865 resultados para stereoselective fungal transformation


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Action research is a methodology that supports practitioner research. This study is an exploration of one researcher's practice using the living-theory approach to action research. Initially, my focus was to improve my practice by asking how I can facilitate transformative learning experiences with the teachers with whom I work. As part of this search, I examined the contradictions between my espoused and implicit values. In keeping with the evolving nature of my inquiry, I unveiled the telos that constituted the impetus for my search, which began as a tension about the quality of my interactions and ended as a quest to find my voice among the others'. I used personal narratives, journal entries, a videotaping session, interactions with critical friends and interviews with colleagues and administrators to engage in a process of continuing self- and interactive reflection. Throughout my study, I explored how theoretical concepts intertwine with personal experiences. In the final chapter, I share the possible connections between my living educational theory and a more general theory of transformative learning. I conclude my study with a look at the transformation process I underwent as a result of the study and the new questions I formulated as I began the action research spiral again.

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The purpose of the study was to determine the ability of certain fungi to biotransform morphine alkaloids into medicinally relevant intermediates. Fungal strains screened for their ability to affect biotransformation of morphine alkaloids include Cunninghamella echinulata, Helicostylum pirijorme, Pycnoporus sanguinea, Pycnoporus cinnabarina, Curvularia lunata and Sporotrichum sulfurescens. The research demonstrated that Cunninghamella echinulata N-demethylated thebaine, hydrocodone, codeine, oripavine and oxycodone into corresponding nor-compounds in varying yields. The study further focused on the characterization of the enzyme responsible for the biotransformation of thebaine into northebaine by Cunninghamella echinulata. The study clearly showed that incubation of the fungal culture with thebaine over a period of 48 hours was required to activate the biotransformation process. The biotransformation studies with [14C] labeled thebaine showed that Ndemethylation by Cunningham ella echinulata does not involve O-demethylation followed by methyl group transfer as suggested in previous studies.

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Compounds containing the pyrrolidine moiety are key substructures of compounds with biological activity and organocatalysts. In particular, annulated chiral pyrrolidines with alpha stereogenic centers have aldostereone synthase inhibition activity. In addition, 5-substituted pyrroloimidazol(in)ium salts precursors to N-heterocyclic carbene (NHC) precatalysts are rare due to a lack of convenient synthetic routes to access them. In this thesis is described a rapid synthesis of NHC precursors and a possible route to 5-substituted pyrroloimidazole biologically active compounds. The method involves the preparation of chiral saturated and achiral unsaturated pyrrolo[I,2- c]imidazol-3-ones from N-Cbz-protected t-Butyl proline carboxamide. The resulting starting materials may be used to prepare the target chiral annulated imidazol(in)ium products by a two-step sequence involving first stereoselective lithiation-substitution, followed by POCh induced salt formation.

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This thesis explored the development of several methodologies for the stereoselective construction of ligand frameworks and some of their applications. The first segment concerns the application of an enantioselective lithiation at an Sp3_ hybridized position adjacent to nitrogen by means of the widely used and typically highly effective enantioselective lithiation with ( -)-sparteine. This investigation was intended to develop a method to install chirality into a system that would be converted into a family of diaminoylidenes for use as phosphine mimics in transition metal catalysis or as nucleophilic reagents. Molecular modeling of the system revealed some key interactions between the substrate and (-)-sparteine that provided general insight into the diamine's mode of action and should lend some predictive value to its future applications. The second portion focuses on the development of methods to access 1,2- disubstituted aminoferrocenes, an underexplored class of metallocenes possessing planar chirality. Two routes were examined involving a diastereoselective and an enantioselective pathway, where the latter method made use of the first BF3-mediated lithiation-substitution to install planar chirality. Key derivatives such as 1,2- aminophosphines, made readily accessible by the new route, were evaluated as ligands for Pd(II), Pt(II) and Ir(I). These complexes show activity in a number of transformations with both achiral and prochiral substrates. Optimization experiments were conducted to prepare enantiomerically enriched 2-substituted-I-aminoferrocenes by direct asymmetric lithiation of BF3-coordinated tertiary aminoferrocenes. A predictive computational model describing the transition state of this reaction was developed in collaboration with Professor Travis Dudding's group (Department of Chemistry, Brock University). The predicted stereochemistry of the process was confirmed by single-crystal X-ray analysis of a 2-phosphino-l-dimethylaminoferrocene derivative. Enantiomerically pure samples of the aminophosphine ligands derived from this new process have given promising preliminary results in the enantioselective hydrogenation of prochiral alkenes and warrant further stUdy in metal-mediated catalysis.

