Polyhomologation is a powerful method to prepare polyethylene-based materials with controlled molecular weight, topology and composition. This dissertation focuses on the discovery of new synthetic routes to prepare polyethylene-based macromolecular architectures by combining polyhomologation with highly orthogonal and efficient linking reactions such as Diels Alder, copper-catalyzed azide-alkyne cycloaddition (CuAAC), and Glaser. Taking advantage of functionalized polyhomologation initiators, as well as of the efficient coupling chemistry, we were able to synthesize various types of polymethylene (polyethylene)-based materials with complex architectures including linear co/terpolymers, graft terpolymers, and tadpole copolymers. In the first project, a facile synthetic route towards well-defined polymethylene-based co/terpolymers, by combining the anthracene/maleimide Diels–Alder reaction with polyhomologation, is presented. For the synthesis of diblock copolymers the following approach was applied: (a) synthesis of α-anthracene-ω-hydroxy-polymethylene by polyhomologation using tri (9 anthracene-methyl propyl ether) borane as the initiator, (b) synthesis of furan-protected-maleimide-terminated poly(ε-caprolactone) or polyethylene glycol and (c) Diels–Alder reaction between anthracene and maleimide-terminated polymers. In the case of triblock terpolymers, the α-anthracene-ω-hydroxy polymethylene was used as a macroinitiator for the ring-opening polymerization of D, L-lactide to afford an anthracene-terminated PM-b-PLA copolymer, followed by the Diels–Alder reaction with furan-protected maleimide-terminated poly (ε-caprolactone) or polyethylene glycol to give the triblock terpolymers. The synthetic methodology is general and potentially applicable to a range of polymers. The coupling reaction applied in the second project of this dissertation was copper-catalyzed “click” cycloaddition of azides and alkynes (CuAAC). Novel well-defined polyethylene-based graft terpolymers were synthesized via the “grafting onto” strategy by combining nitroxide-mediated radical polymerization (NMP), polyhomologation and copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC). Three steps were involved in this approach: (a) synthesis of alkyne-terminated polyethylene-b-poly(ε-caprolactone) (PE-b-PCL-alkyne) block copolymers (branches) by esterification of PE-b-PCL-OH with 4-pentynoic acid; the PE-b-PCL-OH was obtained by polyhomologation of dimethylsulfoxonium methylide to afford PE-OH, followed by ring opening polymerization of ε-caprolactone using PE-OH as a macroinitiator (b) synthesis of random copolymers of styrene (St) and 4-chloromethylstyrene (4-CMS) with various CMS contents, by nitroxide-mediated radical copolymerization (NMP), and conversion of chloride to azide groups by reaction with sodium azide (NaN3) (backbone) and (c) “click” linking reaction to afford the PE-based graft terpolymers. This method opens up new routes for the creation of polyethylene-based graft terpolymers by a combination of polyhomologation, NMP and CuAAC. The third project deals with the synthesis of polyethylene-based tadpole copolymer (c-PE)-b-PSt. Cyclic polymers represent a class of understudied polymer architecture mainly due to the synthetic challenges. Within this dissertation, a new method was reported for the synthesis of cyclic polymers in exceptionally high purity and yield. The main approaches to synthesize macrocycles are based on the end-to-end ring-closure (coupling) of homo difunctional linear precursors under high dilution. Our process relies on the preparation of well-defined linear α, ω-dihydroxy polyethylene and a bromide group at the middle of the chain through polyhomologation of ylide using functionalized initiator, followed by ATRP of styrene monomer. The two hydroxyl groups were transformed into alkyne groups, via esterification reaction, followed by Glaser reaction between terminal alkynes to afford the tadpole-shaped copolymers with PE ring and PSt tail. In Our PhD research, we also studied the self-assembly properties of the amphiphilic copolymers PM-b-PEG in aqueous solution by DLS, Cryo-TEM, and AFM. Furthermore, the critical micelle concentration (CMC) was estimated from the intensity of the pyrene emissions by the fluorescence technique. All the findings presented in this dissertation are emphasizing the utility of polyhomologation for the synthesis of well-defined polyethylene-based complex macromolecular architectures, almost impossible through other kind of polymerization including the catalytic polymerization of ethylene.

