VictorJuiz/thesis huggingface dataset:
Transition metal-mediated routes to inorganic small molecules and macromolecules and the self-assembly of amorphous polyferrocenylsilane diblock coploymers in solution and in the bulk phase

Two model intermediates for the mechanism of the transition metal-mediated ring-opening polymerization (ROP) of silicon-bridged [1]ferrocenophane, Fe(η 5-C5H4)2SiMe2, ( 1) were synthesized, and their catalytic activity was investigated. These studies revealed that the strongly coordinating phosphine ligands blocked catalytic activity of Fe(η5-C5H4) 2Pt(PEt3)2SiMe2. In contrast, the sister compound, Fe(η5-C5H4)2Pt(1,5-cod)SiMe 2, behaved with similar catalytic activity as the parent complex, Pt(1,5-cod) 2, and afforded high molecular weight polyferrocenylsilane (PFS). The addition of BH3•THF co-catalyst activated Fe(η 5-C5H4)2Pt(PEt3) 2SiMe2 towards the ROP of 1, affording low molecular weight cyclic oligoferrocenylsilane. Our studies suggested that fcPt(1,5-cod)SiMe 2 is not the active catalyst, but instead a precursor to a more reactive species, and that the ROP proceeds mainly by a heterogeneous mechanism. Cationic rhodium complexes, [Rh(1,5-cod)2]A (A = OTf, PF 6) exhibited high catalytic activity for the transition metal-mediated ROP of 1, and its copolymerization with tetramethyldisilacyclobutane. However, in the case of PFS, prolonged exposure of the reaction mixture to the catalyst resulted in a dramatic molecular weight decline. This degradation of the PFS backbone was modeled through the catalytic reaction of Fc 2SiMe2 (Fc = Fe(η5-C5H 5)(η5-C5H4)) with the rhodium complex. The solution and solid-state self-assembly of PFS-based diblock copolymers were investigated with particular emphasis on the effects of a semi-crystalline versus amorphous PFS block on the resulting phase segregation. We found that the crystalline nature of the poly(ferrocenyldimethylsilane) (PFDMS) block played a pivotal role in the formation of micellar aggregates in solution, and hindered the formation of well-ordered phase separated morphologies in the bulk. Thus, the diblock copolymer, PFDMS50-b-PDMS 300 formed unexpected cylindrical micelles in n-hexane, while the amorphous analogues, PFMPS40-b-PDMS 240 (PFMPS = polyferrocenylmethylphenylsilane) and PFEMS50- b-PDMS330 (PFEMS = poly(ferrocenylethymethylsilane), formed spherical micelles. In the bulk, the amorphous PS222-b -PFMPS63 and PS374-b-PFEMS 45 copolymers microphase segregated to afford well-ordered nanostructured materials. Thin films of PS374-b-PFEMS45 spontaneously self-assembled to generate vertically-oriented cylinders of PFEMS in a PS matrix. Subsequent pyrolysis of the cross-linked films resulted in the formation of ordered ceramic nanodots. Secondary amine-borane adducts R2NH•BH3 underwent efficient catalytic dehydrocoupling in the presence of rhodium complexes to form cyclic aminoboranes [R2N-BH2]2 (R = Me, cyclo-C4H8). Under similarly mild conditions, the analogous adducts NH3•BH3 and MeNH 2•BH3 yielded the corresponding borazines in yields limited by intermolecular coupling reactions.
Experimental investigation of predictive probabilistic and temporal conflict avoidance displays

Inferring the future intentions and courses of numerous aircraft or ships at various points in time can be problematic for traffic controllers. In this thesis, a new graphical display concept is presented. The displays present predictive information about the times, locations, and probabilities of potential traffic conflicts using topological contours and continuous density graphs superimposed onto existing traffic information. 12 participants engaged in a ship control conflict avoidance task by performing a series of maneuvers to minimize the overall impact of potential conflicts. Results indicate that only during the initial trials participants used significantly fewer maneuvers to resolve potential conflicts and did so with better overall scores when using the new graphical display formats compared to the conventional format. Nevertheless, subjective ratings strongly indicated participants' preferences for the new graphical formats and revealed some interesting underlying strategies and potential applications of the displays for both air and ship traffic management.
"The sound of the rustling of the gold is under my feet where I stand ; we have a rich country": a history of aboriginal mineral resources in Ontario

