This infinite, unanimous dissonance : a study in mathematical existentialism through the work of Jean-Paul Sartre and Alain Badiou

This thesis seeks to elucidate a motif common to the work both of Jean-Paul Sartre and Alain Badiou (with special attention being given to Being and Nothingness and Being and Event respectively): the thesis that the subject 's existence precedes and determines its essence. To this end, the author aims to explicate the structural invariances, common to both philosophies, that allow this thesis to take shape. Their explication requires the construction of an overarching conceptual framework within which it may be possible to embed both the phenomenological ontology elaborated in Being and Event and the mathematical ontology outlined in Being and Event. Within this framework, whose axial concept is that of multiplicity, the precedence of essence by existence becomes intelligible in terms of a priority of extensional over intensional determination. A series of familiar existentialist concepts are reconstructed on this basis, such as lack and value, and these are set to work in the task of fleshing out the more or less skeletal theory of the subject presented in Being and Event.

Geology of the Rankin Inlet area, Northwest Territories /

The Rankin Inlet area, on the west shore of Hudson Bay in the Northwest Territories, is in the Churchill Structural Province. Metamorphosed volcanic and sedimentary rocks, previously mapped as Archean and part of the Kaminak Group, underlie most of the area. The Rankin Inlet Group consists of greywacke, with minor conglomeratic greywacke, quartzite and dolomite, overlain by massive and pillowed basaltic flows. Gabbro sills intrude the sediments near the base of the volcanic sequence and three serpentinite sills outcrop at the base of the volcanic sequence. The sediments are in fault-contact with quartz monzonite to the south and were intruded by granitic rocks to the northwest. Two periods of folding were defined by the mapping. The first generation folds are recumbent isoclinal folds, with northwest-trending and northeast-dipping axial planes, formed through gravitational sliding. The second generation folds are symmetrically disposed about the axis of the granitic intrusion and have east-southeast trending and nearly vertical axial planes. Whole-rock analysis of 64 rock samples indicates that metasomatic alteration accompanied the intrusion of both the granitic rocks and the serpentinite. The volcanic rocks, gabbro and serpentinite were derived from a magma of oceanic tholeiitic affinities. The stratigraphic sequence and chemistry of the volcanic rocks of the Rankin Inlet Group indicate that this assemblage is correlative with the Hurwitz Group rather than the Kaminak Group and is therefore Aphebian in age.

Petrography and geochemistry of the McArthur Township area, Ontario /

The McArthur Township area in the Archean Abitibi Belt of northeast Ontario contains northwesterly trending volcanic rocks which are located on a limb of a large syncline. The axial trace of the syncline passes through the adjacent Douglas Township. The Archean volcanic rocks and associated sedimentary rocks are intruded and deformed by two large plutons and a few smaller hypabyssal intrusions. A petrographic and geochemical study of the Precambrian rocks exposed 1n the study area was undertaken in order to investigate the metamorphic grade and geochemical characteristics of the rocks. All the samples were studied with the microscope and analysis of 20 major and trace elements were determined on a selection of the less altered specimens by x-ray fluorescence. Three different periods of igneous activity have occurred in the study area. The first two periods were dominated by volcanic extrusive rocks accompanied by gabbroic sills. The third cycle is the diapiric intrusion of the granitic plutons and subsequent metamorphism of the older rocks to the low to medium grade. Two periods of sedimentation are also recognized in the study area which occurred after the first and second cycle of volcanism. Chemically, the lavas are subdivided into three main associations: (1) The komatiitic association is characterized by high MgO, high Ni, low Ti02 and a low FeO*/(FeO* + MgO) ratio. They occupy the base of each volcanic cycle and some of the flows exhibit spinifex textures. (2) The tholeiitic association displays distinct iron and titanium enrichment trends in the intermediate membersor -i r (3) The calc-alkaline association contains low FeO* and TI02 and high Ni contents relative to modern calc-alkaline types. They are formed at the end of each cycle of volcanism and overlie the tholeiitic flows. All three associations of the first volcanic cycle are exposed in the study area, while the second cycle is represented by a komatiltic sequence. The volcanic rocks were possibly formed by multiple partial melting of the Archean mantle to produce parental magmas under various P - T conditions.