Denna uppsats använder en kvalitativ analys för att undersöka delar av anföranden i roastprogram framförda av ståuppkomikerna Fredrik Andersson, Messiah Hallberg och NikkiGlaser. Syftet med uppsatsen är att med hjälp av humorteori och forskning förstå hur hemskafenomen kan bli roliga i roast-sammanhang och vilka tekniker som kan nyttjas för att lyckasmed anföranden i roast. Uppsatsen visar på att humor är ett komplext och svårfångat fenomensom bygger mycket på tvetydighet och oväntade vändningar av perspektiv, ofta är skrattet enreaktion på något plötsligt orimligt eller olämpligt. Humorn har flertalet funktioner,exempelvis kan den vara socialt meningsskapande, gruppstärkande, terapeutisk eller ett sättatt utforska världen och nya möjligheter. Analysen visar att hemska fenomen kan bli roliganär de behandlas lekfullt i en kontext som är begränsad i tid och rum, och för att något skauppfattas som roligt behöver publiken genom leksignalering förstå att det rör sig om en lek.Analysen kommer fram till att användningen av absurditet kanske är den mest framträdandeleksignaleringen, samtidigt som den är en av de effektivaste humorteknikerna

No / The Hospital Personnel, Nursing Care and Dying Patients study, undertaken in California in the mid 1960s, generated a body of work that continues to be influential in end of life care research. Key points from the study are summarised, as are contributions from researchers who have responded to Glaser and Strauss invitation to examine further settings and, in so doing, provide data that helps refine their theory. The example of people with heart failure in the contemporary UK is considered. Changes since the 1960s in the epidemiology of chronic illness, the pattern of service provision and in social and professional attitudes have reduced the contemporary relevance of Glaser and Strauss's insights into the ceremonial and temporal order of the clinic. However their findings about awareness contexts and a reluctance to discuss prognosis remain highly relevant.

Submitted by Renata Lopes (renatasil82@gmail.com) on 2017-08-18T17:45:24Z No. of bitstreams: 1 lucastavarescardoso.pdf: 837625 bytes, checksum: 3abd29cb3035fdd6ec6e11d4ea0ae1ae (MD5) / Approved for entry into archive by Adriana Oliveira (adriana.oliveira@ufjf.edu.br) on 2017-08-24T12:02:18Z (GMT) No. of bitstreams: 1 lucastavarescardoso.pdf: 837625 bytes, checksum: 3abd29cb3035fdd6ec6e11d4ea0ae1ae (MD5) / Made available in DSpace on 2017-08-24T12:02:18Z (GMT). No. of bitstreams: 1 lucastavarescardoso.pdf: 837625 bytes, checksum: 3abd29cb3035fdd6ec6e11d4ea0ae1ae (MD5) Previous issue date: 2017-08-03 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / A construção de campos com localização em cordas foi realizada rigorosamente há pouco mais de uma década. Nesta abordagem, os campos são operadores em algum espaço de Hilbert, e portanto não há graus de liberdade não-físicos tais como "ghosts". Além de permitir a construção de campos carregados inteiramente num espaço espaço de Hilbert, os campos com localização em cordas exibem um bom comportamento no regime ultravioleta e, entre outras características, são possíveis candidatos para descreverem consistentemente a matéria escura. No intuito de obter uma prova da renormalizabilidade em modelos perturbativos no esquema de Epstein-Glaser com campos quânticos localizados em cordas, é necessário evidenciar a liberdade que se tem ao definir produtos temporalmente ordenados do Lagrangeano de interação. Este trabalho proporciona um primeiro passo significativo nesta direção. O problema básico é a presença de um conjunto aberto de n-uplas de cordas que não podem ser cronologicamente ordenadas. Nós resolvemos este problema ao mostrar que quase todas (i.e. exceto num subconjunto de medida nula) tais configurações de cordas podem ser dissecadas num número finito de pedaços, os quais por sua vez podem ser cronologicamente ordenados. Com isso, tem-se que o produto temporalmente ordenado de fatores lineares de campos está fixo fora de um conjunto de medida nula de configurações de cordas. A construção do ordenamento temporal geométrico de cordas é feita de modo a servir para o estudo da renormalizabilidade de quaisquer teorias quânticas de campos com localização em cordas. / The construction of string-localized fields was rigorously accomplished a little over a decade ago. In this approach, the fields are operators in some Hilbert space, and therefore there are no unphysical degrees of freedom such as ghosts. In addition to allowing the construction of charged fields entirely in a Hilbert space, the string-localized fields exhibit, in general, a good behavior in the ultraviolet regime and, among other features, the class (representation) of string-localized fields with m = 0 and s = oo are possible candidates to consistently describe dark matter. In order to obtain a proof of renormalizability of perturbative models in the Epstein—Glaser scheme with string-localized quantum fields, one needs to know what freedom one has to define time-ordered products of the interaction Lagrangian. This work provides a first significant step in that direction. The basic issue is the presence of an open set of n-tuples of strings which cannot be chronologically ordered. We resolve it by showing that almost all (i.e. outside a null set) such string configurations can be dissected into finitely many pieces which can indeed be chronologically ordered. This fixes the time-ordered products of linear field factors outside a nullset of string configurations. The construction of the geometric time ordering of strings is realized in such a way that it will serve to study the renormalizability of any quantum field theories with string-localized fields

