THE DESIGN AND SYNTHESIS OF SILOXANE PRECURSORS FOR CHIRAL PERIODIC MESOPOROUS ORGANOSILICA MATERIALS

The development of cost-effective and reliable methods for the synthesis and separation of asymmetric compounds is paramount in helping to meet society’s ever-growing demand for chiral small molecules. Of these methods, chiral heterogeneous supports are particularly appealing as they allow for the reuse of the chiral source. One such support, based on the synergy between chiral organic units and structurally stable inorganic silicon scaffolds are periodic mesoporous organosilicas (PMOs). In the work described herein, I examine some of the factors governing the transmission of chirality between chiral dopants and prochiral bulk phases in chiral PMO materials. In particular, the exploration of 1,1’-binaphthalene-bridged chiral dopants with a focus on the point of attachment into the materials. Moreover, the effects of ordering in the materials are examined and reveal that chirality transfer is more facile in materials with molecular-scale order then those containing amorphous walls. Secondly, the issues surrounding the synthesis and purification of aryl-triethoxysilanes as siloxane precursors are addressed. Both the introduction of a two-carbon linker and the direct attachment of allyl and mixed allyldiethoxysilane species are explored. This work demonstrates that allyldiethoxysilanes are ideal, in that they are stable enough to permit facile synthesis, while still being able to hydrolyze completely to produce well-ordered materials. Lastly, the production of new bulk phases for chiral PMO materials is examined by introducing new prochiral nitrogen-containing siloxane precursors. Biphenyldiamine and bipyridine-bridged siloxane precursors are readily synthesized on reasonable scales. Their use as the bulk siloxane precursor in the production of PMO materials however, is precluded by insufficient gelation and additional siloxane precursors are necessary for the production of ordered materials. In addition to the research detailed above that forms the body of this thesis, two short works are appended. The first details the production of polythiophene assemblies mediated through coordination nanospaces, while the second explores the production of N-heterocyclic carbene functionalized gold nanoparticles through ligand exchange.

Sydenham Street Revived: A Public Space Experiment

In 2015, the Sydenham Street Revived pop-up park project (SSR) transformed Sydenham Street between Princess and Queen Streets into a temporary pedestrian-only public space. The goal of the project was to test out the idea of permanently pedestrianizing this street section. But what did this urban experiment ultimately prove? Using video footage, photographs, and observations recorded before and during the project, this report analyzes the use of the space in order to evaluate the claim that SSR created a successful public space and to make recommendations for a permanent public space on Sydenham Street. Two research methods were used: quantitative data collection, consisting of headcounts of both pedestrians and stationary users of the space; and a qualitative observational survey, based on the criteria for successful public spaces developed by the Project for Public Spaces. Data collection occurred two days one week prior to the project, and two days during the project, on days that were similar in terms of temperature and weather. The research revealed that the SSR did create a successful public space, although additional research is needed in order to determine how the space would function as a public place throughout different seasons, to study the street closure’s impact on surrounding residents and businesses, and to understand how private commercial activity would influence use. Recommendations for a permanent public space on Sydenham Street include considerations for flexible street design and a continuous, barrier-free surface; ensuring that there is an abundance of places to sit; making opportunities for public and community-created art; and to improve walkability by connecting the grid using a mid-block walkway.

An exploration of students’ perceptions and attitudes towards creativity in engineering education

This study used a mixed methods approach to develop a broad and deep understanding of students’ perceptions towards creativity in engineering education. Studies have shown that students’ attitudes can have an impact on their motivation to engage in creative behavior. Using an ex-post facto independent factorial design, attitudes of value towards creativity, time for creativity, and creativity stereotypes were measured and compared across gender, year of study, engineering discipline, preference for open-ended problem solving, and confidence in creative abilities. Participants were undergraduate engineering students at Queen’s University from all years of study. A qualitative phenomenological methodology was adopted to study students’ understandings and experiences with engineering creativity. Eleven students participated in oneon- one interviews that provided depth and insight into how students experience and define engineering creativity, and the survey included open-ended items developed using the 10 Maxims of Creativity in Education as a guiding framework. The findings from the survey suggested that students had high value for creativity, however students in fourth year or higher had less value than those in other years. Those with preference for open-ended problem solving and high confidence valued creative more than their counterparts. Students who preferred open-ended problem solving and students with high confidence reported that time was less of a hindrance to their creativity. Males identified more with creativity stereotypes than females, however overall they were both low. Open-ended survey and interview results indicated that students felt they experienced creativity in engineering design activities. Engineering creativity definitions had two elements: creative action and creative characteristic. Creative actions were associated with designing, and creative characteristics were predominantly associated with novelty. Other barriers that emerged from the qualitative analysis were lack of opportunity, lack of assessment, and discomfort with creativity. It was concluded that a universal definition is required to establish clear and aligned understandings of engineering creativity. Instructors may want to consider demonstrating value by assessing creativity and establishing clear criteria in design projects. It is recommended that students be given more opportunities for practice through design activities and that they be introduced to design and creative thinking concepts early in their engineering education.