Le sujet de cette thèse se situe dans le cadre général des arylations de nucléophiles catalysées par des complexes de métaux de transitions (Cu, Fe) ou réalisées en absence de ces derniers, dans des conditions compétitives et respectueuses de l’environnement. Ces réactions sont d’une importance majeure pour l’industrie chimique. Dans un premier chapitre est tout d’abord décrit un couplage inédit mettant en jeu un sel d’aryldiazonium et un nucléophile azoté (formation de liaison CAr-N). La méthode procède dans des conditions douces via un système catalytique au cuivre peu coûteux et peu toxique. Les produits de couplage obtenus (Ar-NHet) sont d’un intérêt central dans l’industrie pharmaceutique et agrochimique. Dans une deuxième partie nous avons présenté une méthode permettant de réaliser le couplage entre des sels d’aryldiazonium et des dérivés du styrène, à l’aide d’un système t BuOK/DMF. Cette réaction, réalisée pour la première fois en absence de catalyseurs à base de métaux de transition, permet d’accéder, via la formation de liaisons CArsp²-Csp², à des motifs stilbènes variés qui trouvent de nombreuses applications en chimie pharmaceutique. Un deuxième chapitre porte sur l’utilisation de dérivés de l’iode hypervalent permettant la fonctionnalisation de noyaux aromatiques (C-H) ou de dérivés vinyliques (C-H). Une première méthode décrit une réaction de triflimidation directe de composés acétanilides avec une sélectivité exclusive en position para. Deux conditions réactionnelles ont été mises en place pour cette fonctionnalisation. Une première utilise une quantité stœchiométrique de PhI(OAc)2 et une autre utilise une quantité catalytique d’iodotoluène (génération in-situ de l’iode(III)). Cette transformation a conduit à la formation de liaisons CAr-N en présence de bis(trifluorométhane)sulfonimide de lithium (LINTf2) comme nucléophile azoté. Dans une deuxième partie, nous avons montré que l’iodure de bisphosphoranilidène (PNPI), pouvait catalyser la trifluorométhylation vinylique sélective de dérivés du styrène en présence d’un réactif de l’iode hypervalent (l’iode(III)), le réactif de Togni II. Des travaux sont en cours pour tenter de comprendre l’influence positive de l’utilisation de PNPI dans le cas de notre réaction. Un troisième chapitre décrit des résultats préliminaires permettant d’obtenir un rendement honorable (54%) lors du couplage catalysé au fer du 4-iodotoluène avec le phényllithium. Une autre série de test décrit le couplage entre des halogénures d’aryle et des alkyllithium primaires. La méthode semble très efficace, puisque par ailleurs les travaux très récents de la littérature pour des couplages similaires faisant intervenir les mêmes partenaires réactionnels, font appel à des catalyseurs de fer ou de palladium. / This thesis is part of a very general search seek to develop methodologies for environmentally sustainable conversion of small molecules into more valuable substances catalyzed by copper and iron complexes or under metal-free conditions. The work focuses on the functionalization of aromatic rings by C-C or C-N bond formation.In a first chapter, a novel coupling involving an aryldiazonium salt and a nitrogenous nucleophile (CAr-N bond formation) is first described. The method proceeds under mild conditions using a cheap and non-toxic copper catalyst system. The obtained coupling products (Ar-NHet) are of central interest in the pharmaceutical and agrochemical industry. Then in a second part, a method allowing the coupling between aryldiazonium salts and styrene derivatives, using a BuOK / DMF system is presented. This reaction, carried out for the first time in the absence of catalysts based on transition metals, makes it possible to access to various stilbene units which find numerous applications in pharmaceutical chemistry.A second chapter concerns the use of hypervalent iodine derivatives allowing the functionalization of aromatic or vinyl substrates. A first method describes a direct triflimidation reaction of acetanilide compounds with an exclusive selectivity in the para position. Two reactions conditions have been established for this functionalization. One uses a stoichiometric amount of PhI(OAc)2 and another uses a catalytic amount of iodotoluene (in-situ generation of iodine (III)). This transformation resulted in the formation of CAr-N bonds in the presence of lithium bis (trifluoromethane) sulfonimide (LINTf2) as the nitrogen nucleophile. In a second part, we have shown that bisphosphoranilidene iodide (PNPI) can catalyze a selective vinylic trifluoromethylation of styrene derivatives in the presence of a hypervalent iodine reagent (iodine (III)), Togni’s reagent II. Work is under way to try to understand the positive influence of PNPI.A third chapter describes preliminary results of an iron-catalyzed heterocoupling of 4-iodotoluene an phenylithium system allowing the obtention of an honorable yield (54%) during the coupling of 4-iodotoluene with phenyllithium. Another series of tests describes the coupling between aryl halides and primary alkyllithiums. The method seems to be very effective, since very recent work in the literature for similar couplings involving the same reaction partners involves catalysts of iron or palladium.

