Mémoire numérisé par la Direction des bibliothèques de l'Université de Montréal.

The synthesis, characterisation and anion binding properties of a series of mono- and bifunctional Lewis acidic borylferrocene compounds are described within this thesis. The original parent compound FcBMes₂ (3.1), revealed a versatile route for the synthesis of such borylferrocenes and subsequently the analogous compound Fc*BMes₂ (3.2) was synthesised. The anion binding properties of (3.1) and (3.2) were investigated and both were shown to bind one equivalent of cyanide. The binding event was signalled by an electrochemical shift (ca. -560 mV) and a quenching of bands at 510 or 542 nm respectively in the UV/Vis spectrum, while the mode of anion binding in the solid state was established by X-ray crystallography for [ⁿBu₄N]⁺[(3.1)·CN]⁻. Incorporation of a suitable redox active dye (i.e. tetrazolium violet for 3.2) allowed conversion of the electrochemical response to a colorimetric change on cyanide binding. However, a competing response for fluoride is also seen for (3.1) and (3.2). Thus a two component system is reported involving (3.2) and the boronic ester FcB(OR)₂ (3.4), [where (OR)₂ = OCH(Ph)CH(Ph)O], which from previous research is known to selectively bind fluoride, and allows for selective colorimetric cyanide sensing by simple Boolean AND/NOT logic. 1,4-C₆H₄(BMes₂)[B(OR)₂] (3.5), 4,4-C₁₂H₈(BMes₂)[B(OR)₂] (3.6) and 1,1′-fc(BMes2)(B(OR)2) (3.7) were synthesised as possible single molecules for discrimination between cyanide and fluoride. (3.5) and (3.6) proved only capable of binding one equivalent of either anion, (3.7) showed some ability to bind two equivalents of fluoride however based on ESI-MS studies although only in the presence of a large excess of anion. Systematic variation of the para-boryl substituent was investigated by synthesis of compounds FcB(Xyl^F)₂ (4.1), FcB(Xyl)₂ (4.2) and FcB(Xyl^OMe)₂ (4.3). Anion binding studies reveal a linear increase in fluoride binding affinity consistent with that expected based on the para,/em>-Hammett parameters, however with only minor differences, while no pattern is observed with respect to their cyanide binding capabilities. The addition of neutral and cationic peripheral substituents has been investigated through synthesis of [1,2-fc(CH₂NMe₂)BMes₂] (4.6) and [1,2-fc(CH₂NMe₃)BMes₂]⁺ (4.7). Subsequent binding studies revealed (4.6) to be moisture sensitive, however reaction of (4.7) with fluoride and cyanide led to formation of the adducts [(4.7)·F]⁻ and [(4.7)·CN]⁻. The anion affinity of (4.7) exhibits a substantial increase when compared to the parent compound (3.1). Even when compared to the isomeric 1,1′ system an increase of approximately three orders of magnitude is seen attributed to the closer nature of the cationic charge and in the fluoride adduct the presence of a cooperative intramolecular hydrogen bond. The 1,1′-bifunctional analogues of the mono-substituted systems were synthesised [e.g. 1,2-fc(BMes₂)₂ (5.1)] and shown to complex two equivalents of fluoride or cyanide in acetonitrile. The 1:1 cyanide adduct of (5.1) was isolated in chloroform however, no evidence for chelation was observed. The analogous systems 1,2-fc(BMes₂)₂ (5.5), 1,2-fc(BXyl₂)2 (5.7), and 1,2-fc(BMes₂)(BXyl₂) (5.8) were also investigated. Reaction of (5.5) with fluoride and cyanide revealed it to bind only one equivalent of either anion, neither however was bound in a chelating fashion although X-ray crystallography revealed cyanide binds exo whilst fluoride binds endo to the B···B cavity. Finally the kinetics of fluoride binding were studied by UV/Vis spectroscopy and showed a systematic increase in rate constant upon reduction of steric bulk.

