populations of four strains of Listeria recovered in mLRBTD (mLRB plus the time-delayed release tablets of the selective agents) were significantly higher than when those strains were enriched in the U.S. Food and Drug Administration (FDA), International Organization for Standardization (ISO), and U.S. Department of Agriculture (USDA) broths at 24 h. Comparison between artificially contaminated milk and meat samples with a four-strain cocktail of Listeria resulted in cell populations that were significantly higher (P < 0.05) on mLRBTD for contaminated meat than on mLRBTD for contaminated milk at 24 h. FT-IR spectroscopy in the mid-infrared region (4000 to 600 cm-1) and chemometrics was successfully applied to discriminate L. monocytogenes strains belonging to the same EC (ECII or ECIV) (100% accurate spectral classification), intact and heat-killed populations of each EC strain (100% accurate spectral classification), and spectral wavenumbers 1650 to 1390 cm-1 were used to differentiate heat-killed from intact populations. FT-IR spectroscopy and chemometrics in the wavelength region 1800 to 900 cm-1 could successfully discriminate different mixed strains of L. monocytogenes (98.15% accurate spectral classification) and different mixed species of L. monocytogenes and L. innocua (92.06% accurate spectral classification) from individual strains; Wavelength range 1800 to 900 cm-1 was successfully used to discriminate between intact, acid-injured, and heat-injured Listeria, with repaired cells from acid and heat treatments clustering closer to intact cells (93.33% of spectra accurately classified). Delayed-addition of selective agents to broth medium improves recovery of injured Listeria by allowing repair time, could minimize contamination through manual addition of selective agents, and saves analyst time; FT-IR spectroscopy is a highly discriminatory and reproducible technique that can be used for the differentiation of strains and various physiological states of Listeria.

A novel cryptand was synthesized which contained a 3,5-disubstituted-4- oxahexacyclo[5.4.1.02,6.03,10.05,9.08,11] dodecane "cage" moiety. In alkali metal picrate extraction experiments the cryptand exhibited high avidity towards Rb+ and Cs+, when compared with the corresponding model compound. A computational study of a series of cage-functionalized cryptands and their alkali metal-complexes was performed. The X-ray crystal structure of a K+-complexed bis-cage-annulated 20-crown-6 was obtained. The associated picrate anion was found to be intimately involved in stabilization of the host-guest complex. The interaction energy between the host-guest complex and picrate anion has been calculated, and the energy thereby obtained has been corrected for basis set superposition error.

Additive manufacturing is revolutionizing the way of production and use of materials. The clear tendency for shifting from mass production to individual production of net-shape components has encouraged using selective laser melting (SLM) or electron beam melting (EBM). In this thesis, austenitic, duplex and martensitic stainless steel parts were fabricated by laser melting technique using fixed laser scanning parameters. The fabricated steel parts were characterised using XRD, SEM, TEM/STEM, SADP and EBSD techniques. Mechanical properties of the fabricated steel parts were also measured. The mechanism of the evolution of microstructure during laser melting as well as the mechanism of the effect of developed microstructure on the mechanical properties was investigated. It was found that the intense localized heating, non-uniform and asymmetric temperature gradients and subsequently fast cooling introduces unique high level structural hierarchies and microstructure heterogeneities in laser melted steel parts. A unique structural hierarchy from the millimetre scale melt pools down to the sub-micron/nano scale cellular sub-grains was observed. The cellular sub-grains were 0.5-1μm with Molybdenum enriched at the sub-grain boundaries in SLM 316L. The Mo enriched cell boundaries affected the chemical and microstructure stability of the post heat treated samples. Well dispersed and large concentration of dislocations around the cell boundaries and well distributed oxide nano inclusions, imposed large strengthening and hardening effect that led to relatively superior tensile strength (700 MPa), yield strength (456 MPa), and microhardness (325Hv) compared to those of HIP 316L steel. The in-situ formation of oxide nano inclusions provided a unique way for preparation of oxide dispersion-strengthened (ODS) steel in a single process. The formation of oxide nano inclusions in the very low oxygen partial pressure of laser chamber was thermodynamically explained. High concentration of nano size dislocation loops, formation of nitride phases along with nitrogen enriched islands and oxide nano inclusions lead to strong dislocation pinning effect which strengthened the laser melted duplex stainless steel with a total tensile strength of 1321 MPa, yield strength of 1214 MPa and microhardness of 450HV. The grade 420 stainless steel was laser melted in Ar and N2 atmosphere which also showed a two level hierarchy with nanometric martensite lathes embedded in parental austenite cellular grains. The Ar treated sample had relatively higher retained austenite, lower YS (680-790 MPa) and UTS (1120-1200 MPa) compared to those treated in N2 (YS= 770-1100 MPa, UTS=1520-1560 MPa). The mechanism of the effect of atmosphere on phase transformation was explained. / <p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Submitted.</p>