Confocal and two-photon microscopy : image enhancement /

Confocal and two-photon microcopy have become essential tools in biological research and today many investigations are not possible without their help. The valuable advantage that these two techniques offer is the ability of optical sectioning. Optical sectioning makes it possible to obtain 3D visuahzation of the structiu-es, and hence, valuable information of the structural relationships, the geometrical, and the morphological aspects of the specimen. The achievable lateral and axial resolutions by confocal and two-photon microscopy, similar to other optical imaging systems, are both defined by the diffraction theorem. Any aberration and imperfection present during the imaging results in broadening of the calculated theoretical resolution, blurring, geometrical distortions in the acquired images that interfere with the analysis of the structures, and lower the collected fluorescence from the specimen. The aberrations may have different causes and they can be classified by their sources such as specimen-induced aberrations, optics-induced aberrations, illumination aberrations, and misalignment aberrations. This thesis presents an investigation and study of image enhancement. The goal of this thesis was approached in two different directions. Initially, we investigated the sources of the imperfections. We propose methods to eliminate or minimize aberrations introduced during the image acquisition by optimizing the acquisition conditions. The impact on the resolution as a result of using a coverslip the thickness of which is mismatched with the one that the objective lens is designed for was shown and a novel technique was introduced in order to define the proper value on the correction collar of the lens. The amoimt of spherical aberration with regard to t he numerical aperture of the objective lens was investigated and it was shown that, based on the purpose of our imaging tasks, different numerical apertures must be used. The deformed beam cross section of the single-photon excitation source was corrected and the enhancement of the resolution and image quaUty was shown. Furthermore, the dependency of the scattered light on the excitation wavelength was shown empirically. In the second part, we continued the study of the image enhancement process by deconvolution techniques. Although deconvolution algorithms are used widely to improve the quality of the images, how well a deconvolution algorithm responds highly depends on the point spread function (PSF) of the imaging system applied to the algorithm and the level of its accuracy. We investigated approaches that can be done in order to obtain more precise PSF. Novel methods to improve the pattern of the PSF and reduce the noise are proposed. Furthermore, multiple soiu'ces to extract the PSFs of the imaging system are introduced and the empirical deconvolution results by using each of these PSFs are compared together. The results confirm that a greater improvement attained by applying the in situ PSF during the deconvolution process.

Structural, stratigraphic and geochemical studies of the Horwood Peninsula - Gander Bay Area, Northeast Newfoundland /

