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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
51

Soil community dynamics in sagebrush and cheatgrass-invaded ecosystems of the northern Great Basin /

DeCrappeo, Nicole M. January 1900 (has links)
Thesis (Ph. D.)--Oregon State University, 2011. / Printout. Includes bibliographical references (leaves 123-135). Also available on the World Wide Web.
52

Ecologically-Based Manipulation Practices for Managing Bromus tectorum-infested Rangelands

Fowers, Beth 01 August 2011 (has links)
Cheatgrass (Bromus tectorum) is an invasive annual grass common in several semiarid plant communities in the western U.S. B. tectorum presence increases fire frequency and size, reducing species diversity, and leading to annual species-dominated systems with inconsistent livestock forage potential and degraded wildlife habitat value. Most efforts to manage B. tectorum-dominated rangelands have focused on controlling the plant itself rather than addressing the causes of vegetation change. An alternative approach, ecologically-based invasive plant management (EBIPM), identifies treatments that can alter factors associated with the causes of succession, leading to a more desirable vegetation state. This study utilized the EBIPM framework to design a large-scale demonstration project, which implemented a series of manipulation treatments (mowing, prescribed fire, imazapic herbicide, and seeding with perennial species) to suppress B. tectorum and promote desirable species. The treatments were implemented at two semiarid shrubland sites in northwestern Utah. Treatments were evaluated by measuring resident vegetation cover, density, aboveground biomass, and litter and soil seed banks. Herbicide was most effective in reducing B. tectorum cover, density, and biomass, while fire was effective in reducing seed density in the litter seed bank. Treatment interactions were rarely significant; however, by combining fire and herbicide, increased B. tectorum control was achieved. Seedlings of seeded perennial grasses emerged in all treatments; however, establishment by the end of the first growing season was greatest in treatments involving fire. The results of this study indicate that using a decision-making framework to select a series of treatments that alter the causes of succession can improve the management of B. tectroum-dominated rangelands.
53

Characterization of an Amphipathic Alpha-Helix in the Membrane Targeting and Viral Genome Replication of Brome Mosaic Virus

Sathanantham, Preethi 01 March 2022 (has links)
Positive-strand RNA viruses associate with specific organelle membranes of host cells to establish viral replication complexes. The replication protein 1a of brome mosaic virus associates strongly with the nuclear endoplasmic reticulum (ER) membranes, invaginates membranes into the lumen, and recruits various host proteins to establish replication complexes termed spherules. 1a has a strong affinity towards the perinuclear ER membrane, however, the structural features in 1a that dictate its membrane associations and thereby membrane remodeling activities are unclear. This study examined the possible role of an amphipathic α-helix, helix B, in BMV 1a's membrane association. Deletion or single substitution of multiple amino acids of helix B abolished BMV 1a's localization to nuclear ER membranes. Additional reporter-based, gain-of-function assays showed that helix B is sufficient in targeting several soluble proteins to the nuclear ER membranes. Furthermore, we found that the helix B-mediated organelle targeting is a functionally conserved feature among positive-strand RNA viruses of the alphavirus-like superfamily that includes notable human viruses such as Hepatitis E virus and Rubella virus as well as plant viruses such as cucumber mosaic virus and cowpea chlorotic mottle virus. Our results demonstrate a critical role for helix B across members of the alphavirus-like superfamily in anchoring viral replication complexes to the organelle membranes. We anticipate our findings to be a starting point for the development of sophisticated models to use helix B as a novel target for the development of antivirals for positive-strand RNA viruses that belong to the alphavirus-like superfamily. / Doctor of Philosophy / Among the seven classes of viruses, the positive-strand RNA viruses dominate the domain of viral diseases of the world. Brome mosaic virus (BMV) is a positive-strand RNA virus that infects cereal crops such as wheat, barley, and rice. BMV has a simple genome organization and serves as a suitable model virus to study and characterize positive-strand RNA viruses. The replication of all positive-strand RNA viruses occurs at the organelle membranes of the host. Membrane association of the replication is one of the early steps and a crucial event in the life cycle of positive-strand RNA viruses. One of the proteins produced early on during BMV infection is the replication protein 1a, which is also the master regulator of viral replication; 1a recruits viral factors in addition to hijacking the necessary host factors at the membranous sites to initiate replication. Upon reaching the organelle membranes, 1a induces membrane rearrangements to form viral replication complexes that safeguard the recruited factors from the deleterious effects of the host cell. The structural determinants within 1a that are responsible for such membrane association are unknown. This study explored the potential roles of a short helical motif within the 1a protein for its ability to dictate such site-specific membrane associations. We show here that this helical region is necessary and sufficient for 1a's membrane-binding activity. We also discovered it to be a functionally conserved feature that is responsible for membrane associations in various viruses of the alphavirus-like superfamily that includes some of the notable human viruses such as Hepatitis E virus and Rubella virus in addition to plant viruses such as cucumber mosaic virus and cowpea chlorotic mottle virus.
54