Activated carbons as emerging classes of porous materials have gained tremendous attention because of their versatile applications such as gas storage/separations sorbents, oxygen reduction reaction (ORR) catalysts and supercapacitor electrodes. This diversity originates from fascinating features such as low-cost, lightweight, thermal, chemical and physical stability as well as adjustable textural properties. More interestingly, sole heteroatom or combinations of various elements can be doped into their framework to modify the surface chemistry. Among all dopants, nitrogen as the most frequently used element, induces basicity and charge delocalization into the carbon network and enhances selective adsorption of CO2. Transformation of a task-specific and single source precursor to heteroatom-doped carbon through a one-step activation process is considered a novel and efficient strategy. With these considerations in mind, we developed multiple series of heteroatom doped porous carbons by using nitrogen containing carbon precursors. Benzimidazole-linked polymers (BILP-5), benzimidazole monomer (BI) and azo-linked polymers (ALP-6) were successfully transformed into heteroatom-doped carbons through chemical activation by potassium hydroxide. Alternative activation by zinc chloride and direct heating was also applied to ALP-6. The controlled activation/carbonization process afforded diverse textural properties, adjustable heteroatom doping levels and remarkable gas sorption properties. Nitrogen isotherms at 77 K revealed that micropores dominate the porous structure of carbons. The highest Brunauer-Emett-Teller (BET) surface area (4171 m2 g-1) and pore volume (2.3 cm3 g-1) were obtained for carbon synthesized by KOH activation of BI at 700 °C. In light of the synergistic effect of basic heteroatoms and fine micropores, all carbons exhibit remarkable gas capture and selectivity. Particularly, BI and BIPL-5 derived carbons feature unprecedented CO2 uptakes of 6.2 mmol g-1 (1 bar) and 2.1 mmol g-1 (0.15 bar) at 298 K, respectively. The ALP-6 derived carbons retained considerable amount of nitrogen dopants (up to 14.4 wt%) after heat treatment owing to the presence of more stable nitrogen-nitrogen bonds compared to nitrogen-carbon bonds in BILP-5 and BI precursors. Subsequently, the highest selectivity of 62 for CO2/N2 and 11 for CO2/CH4 were obtained at 298 K for a carbon prepared by KOH activation of ALP-6 at 500 °C.

Les relations de distribution sont soumises à différentes contraintes juridiques. Ces contraintes relèvent plus spécialement du droit des contrats et du droit de la concurrence. D'autres matières juridiques, tel le droit du travail ou encore le droit des sociétés, peuvent être concernées. La technique contractuelle permet de répondre et satisfaire à ces contraintes. L'expérience européenne, et en particulier française, a permis de révéler des formules contractuelles identifiables ; il s'agit du contrat de franchise, de concession, de distribution agréée ou sélective et également des contrats de regroupement entre distributeurs. Ces formes particulières d'accords de distribution s'agrègent à des formules plus générales, tel la vente, le mandat, la commission ainsi qu'à des techniques contractuelles tel le contrat-cadre. L'objet de la thèse est d'apprécier la transposition de ces formules de contrats et techniques contractuelles en droit tunisien. L'étude des règles régissant les contrats de la distribution et les rapports entre les différents intervenants, permettra de systématiser un droit de la distribution en Tunisie. / The distribution relationships are subject to various legal obligations and regulations. These obligations rise mainly from contract law and competition law. However, other legal subject matters, such as labor law or corporate law could be involved. The contractual technique allows to meet these obligations. The European experience and more particularly the French one, have allowed to reveal identifiable contractual methods, mostly related to franchising agreements, concession agreements, approved or selective distribution agreements, and consolidation agreements between distributors. These specific distribution agreements aggregates with more general methods such as the sale deeds, the mandates, the commissions in addition to contractual techniques as the master agreement. The subject matter of this thesis is to estimate the transposition of these contractual methods and techniques in Tunisian law. The study and analysis of the rules governing distribution agreements and relationship between the different intervening parties, shall allow to systematize and set standards for distribution law in Tunisia.

