Synthetic approaches to syn-diol containing biologically active compounds /

The deoxy derivative of pancratistatin 1.10 was prepared in good yield through the use of a [4+2] Diels-Alder cycloaddition and Bischler-Napieralski cyclization approach. The Bischler-Napieralski cyclization was shown to yield two additional side products 2.9, 2.10, however, under slightly modified hydrolysis conditions, the tetracyclic product 2.11 was obtained exclusively in greater than 84% yield. Initial screening of the di-hydroxylatgd derivative, and the other complementary pair analogue 1.10' previously prepared in our laboratories gave interesting results. Both of these compounds were shown to exhibit cytostatic activity; the mono-alcohol was marginally active while the di-hydroxylated analogue proved to be more potent although one to two magnitudes less potent than pancratistatin itself Human tumour cell line assay results indicated that the di-hydroxylated derivative exhibited selective cytotoxic inhibition in the following cell lines: non-small cell lung cancer line NCI-H226 (ED50 - 0.65 ^g/mL), leukemia cell lines CCRF-CEM (ED30 = 0.55 Hg/mL) and HL-60(TB) (ED50 = 0.89^ig/mL). Our results demonstrated that the pharmacophore is not a mono-alcohol, and that the minimum pharmacophore contains the hydroxyl group at the C4 position in addition to either, or both, of the hydroxyl groups present at C2 and C3.' The minimum pharmacophore has been narrowed to only three possibilities which are current synthetic targets in several research groups. The controlled Grignard addition to the tartaric acid derived bis-Weinreb amide 1.25 afforded a direct entry to a host of 1,4-diflferentiated tartaric acid derived intermediates (2.12-2.18). This potentially usefiil methodology was demonstrated through the efficient synthesis of the naturally occurring lactone 2.23, which bears the inherent syn-dio\ subunit. Based on this result, a similar approach to the synthesis of syn-dio\ bearing natural products looks very promising? A direct 2,3-diol desymmetrization method using TIPS-triflate was shown to be effective on the selective differentiation of Z,-methyl tartrate (and diisopropyl tartrate). The mono-silyl-protected intermediates 2.31 also proved to be useful when they were selectively differentiated at the 1,4-carboxyl position (2.35, 2.36) through the use of a borohydride reducing agent. Furthermore, the mono-silyl-protected derivative underwent periodate cleavage affording two synthetically useful a,P-unsaturated esters 2.43, 2.44, with one of esters being obtained via a silyl-migration method.''

Developmental patterns of individiuals within a sensory-based learning environment in art education : insights emerging from a case study /

My research permitted me to reexamine my recent evaluations of the Leaf Project given to the Foundation Year students during the fall semester of 1997. My personal description of the drawing curriculum formed part of the matrix of the Foundation Core Studies at the Ontario College of Art and Design. Research was based on the random selection of 1 8 students distributed over six of my teaching groups. The entire process included a representation of all grade levels. The intent of the research was to provide a pattern of alternative insights that could provide a more meaningful method of evaluation for visual learners in an art education setting. Visual methods of learning are indeed complex and involve the interplay of many sensory modalities of input. Using a qualitative method of research analysis, a series of queries were proposed into a structured matrix grid for seeking out possible and emerging patterns of learning. The grid provided for interrelated visual and linguistic analysis with emphasis in reflection and interconnectedness. Sensory-based modes of learning are currently being studied and discussed amongst educators as alternative approaches to learning. As patterns emerged from the research, it became apparent that a paradigm for evaluation would have to be a progressive profile of the learning that would take into account many of the different and evolving learning processes of the individual. A broader review of the student's entire development within the Foundation Year Program would have to have a shared evaluation through a cross section of representative faculty in the program. The results from the research were never intended to be conclusive. We realized from the start that sensory-based learning is a difficult process to evaluate from traditional standards used in education. The potential of such a process of inquiry permits the researcher to ask for a set of queries that might provide for a deeper form of evaluation unique to the students and their related learning environment. Only in this context can qualitative methods be used to profile their learning experiences in an expressive and meaningful manner.