This research examined the critical thinking (CT) skills and conceptions of prospective teachers studying at Foreign Language Education Department at Middle East Technical University. In this way, the study intended to contribute to the field of curriculum and instruction by pointing to the currents status while constituting a basis for further actions in teacher education in terms CT. In this research, data analysis was carried out through both quantitative and qualitative analysis. A survey, including Student Information Form, and Watson and Glaser Critical Thinking Appraisal- Form YM Turkish version were utilized for data gathering. Data were collected from 103 prospective teachers in the junior and senior level during the Spring Semester of 2007- 2008 Academic Year. Results demonstrated that the critical thinking (CT) levels of prospective teachers assessed by WGCTA are in medium level. In addition, WGCTA-YM cannot be predicted from reported regular reading activity, CGPA, and gender. Besides, results showed that, prospective teachers make rudiment or vague statements about critical thinking activities and do not point to a common instructional activity. In terms of critical thinking definitions, prospective teachers mostly perceive CT as a cognitive skill. Furthermore, there is a common sense view of CT rather than an understanding based on literature. The results revealed that prospective teachers are short of the essential CT skills and the CT comprehension to be able to raise individuals with CT ability. Therefore, curriculum renovation movements, projects, and research studies to improve critical thinking skills in teacher education should be developed and implemented.

No description available.

Les macrocycles ont longtemps attiré l'attention des chimistes. Malgré cet intérêt, peu de méthodes générales et efficaces pour la construction de macrocycles ont été développés. Récemment, notre groupe a développé un programme de recherche visant à développer de nouvelles voies vers la synthèse de paracyclophanes et ce mémoire présente l pluspart des efforts les plus récents dans ce domaine. Traditionnellement, la synthèse de paracyclophanes rigides est facilitée par l'installation d'un groupe fonctionnel capable de contrôler la structure de la molécule en solution (ex un élément de contrôle de conformation (ECC)). Cependant, cette approche utilisant des auxiliaires exige que le ECC soit facilement installé avant macrocyclisation et facilement enlevé après la cyclisation. Le présent mémoire décrit une méthode alternative pour guider la macrocyclisations difficile à travers l'utilisation d'additifs comme ECC. Les additifs sont des hétérocycles aromatiques N-alkylé qui sont bon marché, faciles à préparer et peuvent être facilement ajoutés à un mélange de réaction et enlevés suite à la macrocyclisation par simple précipitation et de filtration. En outre, les ECCs sont recyclables. L'utilisation du nouveau ECC est démontré dans la synthèse des para-et métacyclophanes en utilisant soit la métathèse de fermeture de cycle (RCM) ou couplage de Glaser-Hay. / Macrocycles have long attracted the attention of chemists. Despite that interest, few general and efficient methods for the construction of macrocycles have been developed. Recently our group has developed a research program aimed at developing novel routes towards the synthesis of paracyclophanes and the present thesis details the most recent efforts in this area. Traditionally, the synthesis of rigid paracyclophanes is aided by the installation of functional groups capable of controlling the solution state structure of the molecules (ie. a conformational control element (CCE)). However, this auxiliary-like approach requires that the CCE be readily installed prior to macrocyclization and easily removed following the cyclization. In the present thesis describes an alternative method to guiding difficult macrocyclizations through the use of additives as CCEs is described. The additives are N-alkylated aromatic heterocycles that are cheap, easily prepared and can be easily added to a reaction mixture and removed following the macrocyclization through simple precipitation and filtration. In addition, the CCEs are recyclable. The use of the new CCEs is demonstrated in the synthesis of para- and metacyclophanes using either ring closing metathesis (RCM) or Glaser-Hay couplings.