Process_Based Management of Downy Brome in Salt Desert Shrublands: Assessing Pre- and Post-Rehabilitation Soil and Vegetation Attributes

Hirsch, Merilynn Carol 01 May 2011 (has links)
A number of technical approaches had to be employed within the planner, namely, 1) translating expected reward into a probability of goal satisfaction criterion, 2) monitoring belief states with a Rao-Blackwellized particle, and 3) employing Rao-Blackwellized particles in the McLUG probabilistic conformant planning graph heuristic. POND-Hindsight is an action selection mechanism that evaluates each possible action by generating a number of lookahead samples (up to a xed horizon) that greedily select actions based on their heuristic value and samples the actions' observation; the average goal satisfaction probability of the end horizon belief states is used as the value of each action.
55

Nanotubos de carbono de parede dupla submetidos à condições extremas de altas pressões e altas temperaturas / Nanotubes de carbone double parois soumis à des conditions extrêmes de haute pression et de température

Aguiar, Acrísio Lins de January 2012 (has links)
AGUIAR, Acrísio Lins de. Nanotubos de carbono de parede dupla submetidos à condições extremas de altas pressões e altas temperaturas. 2012. 197 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2012. / Submitted by Edvander Pires (edvanderpires@gmail.com) on 2015-05-29T19:28:11Z No. of bitstreams: 1 2012_tese_alaguiar.pdf: 15566235 bytes, checksum: 090d7b1014d9ecd24a1e1d5a822ba0ec (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2015-05-29T19:30:54Z (GMT) No. of bitstreams: 1 2012_tese_alaguiar.pdf: 15566235 bytes, checksum: 090d7b1014d9ecd24a1e1d5a822ba0ec (MD5) / Made available in DSpace on 2015-05-29T19:30:54Z (GMT). No. of bitstreams: 1 2012_tese_alaguiar.pdf: 15566235 bytes, checksum: 090d7b1014d9ecd24a1e1d5a822ba0ec (MD5) Previous issue date: 2012 / Nesta tese apresentamos os resultados referentes aos estudos de nanotubos de carbono de parede dupla submetidos à condições de pressão hidrostática usando ferramentas experimentais e teóricas. A partir de cálculos teóricos de propriedades estruturais e de estrutura eletrônica usando primeiros princípios e potenciais clássicos, estudamos a evolução estrutural dos nanotubos de carbono e suas propriedades vibracionais em função da pressão hidrostática. Estudamos amostras de nanotubos de carbono em feixes bundles puros e modificados quimicamente através da dopagem (intercalação) de moléculas de bromo quando submetidos a condições extremas de altas pressões, utilizando principalmente técnicas de espectroscopia Raman. Medidas de Microscopia Eletrônica de Transmissão (TEM), análise de composição química por XPS e absorção de raios-X foram utilizadas de forma complementar. Apresentamos a perspectiva de entender os efeitos químicos sob o comportamento estrutural dos nanotubos de carbono ao aplicarmos altas pressões. As propriedades vibracionais dos nanotubos foram estudadas até pressões de 30 GPa usando dois diferentes meios de transmissão de pressão: óleo de parafina e NaCl sólido. Estudamos o comportamento do nanotubo interno em relação à estabilidade do nanotubo externo quando submetido a pressão e suas implicações durante o colapso da estrutura. O efeito de incluir uma espécie no interior de um nanotubo também é discutido com respeito ao colapso. O comportamento eletrônico, vibracional e estrutural das moléculas de Bromo intercaladas nos canais intersticiais 1D dos feixes de nanotubos foi estudado e observamos que a formação de poliânions do tipo Brn (n=2,3,5) é preferencial mesmo no regime de altas pressões. Além disso, o comportamento dos poliânions é profundamente modificado quando a estrutura atinge o colapso com o aumento da pressão aplicada. Apresentaremos também resultados de nanotubos de carbono de parede dupla sob condições de altas pressões e altas temperaturas. Estes estudos foram conduzidos com o objetivo de obter novas estruturas de carbono através do colapso da estrutura e/ou criação de ligações sp3 entre os tubos, o qual é potencializado pelo aumento da temperatura em condições extremas de pressão. Diferentes experimentos foram realizados usando a célula Paris-Edinburg que é capaz de submeter um sistema à um ponto específico do diagrama de fase p-T (pressão x Temperatura) ao mesmo tempo. Nossos resultados