Les bactéries symbiotiques facultatives, transmises verticalement de mère à descendants, sont connues pour avoir des effets importants sur la reproduction de leurs hôtes (incompatibilité cytoplasmique et biais de sex-ratio), sur l’adaptation à des situations de stress (spécialisation, résistance aux pathogènes et aux fortes températures) ainsi que sur l’évolution de l’ADN mitochondrial par l’induction de balayages sélectifs. Bemisia tabaci est un complexe d’espèces divisé en nombreux biotypes, principalement différenciés sur la base de marqueurs moléculaires (essentiellement mitochondrial). Cet insecte héberge 7 symbiotes, 1 symbiote nutritionnel obligatoire et 6 symbiotes facultatifs. Nos résultats ont montré une extrême diversité ainsi qu’une prévalence exceptionnelle des bactéries symbiotiques chez B. tabaci. Leur dynamique rapide a entraîné de nombreux balayages sélectifs sur l’ADN mitochondrial influençant nettement son évolution. La très forte fréquence des infections multiples chez cet insecte peut certainement être expliquée par la co-localisation de l’ensemble des bactéries au sein des mêmes cellules, avec le symbiote nutritionnelle. Enfin, la coexistence de différents cytotypes en sympatrie offre l’opportunité d’étudier les interactions qui se mettent en place entre différentes communautés symbiotiques et comment ces systèmes vont évoluer / Facultative endosymbiotic bacteria that are vertically transmitted from mother to offsprings, have important effects on their host reproduction (cytoplasmic incompatibilities and sex-ratio biais), on host adaptation to situation of stress (specialization, resistance against pathogens or high temperature) and also on the evolution of mtDNA, by inducing selective sweeps. Bemisia tabaci is a species complex divided into numerous, mainly differentiated based on molecular markers (essentially mtDNA markers). This insect is infected by 7 bacterial symbionts, one nutritionnal symbiont that is obligatory and 6 facultative symbionts. Our results show an extreme diversity of symbionts in this insect and a very high prevalence in B. tabaci populations. Moreover their rapid dynamic has strongly influenced mtDNA evolution by inducing recurrent selective sweeps. The colocalization of the whole symbiotic community in the same cells, with the nutritional symbiont, might certainly explain the very high frequency of multiple infections in B. tabaci. Finally, coexistence of very different cytotypes in sympatry allows to study the interactions that take place between different symbiotic communities and how these systems will evolve

L’objectif de cette étude est de préparer des catalyseurs bimétalliques Ni-X/SiO2, de les caractériser, et de comparer leur activité en hydrogénation du styrène en éthylbenzène,ainsi que leur sélectivité en hydrogénation de la double liaison oléfinique du styrène, par rapport à l’hydrogénation du noyau benzénique. L’élément X est greffé de manière contrôlée sur le nickel, et est choisi selon son électronégativité, soit inférieure (Zr), soit égale (Sn), soit supérieure (Au) à celle du nickel, dans le but d’étudier les effets géométriques et/ou électroniques qu'il pourrait induire. Parmi les échantillons préparés, le catalyseur Ni-Au/SiO2s’est révélé presque aussi actif que le catalyseur non dopé et nettement plus sélectif dans l’hydrogénation du styrène en éthylbenzène. / The aim of the present study is to prepare silica-supported Ni-X bimetallic catalysts, tocharacterize them, and to compare their catalytic activity in the hydrogenation of styrene, as well as their selectivity in the hydrogenation of the styrene’s olefinic double bond instead of the hydrogenation of the aromatic ring. The element X is grafted in a controlled way on the supported nickel particles, and is chosen according to its electronegativity, which is eitherlower (Zr), or equivalent (Sn), or higher (Au) than the electronegativity of Ni, in order to study the geometrical and/or electronic effects due to the doping of Nickel. Among the prepared samples, the Ni-Au/SiO2 catalyst has exhibited high activity and high selectivity in the hydrogenation of styrene into ethylbenzene, which makes the doping of Ni by Au apromising alternative for PyGas selective hydrogenation catalysts.

