A fast atom bombardment mass spectrometry study of tris (3, 6-dioxaheptyl) amine-alkali metal halide complexes and hydrogen bonded complexes

The objective of this thesis was to demonstrate the potential of fast atom bombardment mass spectrometry (FABMS) as a probe of condensed phase systems and its possible uses for the study of hydrogen bonding. FABMS was used to study three different systems. The first study was aimed at investigating the selectivity of the ligand tris(3,6-dioxaheptyl) amine (tdoha) for the alkali metal cations. FABMS results correlated well with infrared and nmr data. Systems where a crown ether competed with tdoha for a given alkali metal cation were also investigated by fast atom bombardment. The results were found to correlate with the cation affinity of tdoha and the ability of the crown ether to bind the cation. In the second and third studies, H-bonded systems were investigated. The imidazole-electron donor complexes were investigated and FABMS results showed the expected H-bond strength of the respective complexes. The effects of concentration, liquid matrix, water content, deuterium exchange, and pre-ionization of the complex were also investigated. In the third system investigated, the abundance of the diphenyl sulfone-ammonium salt complexes (presumably H-bonded) in the FABMS spectrum were found to correlate with qualitative considerations such as steric hindrance and strength of ion pairs.

The role of motivational systems in community service involvement : initiating and sustaining factors and quality of experience /

Community service participation can have a positive impact on development, especially for youth. Although researchers have found positive outcomes, there has been a notable decline in youth participation over the past few years (Statistics Canada, 2000). Given the positive outcomes and current decline, it has been argued that youth should be encouraged to get involved in service activities. In the present study, quantitative and qualitative data were collected to determine factors that would help youth to initiate and sustain service, along with examining the quality of their experience. Eighty-two university undergraduate students (23 men), ranging in age from 17-20 years completed a 60-minute self-report questionnaire. Initiating and sustaining factors, motivational systems (similar to approach and avoidance dimensions), activity dimensions {Structure, Supportive Social Environment), quality of experience {Positive, Stress-Challenge), and future intention to participate in community service were measured. Eight participants also completed a 20-minute telephone interview to complement and expand on the quantitative data collected. Some initiating and sustaining factors were specific to individuals higher on the avoidance dimension, while others were relevant to those higher on the approach dimension. Several factors also were important to individuals regardless of their motivational system orientation. Positive quality of experience was related positively to experiencing a supportive social environment. In addition, women rated their community service as more positive than did men. A predicted interaction between the avoidance dimension and Structure in predicting positive quality of experience was not supported; however, positive quality of experience was predicted by the interaction of the approach dimension and Structure. A tested interaction between the avoidance dimension and Supportive Social Environment in predicting positive quality of experience was not supported. Similarly, a predicted interaction between the approach dimension and Supportive Social Environment in predicting positive experience quality was not supported. However, Supportive Social Environment was positively related to positive quality of experience. No support was found for a mediational role for positive quality of experience or stress-challenge quality of experience in exploring the relation between motivational orientation and fiiture intention to engage in service activities. The results of this study suggest that participating in a service environment that is supportive and provides the opportunity for social interactions with others would promote positive quality of experience and help youth sustain involvement. Thus, to help youth have positive experiences and to remain active in service, it is important for service agencies to promote these types of environments. In addition, some initiating and sustaining factors were specific to youth higher on the avoidance dimension and some were relevant to youth higher on the approach dimension. Therefore, service agencies may need to consider using different recruitment and retention strategies, depending on the type of youth they wish to recruit.

Identification of novel retinoid receptors and their roles in vertebrate and invertebrate nervous systems

In vertebrates, signaling by retinoic acid (RA) is known to play an important role in embryonic development, as well as organ homeostasis in the adult. In organisms such as adult axolotls and newts, RA is also important for regeneration of the CNS, limb, tail, and many other organ systems. RA mediates many of its effects in development and regeneration through nuclear receptors, known as retinoic acid receptors (RARs) and retinoid X receptors (RXRs). This study provides evidence for an important role of the RA receptor, RAR~2, in ,( '. regeneration ofthe spinal cord and tail of the adult newt. It has previously been proposed that the ability of the nervous system to regenerate might depend on the presence or absence of this RAR~2 isoform. Here, I show for the very first time, that the regenerating spinal cord of the adult newt expresses this ~2 receptor isoform, and inhibition of retinoid signaling through this specific receptor with a selective antagonist inhibits tail and spinal cord regeneration. This provides the first evidence for a role of this receptor in this process. Another species capable of CNS ~~generation in the adult is the invertebrate, " Lymnaea stagnalis. Although RA has been detected in a small number of invertebrates (including Lymnaea), the existence and functional roles of the retinoid receptors in most invertebrate non-chordates, have not been previously studied. It has been widely believed, however, that invertebrate non-chordates only possess the RXR class of retinoid receptors, but not the RARs. In this study, a full-length RXR cDNA has been cloned, which was the first retinoid receptor to be discovered in Lymnaea. I then went on to clone the very first full-length RAR eDNA from any non-chordate, invertebrate species. The functional role of these receptors was examined, and it was shown that normal molluscan development was altered, to varying degrees, by the presence of various RXR and RAR agonists or antagonists. The resulting disruptions in embryogenesis ranged from eye and shell defects, to complete lysis of the early embryo. These studies strongly suggest an important role for both the RXR and RAR in non-chordate development. The molluscan RXR and RAR were also shown to be expressed in the adult, nonregenerating eNS, as well as in individual motor neurons regenerating in culture. More specifically, their expression displayed a non-nuclear distfibution, suggesting a possible non-genomic role for these 'nuclear' receptors. It was shown that immunoreactivity for the RXR was present in almost all regenerating growth cones, and (together with N. Farrar) it was shown that this RXR played a novel, non-genomic role in mediating growth cone turning toward retinoic acid. Immunoreactivity for the novel invertebrate RAR was also found in the regenerating growth cones, but future work will be required to determine its functional role in nerve cell regeneration. Taken together, these data provide evidence for the importance of these novel '. retinoid receptors in development and regeneration, particularly in the adult nervous system, and the conservation of their effects in mediating RA signaling from invertebrates to vertebrates.

Finding the Open Spaces in Closed Systems: An Exploration of Critical Pedagogy with a Social Justice Directive in an Ontario Secondary School Classroom

This study examines the first experience of students, teachers, and an administrator in implementing a teacher-designed Leadership in Social Justice Program at a large urban Ontario secondary school. The program aimed to infuse a Freirean concept of critical pedagogical praxis (Freire, 1970/1993) in a grade 12 integrated educational experience with a social justice directive. Data were collected through two questionnaires and eight in-depth interviews. The data identified three areas of awareness that described ways in which student participants were impacted most profoundly (a) developing self-awareness, (b) understanding a new educational paradigm, and (c) finding a place in the world. The study found that the program was successful in highlighting the possibility for more meaningful education and engaged many students deeply; however, its success was limited by the lead teacher’s failure to fully grasp and implement tenets of Freirean critical pedagogy that involved the role of the teacher in pedagogical processes.