Applications of dihydroarenediols to chemoenzymatic synthesis : approaches to total synthesis of morphine alkaloids

The present studies describe, as a primary goal, our recent progess toward the synthesis of morphine alkaloids from aromatic precursors. Model substrates were synthesized which allowed investigation into Diels-Alder, radical cascade, and palladium-catalyzed bond-forming reactions as possible routes to the morphine alkaloid skeleton. As a secondary objective, three separate series of aromatic substrates were subjected to whole-cell oxidation with Escherichia coli JM 109 (pDTG601), a recombinant organism over-expressing the enzyme toluene dioxygenase. Included in this study were bromothioanisoles, dibromobenzenes, and cyclopropylbenzene derivatives. The products of oxidation were characterized by chemical conversion to known intermediates. The synthetic utility of one of these bacterial metabolites, derived from oxidation of o-dibromobenezene, was demonstrated by chemical conversion to (-)conduritol E.

Resilience factors of university and college students with learning disabilities as revealed through retrospective interviews /

This qualitative study examined resilience factors of eight university and college students with learning disabilities as revealed through retrospective interviews. This study has added to the existing literature surrounding resilience especially as it relates to individuals with learning disabilities. This study may provide additional insight into the emotional impacts of repeated and chronic risks on students with learning disabilities. The major themes that emerged using the interpretive phenomenological analysis method (Smith & Osborn, 2003) were organized under these four major headings: Challenges and Obstacles, Surviving Challenges, Supportive Conditions, and A Journey of Discovery and Hope. An adaptation of the listening guide analytical method (Gilligan, Spencer, Weinberg, & Bertsch, 2003) was also utilized and offered a more personal depiction of the participants and an exploration of the unique contributions their stories made to this study. Specifically, a theme of feeling trapped/wanting to escape emerged as a reaction to adversity faced during elementary school years. Furthennore, this study has demonstrated that for several of the participants, the benefits of positive outlets extended beyond nurturing areas of strength and self-esteem to also include the provision of a short respite from their challenges and enhanced feelings of overall well-being. Additionally, this study may add to the existing literature surrounding character traits evident in resilient students, specifically highlighting the significance of optimism and selfacceptance.

Shop-floor narratives : how six workers and a researcher describe learning activities

I am a part-time graduate student who works in industry. This study is my narrative about how six workers and I describe shop-floor learning activities, that is learning activities that occur where work is done, outside a classroom. Because this study is narrative inquiry, you wilileam about me, the narrator, more than you would in a more conventional study. This is a common approach in narrative inquiry and it is important because my intentions shape the way that I tell these six workers' stories. I developed a typology of learning activities by synthesizing various theoretical frameworks. This typology categorizes shop-floor learning activities into five types: onthe- job training, participative learning, educational advertising, incidental learning, and self-directed learning. Although learning can occur in each of these activities in isolation, it is often comprised of a mixture of these activities. The literature review contains a number of cases that have been developed from situations described in the literature. These cases are here to make the similarities and differences between the types of learning activities that they represent more understandable to the reader and to ground the typology in practice as well as in theory. The findings are presented as reader's theatre, a dramatic presentation of these workers' narratives. The workers tell us that learning involves "being shown," and if this is not done properly they "learn the hard way." I found that many of their best case lean1ing activities involved on-the-job training, participative learning, incidentalleaming, and self-directed learning. Worst case examples were typically lacking in properly designed and delivered participative learning activities and to a lesser degree lacking carefully planned and delivered on-the-job training activities. Included are two reflective chapters that describe two cases: Learning "Engels" (English), and Learning to Write. In these chapters you will read about how I came to see that my own shop-floor learning-learning to write this thesis-could be enhanced through participative learning activities. I came to see my thesis supervisor as not only my instructor who directed and judged my learning activities, but also as a more experienced researcher who was there to participate in this process with me and to help me begin to enter the research community. Shop-floor learning involves learners and educators participating in multistranded learning activities, which require an organizational factor of careful planning and delivery. As with learning activities, which can be multi-stranded, so too, there can be multiple orientations to learning on the shop floor. In our stories, you will see that these six workers and I didn't exhibit just one orientation to learning in our stories. Our stories demonstrate that we could be behaviorist and cognitivist and humanist and social learners and constructivist in our orientation to learning. Our stories show that learning is complex and involves multiple strands, orientations, and factors. Our stories show that learning narratives capture the essence of learning-the learners, the educators, the learning activities, the organizational factors, and the learning orientations. Learning narratives can help learners and educators make sense of shop-floor learning.