A cana-de-açúcar (Saccharum ssp.) é uma cultura valiosa na produção de alimento, fibra e energia para o Brasil e, especialmente, para o estado de São Paulo. Com o advento da biotecnologia, alternativas de melhoramento genético têm despertado a atenção da comunidade científica, sendo etapas cruciais para tais avanços o sequenciamento e a caracterização do genoma das espécies cultivadas. Dada sua natureza poliploide, com frequente aneuploidia, a cana-de-açúcar apresenta dificuldades às práticas convencionais em genômica, de maneira que é vantajoso fazer uso de recursos de sequenciamento de nova geração e de espécies próximas para elucidar de forma mais efetiva o genoma da gramínea. Uma contribuição interessante, nesse sentido, é a caracterização funcional de polimorfismos genéticos existentes entre genótipos do gênero Saccharum, auxiliando investigações relacionadas à genômica de poliploides complexos, desenvolvendo um recurso a ser utilizado futuramente por melhoristas. Esse trabalho realizou a caracterização da variabilidade genômica a partir de dados genotípicos de indivíduos do Painel Brasileiro de Genótipos de Cana-de-Açúcar, obtidos via genotipagem-por-sequenciamento, utilizando como referência o genoma já sequenciado do sorgo. Os sítios variantes (sobretudo polimorfismos de nucleotídeo único) foram detectados com o software FreeBayes e suas possíveis funções e posições foram anotadas com o programa SnpEff. Utilizaram-se estatísticas de genética de populações, como a frequência alélica para várias classes de polimorfimo, o Teste de McDonald & Kreitman (busca de evidêcias de evolução adaptativa) e a heterozigosidade combinada (busca de regiões genômicas com assinatura de seleção), de modo a identificar regiões genômicas potencialmente envolvidas em eventos evolutivos. Os resultados demonstraram a perda de variabilidade entre os genótipos melhorados em relação aos ancestrais, com evidências de assinaturas de seleção, envolvendo questões sensíveis ao funcionamento da maquinaria celular (como respiração e fotossíntese) e a características valoradas para a cultura (destacando-se a resistência a patógenos e a biossíntese da sacarose). Tais indícios fornecem subsídios à compreensão do genoma e ao melhoramento genético desse poliploide. / Sugarcane (Saccharum ssp.) is a valuable crop for food, fiber and energy production in Brazil, especially to the São Paulo State. With the advent of biotechnology, alternatives to breeding have enticed attention of the scientific community, with genome sequencing and characterization being crucial steps to these advances. Because sugarcane is polyploid, with frequent aneuploidy, it presents difficulties to the application of standard practices in genomics, such that it is advantageous to make use of next generation sequencing alternatives and resources from related species to more effectively elucidate the genome of this grass. Thus, an interesting contribution is the functional characterization of genetic polymorphisms from the Saccharum genus, aiding investigations related to genomics of complex polyploids, developing a resource to be used in the future by breeders. Our goal was to perform this characterization with genotypic data from individuals of the Brazilian Panel of Sugarcane Genotypes, obtained by genotyping-by-sequencing (GBS), using as reference the previously sequenced sorghum genome. We called the variants (mainly single nucleotide polymorphisms) with FreeBayes and annotated their functions and positions with SnpEff. We used population genetics statistics, such as the allele frequency, the McDonald & Kreitman Test and the pooled heterozygosity, to identify genomic regions potentially involved in evolutionary events. The results showed a loss of variability between bred genotypes in relation to the ancestors, with evidences of selective sweeps, involving regions related to the cellular machinery (such as respiration and photosynthesis) and specific crop traits (especially disease resistance and sucrose biosynthesis). These results support understanding of the genome and breeding efforts in this polyploid grass.

