The Synthesis and Coordination Chemistry of Two Families of Polydentate Ligands - Exploring Their Potential for the Preparation of Molecule-Based Magnets

The synthesis and studies of two classes of poly dentate ligands are presented as two projects. In project 1, four new carboxamide ligands have been synthesised via the condensation of 2,2',6,6'-tetrachloroformyl-4,4'-bipyridine or 2,6-dichloroformyl pyridine together with heterocyclic amines containing pyridine or pyrazole substituents. The coordination chemistry of these ligands has been investigated and studies have shown that with a Cu(II) salt, two carboxamide ligands LJ and L2 afford large clusters with stoichiometries [Cu8(L1)4Cl16].CHCl3.5H2O.7CH3OH (I) and [Cu9(L2)6Cl6].CH3OH.5H2O.(C2H5)3N (II) respectively. [molecular diagram availabel in pdf]. X-ray diffraction studies of cluster (I) reveal that it has approximate S4 symmetry and is comprised of four ligands and eight copper (II) centers. Here, coordination takes place via amide 0 atoms, and pyrazole nitrogens. This complex is the first reported example of an octanuclear copper cluster with a saddle-shaped structure. The second cluster comprises nine copper ions that are arranged in a cyclic array. Each ligand coordinates three copper centers and each copper ion shares two ligands to connect six ligands with nine copper ions. The amide nitrogens are completely deprotonated and both amide Nand 0 atoms coordinate the metal centres. The cluster has three-fold symmetry. There are six chloride ions, three of which are bridging two neighbouring Cu(II) centres. Magnetic studies of (I) and (II) reveal that both clusters display weak antiferromagnetic interactions between neighbouring Cu(II) centers at low temperature. In the second project, three complexes with stoichiometries [Fe[N302](SCN)2]2 (III), R,R-[Fe[N3O2](SCN)2 (IV) and R,R-]Fe[N3O2](CN)2] (V) were prepared and characterized, where [N302] is a pentadentate macrocycle. Complex (III) was prepared via the metal templated Schiff-base condensation of 2,2',6,6'-tetraacetyl-4,4'-bipyridine together with 3,6-dioxaoctane-I,8-diamine and comprises of a dimeric macro cycle where the two Fe(II) centres are in a pentagonal-bipyramidal environment with the [N302] ligands occupying the equatorial plane and two axial NCS ligands. Complexes (IV) and (V) were prepared via the condensation of 2,6-diacetylpyridine together with a chiral diamine in the presence of FeCh. The synthetic strategy for the preparation of the chiral diamine (4R,5R)-4,5-diphenyl-3,6-dioxa-I,8-octane-diamine was elucidated. The chirality of both macrocycles (IV) and (V) was probed by circular dichroism spectroscopy. The crystal structure of (IV) at 200 K contains two independent molecules in the unit cell, both of which contain a hepta-coordinated Fe(II) and axial NCS ligands. Variable temperature magnetic susceptibility and structural studies are consistent with a high spin Fe(II) complex and show no evidence of any spin crossover behaviour. In contrast, the bis cyanide derivative (V) crystallizes with two independent molecules in the unit cell, both of which have different coordination geometries consistent with different spin states for the two Fe(II) centres. At 250 K, the molecular structure of (V) shows the presence of both 7- and a 6-coordinate Fe(II) complexes in the crystal lattice. As the temperature is lowered, the molecules undergo a structural change and at 100 K the structural data is consistent with a 6- and 5-coordinate Fe(II) complex in the unit cell. Magnetic studies confirm that this complex undergoes a gradual, thermal, spin crossover transition in the solid state. Photomagnetic measurements indicate this is the first chiral Fe (II) sea complex to exhibit a LIESST.

Daily Physical Activity as an Intervention Strategy for Anxious Elementary Students

The focus of this project was twofold: a comprehensive examination of provincially mandated, school-based physical activity programming beyond physical education, as well as an exploration of the potential relationship between school-based physical activity and student anxiety. The data were collected using a descriptive research methodology consisting of a qualitative document analysis of provincial government publications pertaining to school-based physical activity programming and the literature on the relationship between physical activity and student anxiety. The findings revealed inconsistencies between the Canadian provinces and territories in providing mandated school-based physical activity beyond physical education. It was also revealed that regular school-based physical activity has the potential to make a positive impact on students’ lives in many ways. Students are living more sedentary lives, and evidence shows that regular physical activity could prevent and treat student anxiety.