foram discutidos em termos do conhecimento atual na área e contribui com pontos adicionais no diagrama de fase para nanotubos de carbono. Diversas estruturas como grafite desordenado, diamante, nanotubos estruturalmente modificados e possíveis formações polimerizadas de nanotubos foram discutidas em termos dos resultados obtidos neste trabalho. Esses idéias servem de base para a possibilidade de criação de estruturas híbridas com os nanotubos de paredes duplas. Neste caso, o tubo externo participaria ativamente através do ambiente químico externo a fim de obter ligações do tipo sp3 e o tubo interno poderia servir de suporte para o sistema como um todo. / Dans cette thèse, nous présentons les résultats de l’étude nanotubes de carbone double parois soumis à l’application de la pression hydrostatique à l’aide d’outils expérimentaux et théoriques. En utilisant des calculs théoriques ab initio et avec des potentiels classique nous avons étudié l’évolution structurelle sous pression de nanotubes de carbone et ses propriétés électroniques et vibrationnels. En parallèle, nous avons étudié des échantillons de nanotubes de carbone en fagot (bundles) pures et chimiquement modifiés par le dopage (intercalation) avec des molécules de brome (Br2) lorsqu’ils sont étés soumis à des conditions extrêmes de pression très élevée en utilisant principalement la spectroscopie Raman. Des mesures de microscopie de transmission électronique (TEM), l’analyse de composition chimique par spectroscopie de photon-électron par rayons-X (XPS) et l’absorption des rayons X (XAS) ont également été utilisées pour donner une interprétation complémentaire. Ces résultats donnent une meilleure compréhension des effets chimiques sur le comportement de la structure des nanotubes de carbone sous contraintes de pression élevées. Les propriétés vibrationnels de l’échantillon ont été observées jusqu’à des pressions de 30 GPa en utilisant deux milieux de transmission de la pression: l’huile de paraffine et du NaCl solide. En utilisant le spectre Raman des modes tangentiels (G band) et des modes de respirations radial (RBM), nous étudions le comportement du nanotube interne par rapport à la stabilité du nanotube externe lorsqu’il est soumis à la pression et ses implications pour le renforcement de la structure. L’effet de l’inclusion d’une espèce à l’intérieur d’un nanotube est également discuté par rapport à la stabilité du tube. Les propriétés électroniques, vibrationnels et structurales des molécules de brome intercalés dans les canaux interstitiels des fagot de nanotubes 1D a été étudié et on a observé que la formation de chaines de poly anions Brn (n = 2,3,5) est préférée même sous haute pression. Le comportement des polyanions est encore profondément modifié lorsque la structure atteint la pression critique de collapse. Nous présentons ensuite les résultats de l’étude nanotubes de carbone double-parois soumis à des conditions de pressions et températures très élevés. Ces travaux ont été conduits avec l’objectif d’obtenir de nouvelles structures à base de de carbone grâce à le renforcement de la structure par le tube interne et en créant des liaisons sp3 entre les tubes, ce que peut être stimulé par l’augmentation de température dans des conditions extrêmes de pression. Différentes expériences ont été réalisées à l’aide de la cellule Paris-Edimbourg qui peut conduire le système `a un point spécifique du diagramme de phase pT (pression x température). Nos résultats ont été discutés par rapport les connaissances actuelles avec une compilation des études récents pour les nanotubes de carbone soumis à des conditions extrêmes. Plusieurs structures ont été proposées avec les nanotubes double-parois avec la possible formation aussi du graphite désordonné, diamant, nanotubes structurellement modifiés ou des nanotubes polymérises. Ces différentes structures ont été discutées en termes des résultats obtenus dans ce travail après la caractérisation des échantillons traités dans la presse Paris-Edinburg. Ces idées sont le fondement de la possibilité de créer des nouvelles structures hybrides à base des nanotubes de carbone à double-parois. Dans ce cas, le tube externe participe activement pour le system à l’environnement chimique externe peut être à travers des liaisons sp3 et le tube interne pourrait servir de support mécanique pour tout le système.
56