No description available.

La réaction de macrocyclisation est une transformation fondamentale en chimie organique de synthèse. Le principal défi associcé à la formation de macrocycles est la compétition inhérente avec la réaction d’oligomérisation qui mène à la formation de sousproduits indésirables. De plus, l’utilisation de conditions de dilutions élevées qui sont nécessaires afin d’obtenir une cyclisation “sélective”, sont souvent décourageantes pour les applications à l’échelle industrielle. Malgré cet intérêt pour les macrocycles, la recherche visant à développer des stratégies environnementalement bénignes, qui permettent d’utiliser des concentrations normales pour leur synthèse, sont encore rares. Cette thèse décrit le développement d’une nouvelle approche générale visant à améliorer l’efficacité des réactions de macrocyclisation en utilisant le contrôle des effets de dilution. Une stratégie de “séparation de phase” qui permet de réaliser des réactions à des concentrations plus élevées a été developpée. Elle se base sur un mélange de solvant aggrégé contrôlé par les propriétés du poly(éthylène glycol) (PEG). Des études de tension de surface, spectroscopie UV et tagging chimique ont été réalisées afin d’élucider le mécanisme de “séparation de phase”. Il est proposé que celui-ci fonctionne par diffusion lente du substrat organique vers la phase ou le catalyseur est actif. La nature du polymère co-solvant joue donc un rôle crutial dans le contrôle de l’aggrégation et de la catalyse La stratégie de “séparation de phase” a initiallement été étudiée en utilisant le couplage oxidatif d’alcynes de type Glaser-Hay co-catalysé par un complexe de cuivre et de nickel puis a été transposée à la chimie en flux continu. Elle fut ensuite appliquée à la cycloaddition d’alcynes et d’azotures catalysée par un complexe de cuivre en “batch” ainsi qu’en flux continu. / Macrocyclization is a fundamentally important transformation in organic synthetic chemistry. The main challenge associated with the synthesis of large ring compounds is the competing oligomerization processes that lead to unwanted side-products. Moreover, the high dilution conditions needed to achieved “selective” cyclization are often daunting for industrial applications. Despite the level of interest in macrocycles, research aimed at developing sustainable strategies that focus on catalysis at high concentrations in macrocyclization are still rare. The following thesis describes the development of a novel approach aimed at improving the efficiency of macrocyclization reactions through the control of dilution effects. A “phase separation” strategy that allows for macrocyclization to be conducted at higher concentrations was developped. It relies on an aggregated solvent mixture controlled by a poly(ethylene glycol) (PEG) co-solvent. Insight into the mechanism of “phase separation” was probed using surface tension measurments, UV spectroscopy and chemical tagging. It was proposed to function by allowing slow diffusion of an organic substrate to the phase where the catalyst is active. Consequently, the nature of the polymer co-solvent plays a role in controlling both aggregation and catalysis. The “phase separation” strategy was initially developed using the copper and nickel co-catalyzed Glaser-Hay oxidative coupling of terminal alkynes in batch and was also transposed to continuous flow conditions. The “phase separation” strategy was then applied to the copper-catalyzed alkyne-azide cycloaddition in both batch and continuous flow.

Abstact South Bohemian Theatre in České Budějovice is an important kulture institution since the end of the First World War. Against many different peripeties is this theatre with four companies only one profesional scene in the South Bohemian Region. From 2004 till now were here thanks to theatre director Jiří Šesták substantially developed opera, operetta, ballet, drama and theatre for children and teen - agers. Since 2006, when Martin Glaser has become an art chief of the Drama Company, works this company on clear dramaturgy and style of performances. Martin Glaser with dramaturge Olga Šubrtová were focused on contemporary drama, on cooperation with eminent czech theatre directors or creators and specially for this company were created several dramas. Thanks to management and direction by Martin Glaser became the Drama Company of South Bohemian Theatre contemporary, respected and definable.