The assessment of self-directed learning among pre-service students in an Ontario faculty of education

The study determined students' perceptions of self-directed learning in their courses. Tests to assess perceptions are not being used in many programs. Assessments such as the Self-Directed Readiness Scale (SDLRS) and the Oddi continuing Learning Inventory (OCLI) have weaknesses that may have affected the use of tests. In this study, the creation of the Self-Directed Learning Test (SDLT) monitored students' perceptions by addressing what students were told before registration, how much input students had in developing the structure of the course, how much input students have in determining the evaluation for the course, what style of learning is taking place, and the characteristics of learning found among students. Fifty-one students in the pre-service program at Brock University completed the SDLT. Results showed that 47.1% of the sample liked self-directed learning. Several students who stated that they did not like selfdirected learning did not know what self-directed learning was. Results supported Brookfield's (1986) claim for more education on what self-directed learning is. The study did not support Knowles' (1980) assumption that adult students know and want to follow self-directed approaches to learning. The SDLT is a good method for monitoring self-directed learning and how students perceive their courses.

The association of faculty's teaching philosophy and teaching behaviour, and critical thinking and self- direction in learning

The intent in this study was to investigate in what ways teachers· beliefs about education and teaching are expressed in the specific teaching behaviours they employ, and whether teaching behaviours, as perceived by their students, are correlated with students· critical thinking and self-directed learning. To this end the relationships studied were: among faCUlty members· philosophy of teaching, locus of control orientation, psychological type, and observed teaching behaviour; and among students· psychological type, perceptions of teaching behaviour, self-directed learning readiness, and critical thinking. The overall purpose of the study was to investigate whether the implicit goals of higher education, critical thinking and self-direction, were actually accounted for in the university classroom. The research was set within the context of path-goal theory, adapted from the leadership literature. Within this framework, Mezirow·s work on transformative learning, including the influences of Habermas· writings, was integrated to develop a theoretical perspective upon which to base the research methodology. Both qualitative and quantitative methodologies were incorporated. Four faCUlty and a total of 142 students participated in the study. Philosophy of teaching was described through faCUlty interviews and completion of a repertory grid. Faculty completed a descriptive locus of control scale, and a psychological type test. Observations of their teaching behaviour were conducted. Students completed a Teaching Behaviour Assessment Scale, the Self-Directed Learning Readiness Scale, a psychological type test, and the Watson-Glaser Critical Thinking Appraisal. A small sample of students were interviewed. Follow-up discussions with faculty were used to validate the interview, observation, teaching behaviour, and repertory grid data. Results indicated that some discrepancies existed between faculty's espoused philosophy of teaching and their observed teaching behaviour. Instructors' teaching behaviour, however, was a function of their personal theory of practice. Relationships were found between perceived teaching behaviour and students· self-directed learning and critical thinking, but these varied across situations, as would be predicted from path-goal theory. Psychological type of students and instructor also accounted for some of the variability in the relationships studied. Student psychological type could be shown as a partial predictor of self-directed learning readiness. The results were discussed in terms of theory development and implications for further research and practice.