A descoberta de inibidores seletivos é extremamente importante para o desenvolvimento de novos fármacos que possam ser usados no tratamento de pacientes diagnosticados com a doença de Alzheimer (DA). Neste contexto, o desenvolvimento de métodos de triagem para a identificação de novos compostos biologicamente ativos se torna interessante. Butirilcolinesterase (BChE, EC 3.1.1.8) é uma serina hidroxilase que está classicamente associada à hidrólise do neurotransmissor acetilcolina (ACh) formando colina e ácido acético. Este trabalho descreve a imobilização covalente da BChE de soro humano nas paredes internas de capilares de sílica fundida utilizando o agente espaçador glutaraldeído, e sua aplicação na triagem de inibidores seletivos. O ICER-BChE resultante foi conectado a um sistema de cromatografia líquida de alta eficiência com monitoramento on line da atividade catalítica, envolvendo detecção UV. Após os estudos das melhores condições cromatográficas, variações de pH e vazão e a influência de solventes orgânicos na atividade enzimática o método foi validado com o uso de inibidores padrões. O maior valor obtido com o ICER-BChE no parâmetro cinético, constante de Michaelis KM = 33,6 ± 6,9 mM, comparado com a enzima em solução, KM = 0,12 ± 0,02 mM, evidencia o efeito da imobilização sobre a afinidade pelo substrato. No entanto, houve retenção da atividade catalítica e seletividade frente a inibidores padrão. O método foi aplicado na triagem de novos ligantes utilizando cinco coleções de diferentes classes de compostos, entre derivados cumarínicos, complexos metálicos com cobre (Cu), complexos metálicos com cobalto (Co) e zinco (Zn), glicosídeos, e derivados de fenilpropanóides e ácido barbitúrico. Desta triagem foram selecionados sete compostos promissores com os quais foram realizados os estudos sobre a potência mínima inibitória (IC50) e destes quatro foram escolhidos para estudos de mecanismos de ação utilizando o ICER-BChE. Dos complexos metálicos os melhores compostos foram o HPTBCu (IC50 = 8,74 ± 1,5 µM, Ki = 9,6 ± 0,5 M), o NarBCu (IC50 = 8,0 ± 1,4 µM, Ki = 2,0 ± 0,1 M) ambos com mecanismo competitivo o HesFCu (IC50 = 13,6 ± 2,9 µM), o NNINABCu (IC50 = 94,8 ± 16) e o NarFCu (IC50 = 81,7 ± 13). Dos derivados cumarínicos os compostos 17 (IC50 =109 ± 21 µM, Ki = 108 ± 10 M) e 19 (IC50 =128 ± 28 µM, Ki =36.0 ± 5.0 M) apresentaram mecanismo incompetitivo. Os resultados demonstraram que a abordagem proposta é útil na triagem on line de inibidores seletivos, pois fornece resultados rápidos, precisos e reprodutíveis. / The discovery of selective inhibitors is extremely important for the development of drugs that can be used in the treatment of patients diagnosed with the Alzheimer disease (AD). In this context, the development of screening methods for the identification of new, biologically active compounds is a challenging task. Butyrylcholinesterase (BChE, EC 3.1.1.8) is a serine hydroxylase that is classically associated with the hydrolysis of the neurotransmitter acetylcholine (ACh), which yields choline and acetic acid. This paper describes the development of capillary enzyme reactors (ICERs) containing BChE from the human serum, covalently immobilized onto silica fused capillaries, using glutaraldehyde as spacer, and its application in the screening of selective inhibitors. The resulting BChE-ICER was connected to a liquid chromatography system high efficiency where monitoring of activity was online involving UV detection. After studying the best chromatographic conditions, pH variations, flow-rate and the influence of organic solvents on enzyme activity method was validated using standard inhibitors. The higher value obtained with the BChE-ICER in kinetic parameter, constant Michaelis KM = 33.6 ± 6.9 mM, compared with the enzyme in solution, KM = 0.12 ± 0.02 mM, shows the effect of immobilized on the affinity substrate. However, there was retention of catalytic activity and selectivity towards standard inhibitors. The method was applied in the screening of new ligands using collections of five different compounds, among coumarin derivatives, metal complexes with copper (Cu) metal complexes with cobalt (Co) and zinc (Zn), glycosides, phenylpropanoids and derivatives, and barbituric acid. These screenings were selected seven promising compounds with which the studies were made on the minimum inhibitory potency (IC50) and these four were chosen for studies of mechanisms of action using the ICER-BChE. Of the compounds metal complexes best were HPTBCu (IC50 = 8,74 ± 1,5 µM, Ki = 9,6 ± 0,5 M), NarBCu (IC50 = 8,0 ± 1,4 µM, Ki = 2,0 ± 0,1 M) both competitive mechanism, the HesFCu (IC50 = 13.6 ± 2.9 µM), NNINABCu (IC50 = 94.8 ± 16 µM) and NarFCu (IC50 = 81.7 ± 13 µM). Of coumarin derivatives, 17 (IC50 =109 ± 21 µM, Ki = 108 ± 10 M) and 19 (IC50 =128 ± 28 µM, Ki =36.0 ± 5.0 M) showed mechanism uncompetitive. The results demonstrated that the proposed approach is useful in screening for selective inhibitors online because it provides quick results, accurate and reproducible.