Made available in DSpace on 2016-01-26T18:56:33Z (GMT). No. of bitstreams: 1 Dissertacao Cassio.pdf: 89555 bytes, checksum: 2cb8164cead8de20efdda98a794b73c4 (MD5) Previous issue date: 2007-12-10 / Objected with this work to evalue the vegetable matter production, the accumulation of N and relation C/N of phytomass in different stages of single crops and consortiums of pigeon pea (Cajanus cajan), sorghum (Sorghum bicolor) and millet (Pennisetum glaucum). The experimental was conducted in a Experimental Farm of Unoeste, at Presidente Prudente-SP, during March and June, 2006. It was used the randomized experimental design in blocks, in the factorial scheme, with the followings treatments: sorghum monoculture, pigeon pea and millet, and consortium of sorghum + pigeon pea, millet + pigeon pea and millet + sorghum, with stages of collection at 30, 60 e 90 days after seeding. The millet was more expressive in the initial grouth velocity, so that species in consortium were dominated, and it produced more phytomass in the intercropping than in the monocultures. The best period to handle consortiums of millet + pigeon pea and sorghum + pigeon pea were at 60 and 90 days after seeding in off-season time, respectively. The consortium sorghum + pigeon pea submitted better balance in composition to straw, because there was more timing between growth velocity of both species. The monoculture of grass submitted straw with relation C/N more elevated than in the intercropping millet + pigeon pea and sorghum + pigeon pea. / A consorciação de plantas de cobertura tem sido preconizada com o propósito de conciliar a proteção do solo e favorecer a oferta de nutrientes em sistemas de rotação de culturas. Objetivou-se com este trabalho avaliar a produtividade de matéria vegetal, o acúmulo de N e a relação C/N de fitomassas em diferentes estádios de culturas solteiras e consorciadas de guandu-anão (Cajanus cajan), sorgo (Sorghum bicolor) e milheto (Pennisetum glaucum). O experimento foi realizado na Fazenda Experimental da Unoeste, em Presidente Prudente-SP, durante março e junho de 2006. Utilizou-se o delineamento experimental em blocos aos acaso, no esquema fatorial, com os seguintes tratamentos: monocultivos de sorgo, guandu-anão e milheto, e consórcios de sorgo + guandu-anão, milheto + guandu-anão e milheto + sorgo, com épocas de coleta aos 30, 60 e 90 dias após a semeadura. O milheto foi muito expressivo na velocidade de crescimento inicial, de tal forma que as espécies em consórcio ficaram dominadas, produzindo mais fitomassa nas culturas intercaladas do que em monocultivo. As melhores épocas para o manejo das culturas consorciadas de milheto + guandu-anão e sorgo + guandu-anão foram aos 60 e 90 dias após a semeadura no ambiente safrinha, respectivamente. A consorciação sorgo + guandu-anão apresentou maior equilíbrio na composição da palhada, pois houve mais sincronismo entre as velocidades de crescimento de ambas as espécies. Os monocultivos de gramíneas apresentaram palhadas com relações C/N mais elevadas do que nos consórcios milheto + guandu-anão e sorgo + guandu-anão.