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

This thesis explores various artistic and ritual practices of martial arts in relation to its presentation on stage. As a martial artist and actor I believe there are complementary practices in both crafts interdisciplinary of each other. For a martial artist, the individual’s performance and execution of martial arts techniques can be enhanced through emotional availability and characterization. For the actor, the martial arts can help condition the body physically, mentally and emotionally to create a grounded presence of connectivity to the earth. However, sometimes the martial arts are viewed as a militaristic discipline and not as artistic expression. I believe that the martial arts can be both discipline and artistry. Over the past three years of my graduate studies I have explored different methods to merge these methodologies. This thesis examines a successful devised show conceived by students and myself at our martial arts studio (dojang), at Martial Arts World of Powhatan, in Powhatan Virginia. This thesis’ examination describes and evaluates the production we titled M.A. Cirque: the Evolution (Martial Arts Circus: an evolution of martial arts). The M.A. Cirque is a theatrical martial arts performance expanded out of a ten minute competition routine to become a thirty minute production performed in Las Vegas, Nevada. Secondly, an exploration for further analysis of a supplemental martial arts demonstration titled Battle at Olympus: A new martial arts super show, describes the revisit of the theatrical process that was developed when devising the M.A. Cirque.

Novel bis(tetrahydroisoquinoline) N,N'-dioxides 1,2 belong to the group of compounds with axial chirality that act as a Lewis base. These properties make them useful chiral catalysts in reactions such as allylation, opening of epoxides, etc. that exhibit high enantioselectivity. The prepared chiral bis(tetrahydroisoquinoline) N,N'-dioxides (R,Rax,R)-1, (R,Sax,R)-1, (Rax,R)-2 a (Sax,R)-2 were tested as catalysts in enantioselective allylation of variously substituted α,β−unsaturated aldehydes and dienals with allyltrichlorosilane (Scheme 1). All the catalysts exhibited high catalytic activity as well as high asymmetric induction (up to 96% for α,β- unsaturated aldehydes;1 up to 98 % for dienals). Appropriate choice of solvent as a reaction medium3,4 and substitution in α-position in aldehydes were the crucial factors for the successful course of the reaction. The catalytic activity of (R,Rax,R)-1 and (R,Sax,R)-1 was also tested in asymmetric opening of meso-epoxides with tetrachlorosilane (ee up to 69 %) (Scheme 2). N N O O O O 1 N N O O O 2 Scheme 1 Scheme 2 1) Vlašaná, K.; Hrdina, R.; Valterová, I.; Kotora, M. Eur. J. Org. Chem. 2010, 7040. 2) Kadlčíková, A.; Hrdina, R.; Valterová, I.; Kotora, M. Adv. Synth. Catal. 2009, 351,1279. 3) Hrdina, R.; Opekar, F.; Roithová, J.; Kotora, M. Chem. Commun....

Made available in DSpace on 2016-04-26T18:15:21Z (GMT). No. of bitstreams: 1 Elisa de Freitas Weimann Gergull.pdf: 23284441 bytes, checksum: e7e3d90f068cc641e7668b7f15ccabf9 (MD5) Previous issue date: 2015-11-27 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / This research has as objective the multiple and varied ensemble constituted by the illustrations of Lewis Carroll s Alice in Wonderland and has as main objective the analysis of the relationship between verbal text and visual text that are established in them, trying to define what is illustration, which elements the illustrator uses in his works and what meaning effects it causes. We work with the hypothesis that the illustrator is a translator that operates in hisher own language. The research corpus consists of an ensemble of 10 editions of Alice in Wonderland, including the illustrations made by Lewis Carroll himself and by John Tenniel, who was the first and the most famous Alice illustrator after the author. The selection criterion privileges the classic English editions and the best translations to Portuguese of the integral text of Alice. The illustrations of the corpus have different styles and are a sample of different executions of the story and its characters. The methodology consists in bibliographical and documental research, the last one being the search of the referred Alice editions. The theoretical referential use the main authors to deal with intersemioticity, noticeably Roman Jakobson, Julio Plaza, Octavio Paz and Haroldo de Campos; specialists in English literature and Lewis Carroll, like Martin Gardner, Donald Rackin, Jenny Woolf and Morton N. Cohen, specialists in illustrations like Sophie Van der Linden, Martin Salisbury, Morag Styles, Maria Nikolajeva, Carole Scott e Ana Margarida Ramos. The relevance of this research to the area of Communication and Semiotics is in the study of the syncretism between verbal and visual texts, that here is being used to analyze a fundamental work / Esta pesquisa tem como objeto de estudo o conjunto múltiplo e variado constituído pelas ilustrações de Alice no país das maravilhas de Lewis Carroll e como objetivo principal a análise das relações entre o texto verbal e o texto imagético que aí se estabelecem. Busca-se responder o que é a ilustração, que elementos o ilustrador utiliza em seu trabalho e que efeitos de sentido ela desempenha. Trabalhamos com a hipótese de que o ilustrador é um tradutor que opera em língua própria. O corpus de pesquisa consiste em um conjunto selecionado de 10 edições de Alice no País das Maravilhas, incluindo as ilustrações do próprio Lewis Carroll e as de John Tenniel, que, após o autor, foi o primeiro e o mais famoso ilustrador da obra. O critério de seleção privilegia as edições inglesas clássicas e as melhores traduções do texto integral de Alice. Integram o corpus ilustrações com estilos diferentes entre si, suscetíveis de oferecer uma amostra de diferentes execuções da história e de suas personagens. A metodologia consiste em pesquisa bibliográfica e documental, esta segunda consistindo na procura das referidas edições de Alice. Os referenciais teóricos convocam os principais autores a tratar do conceito de intersemioticidade, notadamente Roman Jakobson, Julio Plaza, Octavio Paz e Haroldo de Campos; especialistas em literatura inglesa e na obra de Lewis Carroll, aí incluídos Martin Gardner, Donald Rackin Jenny Woolf e Morton N. Cohen; e especialistas em ilustração como Sophie Van der Linden, Martin Salysbury, Morag Styles, Maria Nikolajeva, Carole Scott e Ana Margarida Ramos. A relevância da pesquisa para a área da Comunicação e Semiótica está no estudo do sincretismo entre o texto verbal e o imagético, que aqui se volta para uma obra máxima