A Needs Assessment: Language Instruction Stakeholders Engaging in Project Based Learning Outside the Classroom for Effective Strategic Problem Solving

Abstract A noted benefit of Project Based Learning (PBL) as a teaching strategy is how it engages the student and enhances learning outcomes as a result of working through challenges intended to depict dilemmas outside the classroom. PBL has seldom been applied outside the parameters of the classroom curriculum. The current needs assessment carried out in this research project examined current practices of language instruction and International Administrative Professionals of both the private and public Language Industry. Participants responded to survey questions on their current administrative practices, strategies, and program characteristics. The study investigated the usefulness of a handbook on the procedure of assisting administrative service teams in language instruction settings to an engaged approach to PBL for student service issues. The diverse opinions, beliefs, and ideas, along with institutional policy, can provide beneficial framework ideas for future tools.

A Comparative Analysis of Community-Based Service Providers for "Extreme" Case ASD: Exploring Activity Program Options

The purpose of my research was to examine how community-based organizations in the Niagara region provide programs for children with Autism Spectrum Disorder (ASD), who are considered to represent “extreme” or “severe” cases. A qualitative, comparative case study was conducted that focused on three organizations who provide summer recreation and activity programs, in order to examine the issues these organizations face when determining program structure and staff training; and to understand what the threshold for physical activity is in this type of setting, and how the unique needs surrounding these “severe” cases are met while attending the program. Purposeful sampling was employed to select a supervisor and senior staff member from each organization to discuss the training process, program development and implementation, and the resources and strategies used within their organization’s community-based program. A confirming comparative analysis was comparative analysis of a parents survey with six mothers whose children are considered “severe” indicated that camp staffs’ expectations are unrealistic where as the parents and supervisors have more realistic expectations within the “real world” of camp. There is no definition of “severe” or “extreme” and therefore severity is dependent upon the context.

Mobile Books: Effect of Engagement on Students’ Motivation and Cognitive Strategy Use

This mixed methods research explores the role of reading engagement in 30 grade 1 students’ motivation to read mobile electronic storybooks (eBooks) and cognitive strategies used during eBook reading. Data collection comprised motivation and parent questionnaires, behavioural observation checklists, cognitive strategies rubric, and teacher interviews. Students’ emotional engagement with and enjoyment of mobile eBooks corresponded to 4 motivational aspects of intrinsic motivation: curiosity, control, choice, and challenge. Post-intervention results indicated that most student participants enjoyed answering eBook comprehension questions and preferred eBooks to print books; by the end of the study, all had access to a mobile device at home. A majority of participants were actively engaged during mobile eBook reading sessions and persisted in answering embedded eBook comprehension questions, which together reflected students’ behavioural engagement and time-on-task during mobile reading. Students’ off-task behaviours related to iPads’ accessibility features and inherent reader-friendliness. All participants successfully answered evaluative questions requiring them to activate prior knowledge, and experienced higher levels of difficulty with making personal connections. The study highlights the importance of making school-based literacy practices relevant to students’ outside worlds, and discusses implications for teacher educators, administrators, curriculum developers, and eBook and other digital developers concerning the need for greater collaboration in order to more closely align technology resources with national curriculum expectations.