The Horwood Peninsula - Gander Bay area is located at NE Newfoundland in the Botwood Zone (Williams et a1., 1974) or in the Dunnage Zone (Williams, 1979) of the Central Mobile Belt of the Newfoundland Appalachians. The area is underlain by Middle Ordovician to possible Lower Silurian rocks of the Davidsville and Indian Islands Groups, respectively. Three conformable formations named informally : the Mafic Volcanic Formation, the Greywacke and Siltstone Formation and the Black Slate Formation, have been recognized in the Davidsville Group. The Greywacke and the Black Slate Formations pass locally into a Melange Formation. From consideration of regional structure and abundant locally-derived mafic volcanic olisto- 1iths in the melange, it is considered to have originated by gravity sliding rather than thrusting. Four formations have been recognized in the Indian Islands Group. They mainly contain silty slate and phyllite, grey cherty siltstone, green to red micaceous siltstone and limestone horizons. Repetition of lithological units by F1 folding are well-demonstrated in one of formations in this Group. The major structure in this Group on the Horwood Peninsula is interpreted to be a synclinal complex. The lithology of this Group is different from the Botwood Group to the west and is probably Late Ordovician and/or Early Silurian in age. The effects of soft-sediment deformation can be seen from the lower part of the Davidsville Group to the middle part of the Indian Islands Group indicating continuous and/or episodic slumping and sliding activities throughout the whole area. However, no siginificant depOSitional and tectonic break that could be assigned to the Taconian Orogeny has been recognized in this study. Three periods of tectonic deformation were produced by the Acadian Orogeny. Double boudinage in thin dikes indicates a southeast-northwest sub-horizontal compression and main northeast-southwest sub-horizontal extension during the D1 deformation. A penetrative, axial planar slaty cleavage (Sl) and tight to isocJ.ina1 F1 folds are products of this deformation. The D2 and D3 deformations formed S2 and S3 fabrics associated with crenulations and kink bands which are well-shown in the slates and phyllites of the Indian Islands Group. The D2 and D3 deformations are the products of vertical and northeast-southwest horizontal shortening respectively. The inferred fault between the Ordovician slates (Davidsville Group) and the siltstones (Indian Islands Group) suggested by Williams (1963, 1964b, 1972, 1978) is absent. Formations can be followed without displacement across this inferred fault. Chemically, the pillow lavas, mafic agglomerates, tuff beds and diabase dikes are subdivided into three rock suites : (a) basaltic komatiite (Beaver Cove Assemblage), (b) tholeiitic basalt (diabase dikes), (c) alkaline basalt (Shoal Bay Assemblage). The high Ti02 , MgO, Ni contents and bimodal characteristic of the basaltic komatiite in the area are comparable to the Svartenhuk Peninsula at Baffin Bay and are interpreted to be the result of an abortive volcano-tectonic rift-zone in a rear-arc basin. Modal and chemical analyses of greywackes and siltstones show the trend of maturity of these rocks increasing from poorly sorted Ordovician greywackes to fairly well-sorted Silurian siltstones. Rock fragments in greywackes indicate source areas consisting of plagiogranite, low grade metamorphic rocks and ultramafic rocks. Rare sedimentary structures in both Groups indicate a southeasterly provenance. Trace element analyses of greywackes also reveal a possible island-arc affinity.

The design, synthesis and characterization of new building blocks for the preparation of molecule-based magnetic materials /

Two new families of building blocks have been prepared and fully characterized and their coordination chemistry exploited for the preparation of molecule-based magnetic materials. The first class of compounds were prepared by exploiting the chemistry of 3,3'-diamino-2,2'-bipyridine together with 2-pyridine carbonyl chloride or 2-pyridine aldehyde. Two new ligands, 2,2'-bipyridine-3,3'-[2-pyridinecarboxamide] (Li, 2.3) and N'-6/s(2-pyridylmethyl) [2,2'bipyridine]-3,3'-diimine (L2, 2.7), were prepared and characterized. For ligand L4, two copper(II) coordination compounds were isolated with stoichiometrics [Cu2(Li)(hfac)2] (2.4) and [Cu(Li)Cl2] (2.5). The molecular structures of both complexes were determined by X-ray crystallography. In both complexes the ligand is in the dianionic form and coordinates the divalent Cu(II) ions via one amido and two pyridine nitrogen donor atoms. In (2.4), the coordination geometry around both Cu11 ions is best described as distorted trigonal bipyramidal where the remaining two coordination sites are satisfied by hfac counterions. In (2.5), both Cu(II) ions adopt a (4+1) distorted square pyramidal geometry. One copper forms a longer apical bond to an adjacent carbonyl oxygen atom, whereas the second copper is chelated to a neighboring Cu-Cl chloride ion to afford chloride bridged linear [Cu2(Li)Cl2]2 tetramers that run along the c-axis of the unit cell. The magnetic susceptibility data for (2.4) reveal the occurrence of weak antiferromagnetic interactions between the copper(II) ions. In contrast, variable temperature magnetic susceptibility measurements for (2.5) reveal more complex magnetic properties with the presence of ferromagnetic exchange between the central dimeric pair of copper atoms and weak antiferromagnetic exchange between the outer pairs of copper atoms. The Schiff-base bis-imine ligand (L2, 2.7) was found to be highly reactive; single crystals grown from dry methanol afforded compound (2.14) for which two methanol molecules had added across the imine double bond. The susceptibility of this ligand to nucleophilic attack at its imine functionality assisted via chelation to Lewis acidic metal ions adds an interesting dimension to its coordination chemistry. In this respect, a Co(II) quaterpyridine-type complex was prepared via a one-pot transformation of ligand L2 in the presence of a Lewis acidic metal salt. The rearranged complex was characterized by X-ray crystallography and a reaction mechanism for its formation has been proposed. Three additional rearranged complexes (2.13), (2.17) and (2.19) were also isolated when ligand (L2, 2.7) was reacted with transition metal ions. The molecular structures of all three complexes have been determined by X-ray crystallography. The second class of compounds that are reported in this thesis, are the two diacetyl pyridine derivatives, 4-pyridyl-2,6-diacetylpyridine (5.5) and 2,2'-6,6'-tetraacetyl-4,4'-bipyridine (5.15). Both of these compounds have been designed as intermediates for the metal templated assembly of a Schiff-base N3O2 macrocycle. From compound (5.15), a covalently tethered dimeric Mn(II) macrocyclic compound of general formula {[Mn^C^XJCl-FkO^Cl-lO.SFbO (5.16) was prepared and characterized. The X-ray analysis of (5.16) reveals that the two manganese ions assume a pentagonal-bipyramidal geometry with the macrocycle occupying the pentagonal plane and the axial positions being filled by a halide ion and a H2O molecule. Magnetic susceptibility data reveal the occurrence of antiferromagnetic interactions between covalently tethered Mn(II)-Mn(II) dimeric units. Following this methodology a Co(II) analogue (5.17) has also been prepared which is isostructural with (5.16).