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A significant number of adults in adult literacy programs in Ontario have specific learning difficulties. This study sought to examine the holistic factors that contributed to these learners achieving their goals. Through a case study design, the data revealed that a combination of specific learning methods and strategies, along with particular characteristics of the instructor, participant, and class, and the evidence of self-transformation all seemed to contribute to the participant's success in the program. Instructor-directed teaching and cooperative learning were the main learning methods used in the class. General learning strategies employed were the use of core curriculum and authentic documents, and using phonics, repetition, assistive resources, and using activities that appealed to various learning styles. The instructor had a history of both professional development in the area of learning disabilities as well as experience working with learners who had specific learning difficulties. There also seemed to be a goodness of fit between the participant and the instructor. Several characteristics of the participant seemed to aid in his success: his positive self-esteem, self-advocacy skills, self-determination, self-awareness, and the fact that he enjoyed learning. The size (3-5 people) and type of class (small group) also seemed to have an impact. Finally, evidence that the participant went through a self-transformation seemed to contribute to a positive learner identity. These results have implications for practice, theory, and further research in adult education.

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Several species of the insect pathogenic fungus Metarhizium are associated with certain plant types and genome analyses suggested a bifunctional lifestyle; as an insect pathogen and as a plant symbiont. Here we wanted to explore whether there was more variation in genes devoted to plant association (Mad2) or to insect association (Mad1) overall in the genus Metarhizium. Greater divergence within the genus Metarhizium in one of these genes may provide evidence for whether host insect or plant is a driving force in adaptation and evolution in the genus Metarhizium. We compared differences in variation in the insect adhesin gene, Mad1, which enables attachment to insect cuticle, and the plant adhesin gene, Mad2, which enables attachment to plants. Overall variation for the Mad1 promoter region (7.1%), Mad1 open reading frame (6.7%), and Mad2 open reading frame (7.4%) were similar, while it was higher in the Mad2 promoter region (9.9%). Analysis of the transcriptional elements within the Mad2 promoter region revealed variable STRE, PDS, degenerative TATA box, and TATA box-like regions, while this level of variation was not found for Mad1. Sequences were also phylogenetically compared to EF-1a, which is used for species identification, in 14 isolates representing 7 different species in the genus Metarhizium. Phylogenetic analysis demonstrated that the Mad2 phylogeny is more congruent with 59 EF-1a than Mad1. This would suggest that Mad2 has diverged among Metarhizium lineages, contributing to clade- and species-specific variation, while it appears that Mad1 has been largely conserved. While other abiotic and biotic factors cannot be excluded in contributing to divergence, these results suggest that plant relationships, rather than insect host, have been a major driving factor in the divergence of the genus Metarhizium.

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Several species of the insect pathogenic fungus Metarhizium are associated with certain plant types and genome analyses suggested a bifunctional lifestyle; as an insect pathogen and as a plant symbiont. Here we wanted to explore whether there was more variation in genes devoted to plant association (Mad2) or to insect association (Mad1) overall in the genus Metarhizium. Greater divergence within the genus Metarhizium in one of these genes may provide evidence for whether host insect or plant is a driving force in adaptation and evolution in the genus Metarhizium. We compared differences in variation in the insect adhesin gene, Mad1, which enables attachment to insect cuticle, and the plant adhesin gene, Mad2, which enables attachment to plants. Overall variation for the Mad1 promoter region (7.1%), Mad1 open reading frame (6.7%), and Mad2 open reading frame (7.4%) were similar, while it was higher in the Mad2 promoter region (9.9%). Analysis of the transcriptional elements within the Mad2 promoter region revealed variable STRE, PDS, degenerative TATA box, and TATA box-like regions, while this level of variation was not found for Mad1. Sequences were also phylogenetically compared to EF-1a, which is used for species identification, in 14 isolates representing 7 different species in the genus Metarhizium. Phylogenetic analysis demonstrated that the Mad2 phylogeny is more congruent with 59 EF-1a than Mad1. This would suggest that Mad2 has diverged among Metarhizium lineages, contributing to clade- and species-specific variation, while it appears that Mad1 has been largely conserved. While other abiotic and biotic factors cannot be excluded in contributing to divergence, these results suggest that plant relationships, rather than insect host, have been a major driving factor in the divergence of the genus Metarhizium.