This inquiry examines the lived experience of a believing Christian seeking authentic space on a secular academic course. It has come about as a result of an experience of both angst and transformation leading to the focus of this inquiry which is looking to answer the question of: 'How does a committed Christian with a belief in foundational truth, authentically relate and integrate their faith and new found knowledge in counselling practice and research on a secular training course'? Research literature acknowledges a growing interest and demand for further debate and research in the domain of integration of faith and psychotherapy and practice, where evidence points to there being a gap in training. Integration is acknowledged as problematic but specific challenges are noted as not being so well researched. The study is written in the form of a paradigmatic case study where the researcher is also the researched. It embraces a pluralistic methodology incorporating aspects of personal narrative, interpretive phenomenological analysis and tacit understanding as advocated by Polanyi. This inquiry explores both the problem encountered and the solution found. The problem was epistemological, that of a personal belief in foundational truth, the central tenet of the Christian faith and the challenge of co-habiting a secular relativist space. The purpose and goal of this inquiry is to both show and tell the process of integration, which allowed authentic space to emerge both personally and theoretically. An exploration of a personal epiphany of 'heart and mind' integration is pivotal in this inquiry. The key finding which made integration possible was the discovery of and engagement with both Michael Polanyi and C.S. Lewis and their progressive theories of knowledge: theories which embrace both fundamental Christian belief and the fundamental values and theories taught in the dialogue of both person-centred and psychodynamic approaches. This study and reflexive analysis has created the basis of a body of work, which can be used as a means of support for Christian trainees who encounter similar challenges in academic spaces and in practice in this postmodern age. It can also be of benefit to trainers and course designers and counselling practitioners as they engage and dialogue with this re emerging phenomena. Finally this inquiry can be the catalyst for further research and development in order to begin to bridge the epistemological gap encountered in training.

Uppsatsens syfte är att undersöka hur drömmen gestaltas i romanen Alice i Underlandet och Tim Burtons filmadaption från 2010. Tillvägagångssättet för att uppnå syftet är en intermedial analys kombinerat med teorier om drömmar i film samt Freuds teorier om drömmar i litteratur. Uppsatsens frågeställning är hur gränsen mellan dröm och verklighet är gestaltad, som besvaras genom en jämförelse mellan romanen och filmadaptionen. Gestaltningen av drömmen syns tydligast i kontrast till Alice vakna verklighet eftersom det då går att se vad som skiljer drömmen från verkligheten. Genom en enskild analys av romanen och filmen, samt en jämförande analys av båda medierna har uppsatsens slutsats fastställts. Slutsatsen är att filmens gestaltning av gränsen mellan dröm och verklighet består av en markerande passage mellan dröm och verklighet, medan romanen gestaltar gränsen mellan dröm och verklighet som en flytande övergång.  Romanen gestaltar övergången till drömvärlden främst genom text där Alice funderande blir en övergång till drömmandet. Filmen möjliggör även tolkningen att Underlandet finns på riktigt och därmed inte är en dröm.