This dissertation analyzes the inherent Aboriginal Title to mineral resources, including oil and gas, under the land and land under water in the context of a long and continuous Native knowledge and use of these resources, which were never relinquished by First Nations in Ontario. Some individual Natives shared their mineral knowledge with the newcomers entering their lands. NonAboriginal mining activities eventually led to disputes between First Nations and the outsiders who, in many cases, attempted to remove minerals without Aboriginal consent and without paying compensation. Under these circumstances, First Nations vigorously petitioned and visited the colonial and settler governments for redress and the negotiation of Treaties, which the governments were reluctant to make. Government inaction prompted numerous Chiefs, First Nation citizens and their allies into disrupting, blocking or otherwise stopping nonNative mining operations in the province thus, precipitating the Treaties which they had demanded. This was the context in which the largest Treaties in Ontario were concluded. First Nations negotiated strong, open-ended Treaties which protected their rights and provided for future economic development and sovereignty. But, because the government unilaterally added and deleted provisions in its printed Treaties, the actual Treaties which First Nations had orally negotiated and agreed to have been obscured. This appears to have been deliberate because the settler government and its successors wanted control of and beneficial interest in the same resources which Native Peoples had retained as the base of their economy: minerals, timber, game, fish, water etc. Following the Confederation of Canada in 1867, Ontario fought to gain control of this largesse. Federal/provincial disputes over ownership and monetary interest in minerals led to numerous court battles, legislation and agreements which upheld the provincial position at the expense of First Nations and Canada. This study demonstrates that First Nations have an inherent Title to minerals, that they have never yielded this and that this Title continues to this day. First Nations have acted consistently to protect and develop these resources which are a part of their birthright. The colonial government and its successors, including Ontario, have behaved inconsistently both admitting and denying Aboriginal ownership and beneficial interest in minerals. These governments have consistently failed to respect Treaty promises. Canada, in particular, has badly mismanaged mineral development on Reserves in Ontario.
Transcriptional regulation of the endothelial nitric oxide synthase (NOS3) gene: an in vivo assessment

Expression of the endothelial nitric oxide synthase (NOS3) mRNA is a complex and multifactorial process involving transcriptional and post-transcriptional contributions. NOS3 mRNA is highly restricted to the endothelium in vivo and constitutive expression is dependent upon two tightly juxtaposed positive regulatory domains in the proximal promoter. Surprisingly the NOS3 promoter is active in non-endothelial cell types in vitro in transient transfections assays. In order to advance our understanding of transcriptional regulation of NOS3, an in vivo model is requisite. We cloned and sequenced 5.2 kb of 5'-flanking sequences of the murine Nos3 gene and observed a high degree of sequence identity with the human promoter, especially the proximal positive regulatory domains responsible for constitutive expression. The Nos3 5'-flanking sequences were then used to develop insertional Nos3-promoter/LacZ-reporter mice. Three independent founders were derived. Expression of the LacZ reporter was highly restricted to the endothelium of large and medium size blood vessels of adult mice. Importantly, all founders evidenced comparable expression patterns that corresponded with the known expression profile of eNOS. We then undertook a comprehensive assessment of eNOS expression during mammalian development. Unlike other endothelial cell (EC)-specific genes, we found that eNOS is a late EC marker, the expression of which onsets with the establishment of unidirectional blood flow. A role for eNOS-derived NO in skeletal myogenesis and the regulation of limb growth was also suggested. The gene was transcriptionally active in the apical ectodermal ridge of developing limb buds and in secondary myocytes during myogenesis. Taken together, this thesis comprehensively characterized eNOS transcription in vivo. Therapeutic implications of this body of work are applicable to the development of gene therapies targeted toward the endothelium and in the development of treatments for congenital limb abnormalities.
Becoming a writer: Social constructions of writing from children with cerebral palsy

Over the years, a great deal of intervention has been focused on enabling children with cerebral palsy to acquire writing skills. Yet the available literature provides little information on the children's perspectives about this important childhood occupation. This qualitative study employed a modified grounded theory approach, guided by a social model of disability framework to explore the classroom writing experiences of children who have cerebral palsy. Eleven primary grade students were interviewed. Data were analyzed using a constant comparative method. The study results revealed ways in which these students make sense of the occupation of writing and ways they see themselves. Writing is described as being hard work. Children with cerebral patsy see themselves as being more the same than different. They highly valued inclusion with their peer group. The significance of the results is discussed along with recommendations for future research.
Limited engagement: three peninsular dramaturgas of the 1980s