Made available in DSpace on 2016-07-18T17:51:15Z (GMT). No. of bitstreams: 1 Dissertacao Cassio.pdf: 89555 bytes, checksum: 2cb8164cead8de20efdda98a794b73c4 (MD5) Previous issue date: 2007-12-10 / Objected with this work to evalue the vegetable matter production, the accumulation of N and relation C/N of phytomass in different stages of single crops and consortiums of pigeon pea (Cajanus cajan), sorghum (Sorghum bicolor) and millet (Pennisetum glaucum). The experimental was conducted in a Experimental Farm of Unoeste, at Presidente Prudente-SP, during March and June, 2006. It was used the randomized experimental design in blocks, in the factorial scheme, with the followings treatments: sorghum monoculture, pigeon pea and millet, and consortium of sorghum + pigeon pea, millet + pigeon pea and millet + sorghum, with stages of collection at 30, 60 e 90 days after seeding. The millet was more expressive in the initial grouth velocity, so that species in consortium were dominated, and it produced more phytomass in the intercropping than in the monocultures. The best period to handle consortiums of millet + pigeon pea and sorghum + pigeon pea were at 60 and 90 days after seeding in off-season time, respectively. The consortium sorghum + pigeon pea submitted better balance in composition to straw, because there was more timing between growth velocity of both species. The monoculture of grass submitted straw with relation C/N more elevated than in the intercropping millet + pigeon pea and sorghum + pigeon pea. / A consorciação de plantas de cobertura tem sido preconizada com o propósito de conciliar a proteção do solo e favorecer a oferta de nutrientes em sistemas de rotação de culturas. Objetivou-se com este trabalho avaliar a produtividade de matéria vegetal, o acúmulo de N e a relação C/N de fitomassas em diferentes estádios de culturas solteiras e consorciadas de guandu-anão (Cajanus cajan), sorgo (Sorghum bicolor) e milheto (Pennisetum glaucum). O experimento foi realizado na Fazenda Experimental da Unoeste, em Presidente Prudente-SP, durante março e junho de 2006. Utilizou-se o delineamento experimental em blocos aos acaso, no esquema fatorial, com os seguintes tratamentos: monocultivos de sorgo, guandu-anão e milheto, e consórcios de sorgo + guandu-anão, milheto + guandu-anão e milheto + sorgo, com épocas de coleta aos 30, 60 e 90 dias após a semeadura. O milheto foi muito expressivo na velocidade de crescimento inicial, de tal forma que as espécies em consórcio ficaram dominadas, produzindo mais fitomassa nas culturas intercaladas do que em monocultivo. As melhores épocas para o manejo das culturas consorciadas de milheto + guandu-anão e sorgo + guandu-anão foram aos 60 e 90 dias após a semeadura no ambiente safrinha, respectivamente. A consorciação sorgo + guandu-anão apresentou maior equilíbrio na composição da palhada, pois houve mais sincronismo entre as velocidades de crescimento de ambas as espécies. Os monocultivos de gramíneas apresentaram palhadas com relações C/N mais elevadas do que nos consórcios milheto + guandu-anão e sorgo + guandu-anão.

Oleogenic yeasts under appropriate conditions produce and accumulate lipids and lipid-soluble metabolites in high amounts. This attribute is characteristic also for red yeasts that except lipids accumulate also carotenoids – natural pigments used in food industry and dietary supplements. The aim of this diploma thesis was designed as a comparative screening study of production properties of strains Cystofilobasidium capitatum, Rhodotorula glutinis, Sporobolomyces roseus and Sporobolomyces shibatanus. Choosen carbon sources were glucose and glycerol as waste by-product in biofuel industry. The best production properties were found in Cystofilobasidium capitatum and Rhodotorula glutinis. These two strains produced increased amounts of lipids as well as higher amounts of carotenoids. Strains were tested by FTIR spectroscopy that enables high-throughput, uncomplicated and accurate analysis.