Impact of cover cropping on arthropods in corn on the western high plains

Davis, Holly N. January 1900 (has links)
Master of Science / Department of Entomology / Larry L. Buschman, Lawrent Buschman / This study evaluated whether using a cover crop with corn would increase the threat from spider mites in western Kansas because cover crops may serve as a winter host. This study also evaluated whether a cover crop could affect corn rootworm and other ground dwelling arthropods in the cornfield. In the first study, downy brome, Bromus tectorum L., was used as the winter cover crop. There were two trials repeated for three years each. Each trial included: two amounts of irrigation, downy brome, and herbicide to control weeds. In the first trial there were no significant differences in corn rootworm, Diabrotica virgifera LeConte, damage across treatments, because there were no differences in brome residue across the treatments. In the second trial, corn rootworm damage was significantly more in plots with higher amounts of downy brome residue. There were no differences in numbers of spider mites: Banks grass mites, Oligonychus pratensis (Banks) or twospotted spider mites, Tetranychus urticae Koch, across treatments. Spider mite populations appeared to be suppressed by the predatory mite Neoseiulus spp., which also overwintered in the cover crop. Corn rootworm samples taken from a no-till irrigation experiment were variable among irrigation treatments but indicated a trend for rootworm damage to increase with increasing irrigation. In the second study, winter wheat, Triticum aestivum L., was used as the winter cover crop. There were three trials repeated for three years each. Each trial included two amounts of irrigation and winter wheat and three amounts of herbicide to control weeds. Upon completion of the agronomy trials, the plots were split into two subplots and one was tilled. Pitfall traps were installed to capture ground dwelling arthropods: (Coleoptera: Carabidae), wolf spiders (Araneae: Lycosidae) and crickets (Orthoptera: Gryllidae). Four carabid genera were more common under no-till conditions. One was more common in tilled plots. Five carabid genera were more common in plots with a history of high weed densities. Two carabid genera were more numerous in plots with the history of a cover crop. Crickets were more common under no-till conditions. Wolf spiders were more common in no tillage with a history of a cover crop.
57

Forage Yield and Quality of Binary Grass-Legume Mixtures of Tall Fescue, Orchardgrass, Meadow Brome, Alfalfa, Birdsfoot Trefoil, and Cicer Milkvetch