With the election of the socialist party in 1982, the theater in Spain was promised an ambitious revision of government policies with regard to greater promotion through education, an increase in public venues, a revamped infrastructure, and a decentralization to stimulate growth beyond the former monopolies. A subsidy system was set up with the objective of establishing a solid, unbiased base for the funding of theatrical development, with a specific eye to promotion of autochthonous writers. While the aims of the socialist government were laudable, systematic interference soon outstripped the best intentions and control of every level, from funding to staging and to publication, gave birth to the concept of economic censorship. Hardest hit by the official policies were the playwrights themselves who either submitted to government preferences or accepted exclusion. Lowest on the ladder of success were the female writers who found it difficult to gain a foothold in the male dominated field. Already suspect in the eyes of critics and colleagues alike who retained traditional gender bias, they were a non-hegemonic discourse eliminated to a great degree from theatrical history and praxis. The socialist subsidy system, far from ameliorating this situation, exacerbated their status. This study concentrates on the trajectories of three women playwrights to dissect the failure of the socialist subsidy system during the transitional decade into democracy. Pombo, a proponent of the renovative vision that stubbornly opposed the traditional mindset, provides a clear example of subsidy exclusion. Considered a heavy financial risk because of this opposition, her awards and status were not enough to garner her access to funding. Concha Romero's work shifts between renovative and complicit strategies, serving to highlight the middle ground of subsidy allotment and its boundaries. Ana Diosdado, unique in maintaining a solid theatrical presence, pre- and post-Franco, is an example of the innovative vision that introduced a new technology of scenography while remaining complicit with traditional mores. What emerges from the disparity between Diosdado's success and Pombo's exclusion is a map of the failure that was the socialist subsidy system during the 80s.
Longing to become, coming to belong: ESL students' engagement of integrative antiracism social justice education

Based on the premise that powerful discourses of national identity, of racialized, culturalist, gendered and language difference unevenly overlap and diverge as they map onto the bodies of ESL learners in processes of becoming Canadian, this dissertation proposes the need for a model of cultural activist anticolonialist English language pedagogy in Canadian public schools. Pursuing this proposal, this dissertation brings critical race, feminist post-structuralist, postcolonial and cultural studies theory to a qualitative study of the identity translation processes of a group of high school ESL students who have participated in an anti-discrimination leadership programme. Incorporating the concepts of cultural translation and identity 'transcreation' from postcolonial translation theory, this research holds two agendas in tension: the first examines the transformative pedagogical aspirations, strategies and assumptions of the anti-discrimination ESL leadership programme in relation to the processes by which they are engaged by participating students; the second agenda asks what insights participant experiences and learning gives us into the specificities of language minority students' negotiations of high-stakes relations of difference, recognition, authority, belonging and meaning within the complex discursive landscape of Canadian schools. The significance of this study lies in its articulation of the fields of second language, integrative antiracism/social justice and critical pedagogy. The interdisciplinary theoretical framework developed here opens onto three urgent questions: (1) How might ESL students be understood as subjects of language difference? (2) How might we conceive of language difference as a form of social difference which articulates with but is distinct from other forms of social difference and systems of discrimination? (3) What processes are recognized and invited into the classroom when we reconceive the learning experiences and socio-discursive negotiations of ESL students as cultural translation and identity transcreation? These questions are pursued in the study through the development and application of a model for the design and evaluation of integrative antiracism social justice educational programmes for ESL students. I conclude with recommendations for the specific equity leadership programme and for transformative ESL pedagogy for new Canadians in a general.

Keywords: Dissertation
The relationship between expectations and exercise adherence in women

Improving rates of exercise adherence for Canadian women is a critical priority. Recent studies argue that decreasing outcome expectations associated with exercise will improve adherence. This recommendation fails to acknowledge that high outcome expectations are critical for exercise adoption, particularly in women. As failure to meet expectations is more detrimental than expectations themselves, do women adequately gauge the time and effort required to achieve the outcomes they expect? The current study examined exercise adherence and exercise expectations in twenty-six women. While no significant relationships were found between adherence and expectations, significant positive relationships were found between adherence and high intensity exercise and adherence and personal training. As high intensity exercise leads to greater physical and mental adaptations and exercise under the supervision of a personal trainer is arguably more effective, it is possible that certain women exhibited higher levels of exercise adherence because their expectations were being met.
Mechanisms of epithelial polarity