The nature of avidyÄ in Buddhism and VedÄ nta

This thesis deals with the nature of ignorance as it was interpreted in the Upani~adic tradition, specifically in Advaita Vedanta, and in early and Mahayana Buddhism , e specially in the Madhyamika school of Buddhism. The approach i s a historical and comparative one. It examines the early thoughts of both the upanis.a ds and Buddhism abou t avidya (ignorance), shows how the notion was treated by the more speculative and philosphically oriented schools which base d themselves on the e arly works, and sees how their views differ. The thesis will show that the Vedinta tended to treat avidya as a topic for metaphysical s peculation as t he s chool developed, drifting from its initial e xistential concerns, while the Madhyamika remained in contact with the e xistential concerns evident in the first discourses of the Buddha. The word "notion" has been chosen for use in referring t o avidya, even though it may have non-intellectual and emotional connotations, to avoid more popular a lternatives such as "concept" or "idea". In neither the Upani,ads, Advaita Vedanta, or Buddhism is ignorance merely a concept or an idea. Only in a secondary sense, in texts and speech , does it become one. Avidya has more to do with the lived situation in which man finds himself, with the subjectobject separation in which he f eels he exists, than with i i i intel lect ual constr ucts . Western thought has begun to r ealize the same with concerns such as being in modern ontology, and has chosen to speak about i t i n terms of the question of being . Avidya, however, i s not a 'question' . If q ue stions we r e to be put regarding the nature of a vidya , they would be more of t he sort "What is not avidya?", though e ven here l anguage bestows a status t o i t which avidya does not have. In considering a work of the Eastern tradition, we f ace t he danger of imposing Western concepts on it. Granted t hat avidya is customari ly r endered i n English as ignorance, the ways i n which the East and West view i gno rance di f f er. Pedagogically , the European cultures, grounded in the ancient Greek culture, view ignorance as a l ack or an emptiness. A child is i gnorant o f certain t hings and the purpose o f f ormal education , in f act if not in theory, is to fill him with enough knowledge so that he can cope wit h t he complexities and the e xpectations of s ociety. On another level, we feel t hat study and research will l ead t o the discovery o f solutions, which we now lack , for problems now defying solut i on . The East, on the o t her hand, sees avidya in a d i fferent light.Ignorance isn't a lack, but a presence. Religious and philosophical l iterature directs its efforts not towards acquiring something new, but at removing t.he ideas and opinions that individuals have formed about themselves and the world. When that is fully accomplished, say the sages , t hen Wisdom, which has been obscured by those opinions, will present itself. Nothing new has to be learned, t hough we do have t o 'learn' that much. The growing interest in t he West with Eastern religions and philosophies may, in time, influence our theoretical and practical approaches to education and learning, not only in the established educati onal institutions, but in religious , p sychological, and spiritual activities as well. However, the requirements o f this thesis do no t permit a formulation of revolutionary method or a call to action. It focuses instead on the textual arguments which attempt to convince readers that t he world in which they take themselves to exist is not, in essence, real, on the ways i n which the l imitations of language are disclosed, and on the provisional and limited schemes that are built up to help students see through their ignorance. The metaphysic s are provisional because they act only as spurs and guides. Both the Upanisadic and Buddhist traditions that will be dealt with here stress that language constantly fails to encompass the Real. So even terms s uch as 'the Real', 'Absolute', etc., serve only to lead to a transcendent experience . The sections dealing with the Upanisads and Advaita Vedanta show some of the historical evolution of the notion of avidya, how it was dealt with as maya , and the q uestions that arose as t o its locus. With Gau?apada we see the beginnings of a more abstract treatment of the topic, and , the influence of Buddhism. Though Sankhara' S interest was primarily directed towards constructing a philosophy to help others attain mok~a ( l iberation), he too introduced t echnica l t e rminology not found in the works of his predecessors. His work is impressive , but areas of it are incomplete. Numbers of his followers tried to complete the systematic presentation of his insi ghts . Their work focuses on expl anat i ons of adhyasa (superimposition ) , t he locus and object of ignorance , and the means by which Brahman takes itself to be the jiva and the world. The section on early Buddhism examines avidya in the context o f the four truths, together with dubkha (suffering), the r ole it p l ays in t he chain of dependent c ausation , a nd t he p r oblems that arise with t he doctrine of anatman. With t he doct rines of e arly Buddhism as a base, the Madhyamika elaborated questions that the Buddha had said t e nded not t o edi f ication. One of these had to do with own - being or svabhava. Thi s serves a s a centr e around which a discussion o f i gnorance unfolds, both i ndividual and coll ective ignorance. There follows a treatment of the cessation of ignorance as it is discussed within this school . The final secti on tries to present t he similarities and differences i n the natures o f ignorance i n t he two traditions and discusses the factors responsible for t hem . ACKNOWLEDGEMENTS I would like to thank Dr. Sinha for the time spent II and suggestions made on the section dealing with Sankara and the Advait.a Vedanta oommentators, and Dr. Sprung, who supervised, direoted, corrected and encouraged the thesis as a whole, but especially the section on Madhyamika, and the final comparison.