Cox, Steven R. 01 May 2013 (has links)
Rising fertilizer prices have led a return to the use of grass-legume mixtures to reduce N costs and improve pasture productivity. The objective of this study was to determine optimal species combinations of binary grass-legume mixtures to improve forage production and pasture nutritive value in irrigated pastures of the Intermountain West. The study was conducted at the Utah State University Intermountain Pature Research Facility near Lewiston, UT. Tall Fescue (TF), Orchardgrass (OG), and meadow brome (MB) were grown with alfalfa (ALF), birdsfoot trefoil (BFTF), and cicer milkvetch (CMV) in legume-grass mixes and monocultures at planting ratios of 25:75, 50:50, 75:25. Grass monocultures were fertilized with 0 (0 N), 67 (67 N), or 134 kg N ha-1 (134 N). Forage was harvested four times each season during 2011-2012. Forage of the mixtures and monocultures from the first and third harvests was analyzed for crude protein (CP) and neutral-detergent fiber (NDF). Average forage production of the unfertilized TF, MB, and OG monocultures was 11.03, 9.76, and 8.10 Mg ha-1, respectively. TF-ALF, OG-ALF, and MB-ALF grass-legume mixes averaged 24.0, 35.0, and 41.0% higher forage production than their respective unfertilized grass monocultures. The grass-legume mixtures with the highest CP were MB-ALF 159, TF-ALF 159, and TF-OG-159 g kg-1 and average 59, 43 and 51% higher than their respective unfertilized grass monocultures. Likewise, the mixtures with the lowest NDF were OG-ALF 453 g kg-1, OG-BFTF 469 g kg-1, and MB-ALF 480 g kg-1. These mixtures had 10, 7, and 18% lower NDF than their respective unfertilized grass monocultures. Individual harvests had similarly higher yields and CP, with lower NDF for the mixtures than the unfertilized grass monocultures. The grass-legume mixture with the 50:50 planting ratio were most productive and had high forage quality. The grass-legume mixtures had similar forage production as the grass monocultures at 134 kg N ha-1. The grass-legume mixtures also had higher CP and lower NDF than the grass monocultures. Cicer milkvetch did not perform well in irrigated pastures. Grass-legume mixtures with ALF and BFTF can be used to replace commercial N while increasing forage nutritive value.
58

Playgoing in Early Modern London After Shakespeare (1616-1642)

Tröger, Tim-Christoph 05 September 2016 (has links)
Das Hauptziel der Arbeit ist die Rekonstruktion der sozialen und kulturellen Rahmenbedingungen, unter denen dramatische Stücke zwischen Shakespeares Tod im Jahre 1616 und der Schließung der Theater im Jahre 1642 produziert wurden. Mithilfe einer Vielfalt zeitgenössischer Quellen erfolgt eine Rekonstruktion des historischen Kontextes aus zeitgenössischer Sicht. Die Arbeit analysiert wer die Menschen waren, für die Shakespeares Nachfolger ihre Stücke für die öffentlichen und privaten Bühnen Londons schrieben. Des Weiteren stellt die Arbeit dar, wie der Gang ins Theater in einer bisher von der Forschung nur wenig beachteten Epoche aussah und zeigt auf, wer genau in diesen Jahren ins Theater ging und wie diese Zuschauer und ihre Erwartungen an die Bühne durch eine Vielzahl externer und stetig wechselnder kultureller, politischer und sozialer Faktoren (z.B. Bärenhatzen, Prostitution, Hinrichtungen etc.) beeinflusst wurden. Zudem liegt ein weiteres Hauptaugenmerk der Arbeit darauf, wie die drei Autoren John Ford, Richard Brome und James Shirley in den Prologen und Epilogen zu ihren Stücken die Gegenwart der Zuschauer thematisiert und die Entwicklung des frühneuzeitlichen Theaters metadramatisch und selbstreflexiv angesprochen haben.
59

Approches de synthèse du tricycle ABC du FR182877.