The Role of Experience in the Organization and Refinement of Face Space

Adults code faces in reference to category-specific norms that represent the different face categories encountered in the environment (e.g., race, age). Reliance on such norm-based coding appears to aid recognition, but few studies have examined the development of separable prototypes and the way in which experience influences the refinement of the coding dimensions associated with different face categories. The present dissertation was thus designed to investigate the organization and refinement of face space and the role of experience in shaping sensitivity to its underlying dimensions. In Study 1, I demonstrated that face space is organized with regard to norms that reflect face categories that are both visually and socially distinct. These results provide an indication of the types of category-specific prototypes that can conceivably exist in face space. Study 2 was designed to investigate whether children rely on category-specific prototypes and the extent to which experience facilitates the development of separable norms. I demonstrated that unlike adults and older children, 5-year-olds rely on a relatively undifferentiated face space, even for categories with which they receive ample experience. These results suggest that the dimensions of face space undergo significant refinement throughout childhood; 5 years of experience with a face category is not sufficient to facilitate the development of separable norms. In Studies 3 through 5, I examined how early and continuous exposure to young adult faces may optimize the face processing system for the dimensions of young relative to older adult faces. In Study 3, I found evidence for a young adult bias in attentional allocation among young and older adults. However, whereas young adults showed an own-age recognition advantage, older adults exhibited comparable recognition for young and older faces. These results suggest that despite the significant experience that older adults have with older faces, the early and continuous exposure they received with young faces continues to influence their recognition, perhaps because face space is optimized for young faces. In Studies 4 and 5, I examined whether sensitivity to deviations from the norm is superior for young relative to older adult faces. I used normality/attractiveness judgments as a measure of this sensitivity; to examine whether biases were specific to norm-based coding, I asked participants to discriminate between the same faces. Both young and older adults were more accurate when tested with young relative to older faces—but only when judging normality. Like adults, 3- and 7-year-olds were more accurate in judging the attractiveness of young faces; however, unlike adults, this bias extended to the discrimination task. Thus by 3 years of age children are more sensitive to differences among young relative to older faces, suggesting that young children's perceptual system is more finely tuned for young than older adult faces. Collectively, the results of this dissertation help elucidate the development of category-specific norms and clarify the role of experience in shaping sensitivity to the dimensions of face space.

Best Practices of Sport For Development: A Case Study of An African Organization

Sport-for-development is the active practice of achieving social ideals through the use of sport and other traditional development programs. The purpose of this thesis was to evaluate SFD best practices from the context of an African organization development project. The case was a development organization in Zambia, Africa that was utilizing sport within its strategy. The data collection and analysis framed using Curado and Bontis (2007) MIC Matrix, the Sport For Development International Working Group’s (2007) best practices model, and B. Kidd’s (2011) Sport-in-Development Logic Model. The research supports that a SFD project is multi-faceted and should include the employment of strategic community programming on the basis of collaborative and integrative sport, health care and education. Further, the researcher found that the best practices include setting specific goals and objectives, as well as instituting regular monitoring and evaluation strategies

Evaluating Knowledge of a Function-based Cognitive-Behavioural Treatment for Obsessive Compulsive Behaviour in Autism Spectrum Disorder

Children with Autism Spectrum Disorder (ASD) have restricted and repetitive behaviours (RRBs) which may be similar to obsessions and compulsions in Obsessive Compulsive Disorder (OCD). These behaviours can be intrusive and interfere in the lives of the child and their family. Preliminary studies have shown success in using adapted Cognitive Behavioural Therapy (CBT) to treat these behaviors in children with high functioning ASD. Using a hypothetical vignette, this thesis attempted to examine procedural knowledge that the children and their parents gained while participating in a CBT treatment that was evaluated in a Randomized Controlled Trial. For both parents and children, there was a significant increase in number of strategies generated from pre to post-treatment. Further, children in the experimental group generated significantly more strategies than the treatment as usual (TAU) group post-intervention. There was no significant correlation between number of strategies generated and the child’s treatment success, age, or IQ.

The perceptions of commune health workers about an education strategy received for counselling fathers about infant and breastfeeding involvement

Objective To evaluate the perceptions of healthcare workers in Vietnam about the efficacy of a continuing education strategy about father involvement and breastfeeding counselling. Design One group, post-test only, quasi-experimental design Method A questionnaire based on Social Cognitive Theory (SCT; Bandura, 2004) was disseminated to participants (N=28). This questionnaire measured self-efficacy, outcome expectations, socio-structural factors, goal setting and behaviour. Multiple regressions were analyzed predicting participants’ practice of client focused father involvement consulting. Results Bivariate correlations demonstrated the anticipated patterns of association between SCT-based constructs. Multiple regression analysis indicated that outcome expectations and barriers were significant predictors of client focused father involvement consulting. Conclusions Participants reported that the education increased their self-efficacy, outcome expectations and client focused father involvement consulting behaviour. Future education should be accessible, increase counselling confidence and address beliefs about the outcomes and challenges of father involvement consulting.