Therapeutic riding : learning and recovery for people with disabilities

The purpose ofthis study was to explore the process oftherapeutic riding as an experiential and holistic approach to learning and recovery for people with disabilities as perceived by the providers oftherapeutic riding. To enhance the connection between theory and practice and to suggest future research, the researcher endeavoured to develop a theory that contributed to the knowledge base oftherapeutic riding, animal-assisted therapy and education, experiential education, and experiential therapy in addition to contributing to connections among them. This topic was investigated because ofthe lack ofresearch about the process of therapeutic riding, particularly from learning and a recovery perspective. Few studies have addressed how therapeutic riding outcomes are achieved or how the therapeutic riding process actually works. This study was identified as grounded theory using qualitative data through interviews and narrative reflections with therapeutic riding providers, a researcher's journal, field notes, and written documents. Grounded theory analysis was used to analyze the qualitative data. This consisted ofdoing open, axial, and selective coding. This study provided detailed descriptions ofthe research approach, researcher's involvement, participant and site selection, data collection and analysis, methodological assumptions and limitations, credibility established, and ethical considerations. The findings ofthe data analysis revealed the theme ofrelationships as central to the learning and recovery process oftherapeutic riding for people with disabilities. The significance ofthe team relationships, the horse and rider relationship, and the providers and rider relationship was found. The essential components ofthe learning and recovery process were presented in a diagram in the selective coding phase. Goals oftherapeutic riding included psycho-education; behavioural and social; physical; and equestrian. Parts ofthe process ofhow outcomes were achieved included motivation; "opens new doors;" risk; task analysis; control; communication; and environmental factors. Outcomes of therapeutic riding included independence and mobility; confidence; and transfer abilities or skills. The implications ofthese findings for theory, practice, and further research were also. explored.

Show me, help me, let me : supporting teachers' changing conceptions of reading assessment and reading instruction

This qualitative inquiry used case study methodology to explore the change processes of 3 primary-grade teachers throughout their participation in 7 -month professional learning initiative focused on reading assessment and instruction. Participants took part in semimonthly inquiry-based professional learning community sessions, as well as concurrent individualized classroom-based literacy coaching. Each participant's experiences were first analyzed as a single case study, followed by cross-case analyses. While their patterns of professional growth differed, findings documented how all participants altered their understandings of the roles and relevancy of individual components of reading instruction (e.g., comprehension, decoding) and instructional approaches to scaffold students' growth (e.g., levelled text, strategy instruction), and experienced some form of conceptual change. Factors identified as affecting their change processes included; motivation, professional knowledge, professional beliefs (self-efficacy and theoretical orientation), resources (e.g., time, support), differentiated professional learning with associated goal-setting, and uncontrollable influences, with the affect of each factor compounded by interaction with the others. Comparison of participants' experiences to the Cognitive-Affective Model of Conceptual Change (CAMCC) and the Interconnected Model of Teacher Professional Growth (IMTPG) demonstrated the applicability of using both conceptual models, with the IMTPG providing macrolevel insights over time and the CAMCC microlevel insights at each change intervaL Recommendations include the provision of differentiated teacher professional learning opportunities, as well as research documenting the effects of teacher mentorship programs and the professional growth of teacher educators. ii

Development of thermally stable versions of the Burgess Reagent : approaches to the chemoenzymatic total synthesis of morphine

The present studies describe our recent work on expanding the use of the Burgess reagent and its reaction with oxiranes. Several new variants of the Burgess reagent and its chiral auxiliary version were evaluated for their thermal stability by NMR spectroscopy. Three new versions of the reagent were synthesized and their stability was determined. The reactivity of all five Burgess reagents was compared in a dehydration reaction and reactions with epoxides and diols. Progress toward a chemoenzymatic synthesis of morphine is also included in this report. The synthesis began with the whole cell oxidation of bromobenzene by Escherichia coli JMI09(pDTG601). The preparation of several precursors for a key step involving the lohnson-Claisen rearrangement and progress toward the total synthesis are described.