Funel, Jacques-Alexis 11 October 2004 (has links) (PDF)
Ce manuscrit présente les travaux effectués à l'Ecole Polytechnique (novembre 2001- septembre 2004) sous la direction du Dr. Joëlle Prunet dans le laboratoire de Synthèse Organique dirigé par le Pr. Samir Zard. Il détaille plusieurs approches de synthèse du tricycle ABC du FR182877, un nouvel agent antimitotique naturel découvert en 1998. Après avoir présenté le FR182877 ainsi que les différents approches de la littérature en vue de sa synthèse totale, la rétrosynthèse envisagée pour construire le système tricyclique ABC selon une stratégie impliquant une réaction de Diels-Alder intermoléculaire et une réaction de métathèse ène-yne sera détaillée (Chapitre I). La réaction de métathèse ène-yne fera ensuite l'objet d'une étude bibliographique (Chapitre II) puis sa mise en place dans le contexte d'une approche de synthèse du cycle A du FR182877 sera décrite (Chapitre III). Le chapitre suivant (Chapitre IV) concerne la seconde étape-clé du schéma rétrosynthétique : la réaction de Diels-Alder intermoléculaire et se concentre sur une étude méthodologique réalisée dans le but de comprendre l'origine d'une sélectivité inattendue dans l'étape de cycloaddition. Le chapitre V expose les résultats obtenus dans le contexte d'une seconde rétrosynthèse du FR182877 fondée sur une réaction d'addition conjuguée de Michael. Enfin, dans la continuité de ces travaux, un accès rapide et original à des systèmes tricycliques fonctionnalisés fondé sur une succession de réactions de métathèse en tandem a été développé et sera exposé dans le dernier chapitre (Chapitre VI). Les protocoles expérimentaux ainsi que la description des produits synthétisés seront présentés dans la partie expérimentale, rédigée en anglais.
60

Modification des propriétés du polypropylène par mise en oeuvre réactive/Modification of polypropylene properties by reactive processing