In der vorliegenden Arbeit wurde das Wachstum von Bergahorn und Buche mit dendroökologischen Methoden untersucht. Dies geschah vor dem Hintergrund der Ausbreitung des Bergahorns und der Eutrophierung der Landschaft. Die daran anknüpfende Fragestellung ist: Begünstigt Eutrophierung den Bergahorn? Die Untersuchung fand in einem Waldstück in Mecklenburg-Vorpommern statt. Dabei wurden von 42 Bergahornen und 38 Buchen Bohrkerne für die Vermessung der Jahrringe genommen. Weiterhin wurde neben jedem beprobten Baum das C/N-Verhältnis des Oberbodens bestimmt (n=80). Die Auswertung der Daten erfolgte durch drei Ansätze: 1.) Der Einfluss einer Hähnchenmastanlage auf beide Baumarten wurde untersucht. 2.) Die Beziehung zwischen dem C/N-Verhältnis des Bodens und dem Wachstum der Bäume wurde verglichen. 3.) Auf unterschiedlichen Standorten (C/N-Verhältnis) wurde die Abhängigkeit des Wachstums der Bäume vom Klima untersucht. Dabei wurde die Reaktion der beiden Arten auf das Klima verglichen. Die deutlichsten Ergebnisse wurden durch den zweiten Ansatz erzielt. Das C/N-Verhältnis des oberen Bodens lag zwischen 12,4 und 17,4. In diesem Bereich wurde eine positive Korrelation zwischen dem C/N-Verhältnis des Bodens und dem Wachstum der Bäume festgestellt. Die Ergebnisse deuten auf eine Schädigung der beiden Arten durch Stickstoff hin, welche beim Bergahorn (R² = 0,30) stärker als bei der Buche (R² = 0,18) ausgeprägt ist. Daraus folgt, dass der Bergahorn durch die Eutrophierung geschwächt wird. Ein Einfluss der Mastanlage auf das Wachstum der Bäume wurde nicht festgestellt. Auf das Klima reagierten beiden Arten ähnlich. Es bestand ein positiver Zusammenhang zwischen dem Niederschlag und dem Wachstum der Bäume. Der Einfluss des Standorts auf die Klimareaktion der Bäume war uneindeutig. / Within this thesis the growth of sycamore (Acer pseudoplatanus L.) and beech (Fagus sylvatica L.) was investigated by applying dendroecological methods. The overall idea derived from the distribution of sycamore and the eutrophication of the environment leading to the question whether eutrophication promotes the spread of sycamore. The investigated forest was located in Mecklenburg-Vorpommern. To inspect the annual rings of the trees 42 samples were taken off the trunk of sycamore while 38 samples were gathered from beech. Apart from that the ratio of carbon and nitrogen within the topsoil of every single tree was analysed (n=80). The evaluation of the data employed three approaches. 1.) The impact of a poultry farm on both species was investigated. 2.) The relation of the C/N-ratio of the soil was compared to the growth of the trees. 3.) The connection between the growth of the trees and the climate was examined for the various sites (in terms of the C/N-ratio). Thereby the response of the species onto the climate was compared. The most precise results were achieved within the second approach. Values for the C/N-ratio of the upper soil lay between 12.4 and 17.4. A positive correlation between the C/N-ratio of the soil and the growth of the trees was discovered within this range. The results suggest an adverse effect to both of the species. This effect is more intense regarding sycamore (R² = 0,30) compared to beech (R² = 0,18). It can therefore be concluded that sycamore is weakened by eutrophication. An effect of the poultry farm on the species was not observed. Both species responded similarly regarding climate parameters. A positive relation between precipitation and growth of the trees was found. The impact of the location on the climate reaction of the trees was ambiguous.

Cette thèse présente le développement du réarrangement photochimique des lactames N -hétérosubstituées ainsi que son potentiel d'application en synthèse organique. Le premier chapitre traite de l'étude des possibilités et limitations de la photolyse des N -chlorolactames, les premiers précurseurs rapportés pour cette nouvelle contraction de cycle. Une variété de substrats ont été synthétisés et réarrangés afin d'établir la généralité de cette nouvelle réaction. Une discussion élaborée sur les résultats obtenus ainsi que les preuves mécanistiques apportées par ceux-ci y est faite. Une proposition mécanistique de cette nouvelle réaction est également apportée. Le deuxième chapitre présente la synthèse et contraction de cycle des N -mésyloxylactames. Celles-ci ont été élaborées afin d'inhiber la voie radicalaire secondaire en compétition lors de la photolyse des N -chlorolactames et par ce fait augmenter le rendement provenant de cette nouvelle migration [1,2].Cette nouvelle modification réactionnelle a démontré des rendements beaucoup plus élevés et synthétiquement viables pour les carbamates isolés et une bonne généralité pour le type de précurseurs pouvant subir cette migration stéréospécifique. Le réarrangement photochimique des lactames N -hétérosusbtituées est donc devenu une méthode fiable et prévisible pour la formation de liens C-N de manière stéréospécifique et ainsi une nouvelle réaction complémentaire aux réarrangements ioniques existants. Le troisième chapitre traite de l'application de cette nouvelle méthodologie vers la synthèse de la (+)-géphyrotoxine. Deux approches synthétiques racémiques ont été développées et un précurseur avancé vers cet alcaloïde a été synthétisé de manière expéditive avec un bon rendement et la bonne stéréochimie relative. Une version énantiosélective a été proposée en employant cette nouvelle stratégie.