Globalization and Its Impact on Assessment: Moving Toward a New Story

Globalization has resulted in large-scale international and local assessments closely tied to notions of accountability and competitiveness in a globalized economy. Although policy makers seek to ensure citizens meet the demands of a global knowledge-based economy, such assessments may also impede the development of requisite 21st century skills. While standardization currently is viewed as the most effective measurement of student achievement, several Canadian and international jurisdictions are moving toward assessment for learning (AfL). This conceptual study sought to identify whether AfL or standardized assessment most effectively meets 21st century learning goals in the wake of rapid global change. It applies a Story Model theoretical framework to understand the current, the new emerging, and the future ideal story of education from a personal, cultural, and global lens. The study examines the main critiques and/or challenges of standardized testing, the benefits of AfL for student learning, and new teaching and assessment approaches to the development of 21st century learning goals. The study applies the Story Model’s inside-outside/past-future approach to determine the future direction of assessment. Results show that the new story of assessment will most likely entail a model that integrates both standardized testing and in-class assessments in the form of AfL and PBL.

Whose Voice Is Present?: An Examination of Power and Privilege in Service-Learning in Ontario Universities

This research paper examines themes of power and privilege that occur within service-learning as described by 3 Ontario universities on their service-learning websites. Due to size and time restrictions, this paper was able to examine only 3 Ontario universities: Brock, Wilfrid Laurier, and Lakehead. The purpose of this study is geared towards service-learning practitioners in order for the universities and students to become more self-aware of their immense place of privilege within the service-learning context. Qualitative narrative analysis research methods were employed in this purposeful sample to examine how each university’s story of service-learning reflected themes of power and privilege. The research found that each university posed a unique narrative of service-learning representing various stakeholders’ voices and presence in different ways on their website. Brock largely focuses on faculty and student voices. Laurier intentionally attempts to include all three stakeholder voices, although still favours students and the university as an audience over the community. Lakehead’s unique program includes a plethora of voices and intends much of their information for the community members, students, and the university. The implications of this research demonstrate that universities have a large amount of power and privilege, which is carried through to the students within the service-learning partnership.

The effects of consistency and inconsistency between attentional focus and task objective in learning a golf putting task

Converging evidence has demonstrated learning advantages when an individual is instructed to focus their attention externally. However, many of the motor tasks utilized in past research had clear external objectives (i.e., putting accuracy), creating a compatible relationship between an external focus of attention (i.e., outcome) and an external task objective (i.e., putting accuracy). The present study examined whether or not the consistency of instructions and task objective would differentially impact the acquisition of a golf putting task. Participants performed a putting task in a control condition or in one of four experimental conditions resulting from the factorial interaction of task instructions (internal or external) and task objective (internal or external). The retention and transfer data revealed that participants who received an external task objective demonstrated superior outcome scores. Participants who received technique information paired with outcome information demonstrated superior technique scores.

Algal and protozoan response to Holocene climate change and anthropogenic impact: a case study from Sluice Pond, MA

Sluice Pond is a small (18 ha) and deep (Zmax 20.0 m) partially meromictic, pond in Lynn, Massachusetts that contains a diverse dinocyst record since the early Holocene. High dinocyst concentrations, including morphotypes not previously described, as well as the preservation of several specimens of cellulosic thecae are attributed to low dissolved oxygen (DO) in the basin. The fossil protozoan record supports the interpretation- thecamoebians were unable to colonize the basin until the middle Holocene and only became abundant when the drought-induced lowstand oxygenated the bottom waters. Protozoans tolerant of low DO became abundant through the late Holocene as water levels rose and cultural eutrophication produced a sharp increase in biochemical oxygen demand (BOD) beginning in the 17th century. Recent sediments contain a dominance of Peridinium willei, indicating cultural eutrophication and the planktonic ciliate Codonella cratera and the thecamoebian Cucurbitella tricuspis in the deep basin. Above the chemocline however, a diverse difflugiid thecamoebian assemblage is present.