Henry, Gaëtan 26 April 2006 (has links)
Ce travail s'inscrit dans le cadre d'un projet soutenu par la Région wallonne et a été réalisé en collaboration entre les unités de Chimie Organique et Médicinale (CHOM), de Chimie Structurale et des Mécanismes Réactionnels (CSTR), et de Chimie et Physique des Hauts Polymères (POLY). Il concerne la modification des propriétés du polypropylène (PP) isotactique par mise en œuvre réactive, et plus particulièrement le contrôle de sa cristallinité par l'action d'un composé bromé (N-bromosuccinimide) en présence d'un initiateur de radicaux libres à haute température (entre 180 et 260°C). L'objectif principal de cette étude est de parvenir à identifier et à contrôler les modifications induites au sein des produits, ce qui implique une compréhension fine des mécanismes chimiques intervenant lors de la mise en œuvre réactive du PP. Ces connaissances permettraient en outre de substituer la N-bromosuccinimide (qui génère des sous-produits toxiques et polluants) par un autre additif en vue d'une meilleure valorisation du procédé et des produits. La stratégie repose sur une double approche, basée d'une part sur une étude des divers paramètres qui influencent la réaction sur polymère, et d'autre part sur la synthèse d'un composé modèle du PP : le 2,4,6,8,10-pentaméthylundécane (PMU). Par extrusion réactive du polymère, nous avons obtenu des PP à cristallinité contrôlée (PPCC ; de semi-cristallin à amorphe), dont certains présentent un caractère élastomère marqué. Des études effectuées principalement par analyse thermique et par résonance magnétique nucléaire ont permis de corréler ces propriétés macroscopiques à une microstructure à stéréoblocs isotactiques/atactiques (épimérisation des carbones tertiaires du PP), combinée à la présence de branchements longs (recombinaison de macroradicaux). Par ailleurs, nous avons mis en évidence les différents paramètres susceptibles d'influencer la réaction d'épimérisation du PP. Bien que les informations découlant de ces études nous aient permis de proposer les principaux mécanismes qui entrent en jeu lors de la réaction, seule une étude sur composé modèle peut néanmoins donner accès aux méthodes d'analyses nécessaires à la confirmation de ces mécanismes. Nous avons par conséquent entrepris la synthèse d'un oligomère de propylène pour permettre cette étude sur composé modèle. La synthèse du PMU telle que rapportée dans la littérature s'est avérée plus difficile que prévu, principalement du fait d'un manque de reproductibilité au niveau de l'étape clé. Nous avons donc établi une voie de synthèse originale permettant l'obtention du PMU (mélange de stéréoisomères) avec un rendement global de 45% sur 7 étapes (à l'échelle de plusieurs grammes de produit). En outre, cette voie nous a donné accès au 6-hydroxyméthyl-2,4,8,10-tétraméthylundécane et au 6-p-toluènesulfonyloxyméthyl-2,4,8,10-tétraméthylundécane, pour lesquels des techniques chromatographiques ont permi une séparation des diastéréoisomères. La transposition de ces expériences à plus grande échelle permettra d'envisager l'obtention du (4R,6s,8S)-PMU, en vue de futures études mécanistiques relatives à l'épimérisation du PP de configuration initialement isotactique. / This work is part of a project supported by the Walloon Region, and it was performed in collaboration between the Chimie Organique et Médicinale (CHOM), Chimie Structurale et des Mécanismes Réactionnels (CSTR), and Chimie et Physique des Hauts Polymères (POLY) laboratories. Its object is the modification of the isotactic polypropylene (PP) properties by reactive processing, and more especially the control of PP crystallinity by means of a brominated additive (N-bromosuccinimide) in presence of a free radical initiator at high temperatures (between 180 and 260°C). The main objective of this study is to identify and to control the modifications induced in the products, which implies a fine understanding of the chemical mechanisms occuring during the PP reactive processing. This knowledge would allow us, subsequently, to substitute another additive for the N-bromosuccinimide (which yields toxic and polluting by-products), in order to achieve a better applicability of both the process and the products. The strategy relies on a double approach : on one side, on a study of the various parameters affecting the reaction on the polymer, and on the other side on the synthesis of a model compound of PP : 2,4,6,8,10-pentamethylundecane (PMU). By means of reactive extrusion of the polymer, we obtained controlled crystallinity PP's (from semi-crystalline to amorphous), including some with an elastomeric behaviour. Studies carried out mainly by thermal analysis and nuclear magnetic resonance allowed us to correlate these macroscopic properties to an isotactic/atactic stereoblock microstructure (epimerization of the PP tertiary carbons), combined with the presence of long chain branchings (recombination of macroradicals). Moreover, we highlighted the various parameters that are able to influence the yield of the epimerization reaction. Even if the informations arising from these studies allowed us to propose the main mechanisms involved in the PP modification, only a mechanistic study carried out on a model compound would give us access to the characterization methods required for the confirmation of these mechanisms. We undertook, subsequently, the synthesis of a propene oligomer. The PMU synthesis, as stated in the litterature, revealed itself more difficult than initially foreseen, mainly due to a lack of reproducibility concerning the key step. Therefore we established a new synthesis pathway for the PMU (as a mixture of stereoisomers) with a global yield of 45% over 7 steps (multigram scale). Moreover, this pathway gave us access to 6-hydroxymethyl-2,4,8,10-tetramethylundecane and 6-p-toluenesulfonyloxymethyl-2,4,8,10-tetramethylundecane, for which chromatographic techniques allowed a separation of the diastereoisomers. The transposition of these experiments on a larger scale would allow us to obtain the (4R,6s,8S)-PMU for future mechanistic studies relative to the epimerization reaction of initially isotactic PP.

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