Since their introduction to Lake Erie, dreissenid mussels may have reengineered the cycling of nutrients in the lake so that the nearshore benthic community intercepts, retains, and recycles greater quantities of nutrients. This study traces particulate matter on a basin scale by characterizing the chemical composition (POC and PN concentrations, POC/PN mass ratios, δ¹³C and δ¹⁵N) of suspended particulate matter in Lake Erie, three tributary inflows, and the lake outflow between May and October, 2002. The data are used to 1) determine the relative contributions of allochthonous and autochthonous sources to suspended particulate matter, 2) identify possible sources of suspended particulate matter, and 3) compare suspended particulate matter in the eastern basin of Lake Erie with that in the central and western basins. Mean POC concentrations range from 175 to 4494 ??g/L and mean PN concentrations range from 33 to 812 ??g/L in this system. Mean POC/PN mass ratios are similar across all sampling locations, ranging between 4. 5 and 6. 9, and indicate that suspended particulate matter at these sites is mainly derived from autochthonous sources, particularly plankton. The ranges of δ¹³C (-34 to -22 ?) and δ¹⁵N (1 to 12 ?) identify terrestrial plants and soil matter, aquatic macrophytes, phytoplankton, and sewage as possible sources of suspended particulate matter at all sites. Plankton is probably the dominant source of suspended particulate matter at each site, with smaller contributions from allochthonous and other autochthonous sources. Significant differences in the concentration and isotope data between inflow and lake or outflow sites indicate that tributary inflows may receive greater contributions from terrestrial plants and soils and aquatic macrophytes than the lake and outflow. δ¹⁵N signatures also identify animal manure as a possible source of suspended particulate matter at the inflows. PN concentrations and δ¹⁵N signatures suggest that the shallowest nearshore sites close to Peacock Point in the eastern basin receive PN from a source that is not present at the other eastern basin sites or at the sites in the central and western basins. This source may be related to dreissenid mussels at these nearshore sites recycling nitrogen back into the water column.

Telomeres are nucleoprotein complexes found at the ends of linear eukaryotic chromosomes. Telomeres consist of a short sequence of repetitive double stranded DNA, TTAGGG repeats in humans (and all mammals), and a complex of 6 proteins, termed the shelterin complex. The length of the telomeres varies greatly between species, from approximately 300 base pairs in yeast to many 10-15 kilo bases in humans, because of the end replication problem this length get shorten with each cell division and ultimately leads to cell death. However the immortal eukaryotic cells and some transformed human cells over come this incomplete end replication problem with the use of enzyme called Telomerase. Telomerase is a ribonucleoprotein enzyme that adds a specific DNA sequence repeats (TTAGGG) to the 3¢ end of DNA strands in the telomere regions. However from the telomerase activity studies, it was concluded that telomerase is active in almost 90% of human cancers but not in normal somatic tissues. Finally, the low or transient expression of telomerase in normal tissues, including normal stem cells, and the generally longer telomeres in normal cells versus tumor cells provide a degree of tumor specificity to telomerase-based drugs and reduce the probability of toxicity to normal tissue. All of these factors suggest that cancer drugs based on telomerase might have a broad therapeutic window. This dissertation focusing on the synthesis of acridine derivatives that have the capability to inhibit the enzyme telomerase. Several N-acridyl maleimide (NAM), N-acridyl succinimide (NAS) and N-acridyl phthalimide (NAP) derivatives have been synthesized and evaluated for their anti cancer activity against various cancer cell lines. While synthesizing acridine derivatives it was required to form the C-N bonds at various stages. Developed a copper-nicotinic acid complex, which catalyzes the coupling of aryl halides with N-formyl amines and cyclic imides to form C-N bond. Explored Cu (II) catalyzed formation of C-N bond by coupling aryl halides with various N-nucleophiles such as formamide, N,N-dimethyl formamide, N-formyl amines and various cyclic imides.