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While nitrogen is critical for all plants, they are unable to utilize organically bound nitrogen in soils. Therefore, the majority of plants obtain useable nitrogen through nitrogen fixing bacteria and the microbial decomposition of organic matter. In the majority of cases, symbiotic microorganisms directly furnish plant roots with inorganic forms of nitrogen. More than 80% of all land plants form intimate symbiotic relationships with root colonizing fungi. These common plant/fungal interactions have been defined largely through nutrient exchange, where the plant receives limiting soil nutrients, such as nitrogen, in exchange for plant derived carbon. Fungal endophytes are common plant colonizers. A number of these fungal species have a dual life cycle, meaning that they are not solely plant colonizers, but also saprophytes, insect pathogens, or plant pathogens. By using 15N labeled, Metarhizium infected, wax moth larvae (Galleria mellonella) in soil microcosms, I demonstrated that the common endophytic, insect pathogenic fungi Metarhizium spp. are able to infect living soil borne insects, and subsequently colonize plant roots and furnish ts plant host with useable, insect-derived nitrogen. In addition, I showed that another ecologically important, endophytic, insect pathogenic fungi, Beauveria bassiana, is able to transfer insect-derived nitrogen to its plant host. I demonstrated that these relationships between various plant species and endophytic, insect pathogenic fungi help to improve overall plant health. By using 13C-labeled CO2, added to airtight plant growth chambers, coupled with nuclear magnetic resosnance spectroscopy, I was able to track the movement of carbon from the atmosphere, into the plant, and finally into the root colonized fungal biomass. This indicates that Metarhizium exists in a symbiotic partnership with plants, where insect nitrogen is exchanged for plant carbon. Overall these studies provide the first evidence of nutrient exchange between an insect pathogenic fungus and plants, a relationship that has potentially useful implications on plant primary production, soil health, and overall ecosystem stability.

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The aim of this paper is to demonstrate that, even if Marx's solution to the transformation problem can be modified, his basic conclusions remain valid. the proposed alternative solution which is presented hare is based on the constraint of a common general profit rate in both spaces and a money wage level which will be determined simultaneously with prices.

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Un atout majeur des organisations consiste en leur capacité à créer et exploiter l’information et les connaissances, capacité déterminée entre autres par les comportements informationnels. Chargés de décisions stratégiques, tactiques et opérationnelles, les cadres intermédiaires sont au cœur du processus de création des connaissances, et leurs comportements informationnels doivent être soutenus par des systèmes d’information. Toutefois, leurs comportements informationnels sont peu documentés. La présente recherche porte sur la modélisation des comportements informationnels de cadres intermédiaires d’une organisation municipale. Plus spécifiquement, elle examine comment ces cadres répondent à leurs besoins d’information courante dans le contexte de leurs activités de gestion, c’est-à-dire dans leur environnement d’utilisation d’information. L’étude répond aux questions de recherche suivantes : (1) Quelles sont les situations problématiques auxquelles font face les cadres intermédiaires municipaux ? (2) Quels sont les besoins informationnels exprimés par les cadres intermédiaires municipaux lors de situations problématiques ? (3) Quelles sont les sources d’information qui soutiennent les comportements informationnels des cadres intermédiaires municipaux ? Cette recherche descriptive s’inscrit dans une approche qualitative. Les 21 cadres intermédiaires ayant participé à l’étude proviennent de deux arrondissements d’une municipalité québécoise fusionnée en 2002. Les modes de collecte de données sont l’entrevue en profondeur en personne et l’observation directe auprès de ces cadres, et la collecte de documentation pertinente. L’incident critique est utilisé comme technique de collecte de données et comme unité d’analyse. Les données recueillies font l’objet d’une analyse de contenu qualitative basée sur la théorisation ancrée. Les résultats indiquent que les rôles de gestion proposés dans les écrits pour les cadres supérieurs s’appliquent aussi aux cadres intermédiaires, bien que le rôle conseil ressorte comme étant particulier à ces derniers. Ceux-ci ont des responsabilités de gestion aux trois niveaux d’intervention opérationnel, tactique et stratégique, bien qu’ils œuvrent davantage au plan tactique. Les situations problématiques dont ils sont chargés s’inscrivent dans l’environnement d’utilisation d’information constitué des composantes suivantes : leurs rôles et responsabilités de gestion et le contexte organisationnel propre à une municipalité en transformation. Les cadres intermédiaires ont eu à traiter davantage de situations nouvelles que récurrentes, caractérisées par des sujets portant principalement sur les ressources matérielles et immobilières ou sur des aspects d’intérêt juridique, réglementaire et normatif. Ils ont surtout manifesté des besoins pour de l’information de nature processuelle et contextuelle. Pour y répondre, ils ont consulté davantage de sources verbales que documentaires, même si le nombre de ces dernières reste élevé, et ont préféré utiliser des sources d’information internes. Au plan théorique, le modèle de comportement informationnel proposé pour les cadres intermédiaires municipaux enrichit les principales composantes du modèle général d’utilisation de l’information (Choo, 1998) et du modèle d’environnement d’utilisation d’information (Taylor, 1986, 1991). L’étude permet aussi de préciser les concepts d’« utilisateur » et d’« utilisation de l’information ». Au plan pratique, la recherche permet d’aider à la conception de systèmes de repérage d’information adaptés aux besoins des cadres intermédiaires municipaux, et aide à évaluer l’apport des systèmes d’information archivistiques à la gestion de la mémoire organisationnelle.