Analysis of the mechanisms that control epithelial polarization has revealed that cues for polarization are mediated by transmembrane proteins that operate at the apical, the lateral, or the basal membrane of epithelial cells. Crumbs is a key regulator of epithelial polarity in Drosophila that localizes to the apical membrane of epithelial cells. Here I have characterized a C. elegans homolog of the Drosophila gene crumbs (Cecrumbs). Cecrumbs is expressed predominantly in epithelial cells, and the CeCrumbs protein localizes to the apical membrane of these cells. Two deletion mutations that severely truncate the CeCrumbs protein were isolated. Animals homozygous for these mutations are viable, fertile, and do not show any morphological defects suggesting that Cecrumbs is not an essential gene. In Drosophila ovaries, I have characterized the development of polarity in the follicular epithelium. I found that the follicular epithelium uses three different polarization mechanisms, each operating at one of the three main epithelial membrane domains. I used mosaic analysis to show that Crumbs is required for the formation and maintenance of the follicular epithelium. Discs Lost, a cytoplasmic binding partner of Crumbs, overlaps precisely in its distribution with Crumbs as shown by immunoelectron microscopy. I show that Discs Lost uses Crumbs-dependent and Crumbs-independent mechanisms for apical targeting. Furthermore, I show that the cadherin-catenin complex is not required for the formation of the follicular epithelium but only for its maintenance. I carried out a genetic screen to identify Drosophila genes that interact with crb. In this screen I have identified functional interactions between crb and lethal giant larva mutations. The Lethal Giant Larva protein regulates epithelial polarization in Drosophila but does not interact physically with Crumbs as the two proteins localize to the basolateral and apical membrane, respectively. These interactions extend to other genes within the crumbs (stardust) and lethal giant larva (discs large; scribbled) pathways. My results suggest that the crumbs and lethal giant larva pathways act competitively to define apical and basolateral surface territories. Moreover, I show that crumbs and lethal giant larva function and their interactions are limited to early epithelial differentiation where they cooperate in zonula adherens formation. However, the requirement of crumbs and lethal giant larva pathway activity for the maturation of epithelial polarity is transient as polarity is re-established in lethal giant larva and crumbs mutant embryos at later stages of development.
The ESAT-6/CFP-10 secretion system of Mycobacterium marinum modulates phagosome maturation

The ESAT-6/CFP-10 secretion system is an important virulence determinant of Mycobacterium tuberculosis. However, the specific functions of the secretion system are currently unclear. Genes encoding the ESAT-6/CFP-10 secretion system is conserved in pathogenic Mycobacterium marinum, a close relative of M. tuberculosis. An M. marinum mutant with a non-functional ESAT-6/CFP-10 secretion system is characterized in this study. Results show that mutant bacteria were unable to replicate in J774 macrophages. Comparative analysis of phagosome maturation by assessing phagosome acquisition of late endosome/lysosome marker LAMP-1, phagosome acidification and phagolysosome fusion demonstrates that in contrast to wild type parental strain, a significantly higher percentage of the mutant bacteria resided in acidified, LAMP-1 positive phagosomes and are fused with lysosomes. These results suggest a novel function for the secretion system in modulating phagosome maturation and thereby promotion of intracellular survival. This finding provides a mechanism by which the ESAT-6/CFP-10 secretion system may potentiate the virulence of pathogenic mycobacteria.
Analysis of lower limb skeletal geometry in children with cerebral palsy

Clinical gait assessment of children with cerebral palsy (CP) is common practise, yet the gait models used are often based on the anthropometry of average-sized healthy adults. This study investigated the variability in skeletal landmarks of the lower extremities between able-bodied adults, able-bodied children, and children with spastic CP. The accuracy of femoral anteversion (FAV) and tibial torsion (TT) measurements from clinical and MRI estimates was examined. Statistical analysis on landmark data showed very little significant differences between the two child groups, however, a substantially higher number of significant differences were found between the able-bodied adults and both child groups. Clinical measurements of FAV and TT were found to be poor predictors of the MRI measurements. FAV and TT were sensitive to the estimate of the shaft axis. Findings from this study provide a strong motivation for developing better scaling and landmark prediction methods for children with CP.
Early exercise intervention after stroke: influence on aerobic and functional capacity

In the stroke population, regular physical activity has the potential to positively influence both stroke-related outcomes and risk factors for recurrent events. The overall objective of this work was to determine the feasibility and effects of exercise testing and early aerobic training in the sub-acute stroke population. The feasibility of maximal exercise testing on a semi-recumbent cycle ergometer was established, and recommendations were provided for test termination and criteria for maximal effort during exercise testing. Individuals with stroke who participated in an early aerobic exercise program on a semi-recumbent cycle ergometer in addition to conventional rehabilitation demonstrated significant improvement in VO2peak and a trend towards greater improvement in peak work rate and functional ambulation, compared to those who received conventional rehabilitation only. Results contribute to our knowledge about the influence of physical activity among stroke survivors, and have implications on shaping the clinical practice in stroke rehabilitation.