Since their introduction to Lake Erie, dreissenid mussels may have reengineered the cycling of nutrients in the lake so that the nearshore benthic community intercepts, retains, and recycles greater quantities of nutrients. This study traces particulate matter on a basin scale by characterizing the chemical composition (POC and PN concentrations, POC/PN mass ratios, δ¹³C and δ¹⁵N) of suspended particulate matter in Lake Erie, three tributary inflows, and the lake outflow between May and October, 2002. The data are used to 1) determine the relative contributions of allochthonous and autochthonous sources to suspended particulate matter, 2) identify possible sources of suspended particulate matter, and 3) compare suspended particulate matter in the eastern basin of Lake Erie with that in the central and western basins. Mean POC concentrations range from 175 to 4494 µg/L and mean PN concentrations range from 33 to 812 µg/L in this system. Mean POC/PN mass ratios are similar across all sampling locations, ranging between 4. 5 and 6. 9, and indicate that suspended particulate matter at these sites is mainly derived from autochthonous sources, particularly plankton. The ranges of δ¹³C (-34 to -22 ?) and δ¹⁵N (1 to 12 ?) identify terrestrial plants and soil matter, aquatic macrophytes, phytoplankton, and sewage as possible sources of suspended particulate matter at all sites. Plankton is probably the dominant source of suspended particulate matter at each site, with smaller contributions from allochthonous and other autochthonous sources. Significant differences in the concentration and isotope data between inflow and lake or outflow sites indicate that tributary inflows may receive greater contributions from terrestrial plants and soils and aquatic macrophytes than the lake and outflow. δ¹⁵N signatures also identify animal manure as a possible source of suspended particulate matter at the inflows. PN concentrations and δ¹⁵N signatures suggest that the shallowest nearshore sites close to Peacock Point in the eastern basin receive PN from a source that is not present at the other eastern basin sites or at the sites in the central and western basins. This source may be related to dreissenid mussels at these nearshore sites recycling nitrogen back into the water column.

This study used the sediment samples collected in May (dry season) and September (wet season) 2010 in a river delta and tidal flat complex around Jhoushuei River mouth in Central Taiwan to examine seasonal sediment transport pathways and sources. Four different approaches were used in the analysis of grain-size distribution pattern. They include (1) the McLaren-Bowles method, and (2) the transport vector technique (Gao-Collins method), and (3) a combination of `filtering' and the empirical orthogonal (eigen) function (EOF) analysis technique, and (4) C/N elemental ratios of organic sediments. The results of surface grain size distributions of sediment range from clay to medium sand towards the sea, and very fine sand deposited in the river delta. On the upper tidal flat, mud content of the wet season is higher than dry season due to higher river output of organic sediment and low-energy sediment transport. In wet season, according to the fine-grained sediment from the Jhoushuei River is therefore mainly discharged to the offshore area and little remain around the tidal flat, the influence of river on the grain-size distribution is the least. The results based on McLaren-Bowles method indicate that there were two type sediment transport pathways, (1) the river carried sediment to the coast, then alone the northeast-southwest direction by the longshore current, and (2) during the flood tide, the riverine sediment move to northeast and east through the river delta and tidal creek to the upper tidal flat, respectively. The results based on Gao-Collins method indicate that there was possible seasonal variation of sediment transport pathways on the river delta front, where the significant transport was seaward in the wet season whereas the transport was the opposite in the dry season. On the tidal flat, the model results indicate that seaward transport seems to be controlled by ebb tidal current perhaps due to the sampling at low-tide.