Lewis‘ woodpeckers (Melanerpes lewis) are generally associated with open ponderosa pine (Pinus ponderosa), open riparian, and burned pine habitats in the West; however, this species has recently been found to nest in aspen (Populus tremuloides) stands in Utah. This study describes the habitat characteristics of Lewis‘ woodpecker nest sites in aspen and investigates how well aspen stand characteristics predict Lewis‘ woodpecker occupancy. I surveyed for Lewis‘ woodpeckers at previously occupied nesting locations in aspen and took habitat measurements at nest sites. In addition, nest-centered Forest Inventory and Analysis (FIA)-type plots provided stand-level habitat characteristics. I used logistic regression to determine which stand-level habitat variables were associated with nest locations; significant variables were then used to select FIA plots in Utah that contained predicted suitable nesting habitat. Criteria used to select FIA plots were aspen type stands, percent canopy cover less than 46%, and average tree diameter at breast height greater than 27.9 cm (11 inches). I then conducted occupancy surveys at FIA plots predicted to contain “suitable” and “non-suitable” Lewis’ woodpecker habitat to field validate the predictive model. No predicted non-suitable plots (n=26) were occupied and only one predicted suitable plot (n=49) was occupied. My results indicated that Lewis’ woodpeckers are rare throughout Utah in aspen stands even though there seems to be abundant nesting habitat available. My results also indicated that variables measured by FIA do not, in isolation, provide sufficient capability to predict Lewis’ woodpecker nesting habitat or actual use, and that more data are needed to accurately predict Lewis’ woodpecker nesting habitat, such as distance to, age, and severity of fires.

Mon travail de thèse a porté sur le ciblage de la vascularisation tumorale : des molécules ciblant l'endothélium tumoral ont été recherchées dans le but d'amener des molécules thérapeutiques spécifiquement vers l'endothélium tumoral afin de le détruire et d'atteindre la tumeur qui en dépendait. D'après les données de la littérature, deux cibles ont été choisies pour notre étude : la sélectine E et l'endogline. La sélectine E est une glycoprotéine surexprimée à la surface de l'endothélium activé des zones inflammatoires et tumorales. Classiquement, des antagonistes de son ligand naturel, le SleX, sont recherchés. En nous appuyant sur les groupements clés de l'interaction entre la sélectine E et le SleX, plusieurs familles de mimes du SleX ont été élaborées. La capacité de ces mimes à déplacer l'interaction du SleX exprimé à la surface des cellules HL-60 avec la sélectine E a été évaluée dans un test d'adhésion. Cependant, aucun des mimes testés n'a présenté une affinité suffisante pour envisager son utilisation comme tête de ciblage. Une deuxième stratégie a consisté à rechercher des ligands peptidiques de la sélectine E en criblant des HUVECs activées avec une banque de peptides sur phages. Plusieurs phages-peptides testés en ELISA ont montré une meilleure affinité pour la sélectine E et / ou avec la sélectine P par rapport au phage sans insert. Des tests de compétition avec des peptides synthétiques correspondants permettront d'évaluer leur spécificité pour la cible. En ce qui concerne l'endogline, des ligands peptidiques ont été recherchés avec une banque de peptides sur phages. Dans un premier temps, le gène codant l'endogline humaine a été cloné dans un vecteur d'expression eucaryote afin de réaliser la sélection sur la protéine cellulaire. Une sélection sur la protéine recombinante a été réalisée par la suite pour diminuer le bruit de fond lié aux cellules. Parmi les peptides obtenus, certains ont montré des homologies de séquence avec des ligands de l'endogline et le test de ces phages-peptides en ELISA sur la protéine recombinante a donné un fort signal par rapport au phage sans insert. Ces peptides seront caractérisés prochainement. En conclusion, des ligands peptidiques des sélectines E et P et de l'endogline ont peut-être été identifiés. Ce travail a par ailleurs permis de mettre en place les outils nécessaires à l'utilisation de la technologie de sélection avec des banques de peptides sur phages dans les meilleures conditions possibles.