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RÉSUMÉ L‘hébergement en centre de soins de longue durée d'un parent âgé atteint de démence marque une transition pour les personnes qui occupent un rôle d’aidant familial principal. Ces personnes, principalement des femmes, poursuivent leur engagement après l’hébergement et souhaitent être impliquées dans les décisions concernant les soins offerts à leur parent. Souvent l'hébergement survient au moment où la personne âgée n'est plus en mesure, compte tenu de ses déficiences cognitives, d'exprimer clairement ses besoins; les aidantes accordent alors une place centrale au rôle de représentante de leur proche hébergé. Cette étude avait pour but d’expliquer la transformation du rôle de représentante chez des aidantes familiales dont le parent atteint de démence vit dans un centre d’hébergement et de soins de longue durée (CHSLD). La méthode qualitative de la théorisation ancrée a été retenue pour expliquer ce processus social. Les résultats obtenus reposent sur 14 entrevues en profondeur réalisées auprès de filles dont le parent atteint de démence était hébergé depuis plus de six mois dans un CHSLD. Ces aidantes ont été sélectionnées selon une procédure d’échantillonnage théorique et l’analyse des données a été réalisée à partir de la transcription intégrale des entrevues en suivant trois niveaux d'analyse, soit la codification ouverte, axiale et sélective. Une proposition théorique, générée par voie inductive, met en lumière trois processus intermédiaires interreliés expliquant la transformation du rôle de représentante pendant l’hébergement du proche : 1) l’intégration dans le milieu ; 2) l’évaluation de la qualité des soins et 3) le développement de la confiance envers le milieu d’hébergement. Plus précisément, les aidantes déploient différentes stratégies d’intégration dans le milieu d’hébergement, soit l’établissement de relations de réciprocité et d’une collaboration avec le personnel soignant, ainsi que l’utilisation d’un style de communication diplomatique. Parallèlement, elles évaluent la qualité des soins en trois étapes : jugement, pondération et action. Finalement, une relation de confiance avec les membres du personnel de l’établissement se développe en lien avec cinq facteurs spécifiques, soit les premières impressions, la comparaison avec d’autres CHSLD, l’intérêt démontré par le personnel envers le proche, le fait d’être entendue et prise au sérieux et la transparence du milieu d’hébergement. Ces trois processus contribuent au bien-être du parent hébergé et à celui de l’aidante. Le développement de la confiance étant associé aux deux autres processus intermédiaires ainsi qu’au bien-être de l’aidante, il est le processus central de la théorie contextuelle qui émerge de cette recherche. Cette étude contribue au développement des connaissances, notamment en fournissant plusieurs éléments inédits de compréhension du processus de transformation du rôle de représentante des aidantes familiales, de même que des pistes pour soutenir ces aidantes dont le parent, souffrant de démence, n’est plus en mesure de prendre des décisions. La théorie contextuelle proposée dans le cadre de cette étude constitue les prémices d’une théorie de niveau intermédiaire portant sur le rôle de représentant des aidants familiaux dans le contexte plus général du système de santé. Des études réalisées dans d’autres contextes de soins et auprès d’aidants de proches vulnérables ayant d’autres types d’affections sont ainsi recommandées.