Aspects of the hemes and modulation of hydrogen donors in catalases from bovine liver, yeast, and escherichia coli

Catalase is the enzyme which decomposes hydrogen peroxide to water and oxygen. Escherichia coli contains two catalases. Hydroperoxidase I (HPI) is a bifunctional catalase-peroxidase. Hydroperoxidase II (HPII) is only catalytically active toward H202. Expression of the genes encoding these proteins is controlled by different regimes. HPJI is thought to be a hexamer, having one heme d cis group per enzymatic subunit. HPII wild type protein and heme containing mutant proteins were obtained from the laboratory of P. Loewen (Univ. of Manitoba). Mutants constructed by oligonucleotidedirected mutagenesis were targeted for replacement of either the His128 residue or the Asn201 residue in the vicinity of the HPII heme crevice. His128 is the residue thought to be analogous to the His74 distal axial ligand of the heme in the bovine liver enzyme, and Asn201 is believed to be a residue critical to the function of the enzyme because of its role in orienting and interacting with the substrate molecule. Investigation of the nature of the hemes via absorption spectroscopy of the unmodified catalase proteins and their derived pyridine hemochromes showed that while the bovine and Saccharomyces cerevisiae catalase enzymes are protoheme-containing, the HPII wild type protein contains heme d, and the mutant proteins contain either solely protoheme, or heme d-protoheme mixtures. Cyanide binding studies supported this, as ligand binding was monophasic for the bovine, Saccharomyces cerevisiae, and wild type HPII enzymes, but biphasic for several of the HPII mutant proteins. Several mammalian catalases, and at least two prokaryotic catalases, are known to be NADPH binding. The function of this cofactor appears to be the prevention of inactivation of the enzyme, which occurs via formation of the inactive secondary catalase peroxide compound (compound II). No physiologically plausible scheme has yet been proposed for the NADPH mediation of catalase activity. This study has shown, via fluorescence and affinity chromatography techniques, that NADPH binds to the T (Typical) and A (Atypical) catalases of Saccharomyces cerevisiae, and that wild type HPII apparently does not bind NADPH. This study has also shown that NADPH is unlike any other hydrogen donor to catalase, and addresses its features as a unique donor by proposing a mechanism whereby NADPH is oxidized and catalase is protected from inactivation via the formation of protein radical species. Migration of this radical to a position close to the NADPH is also proposed as an adjunct hypothesis, based on similar electron migrations that are known to occur within metmyoglobin and cytochrome c peroxidase when reacted with H202. Validation of these hypotheses may be obtained in appropriate future experiments.

Exploring the effects of change on nursing practice in acute ambulatory care settings : a qualitative study

As a result of the current changes taking place in the delivery of acute care services, the emergence of acute ambulatory care (AAC) settings is expanding. According to a literature review, the volume, acuity, and complexity of patient care in these settings is increasing while the time the patients spend under the care of nurses is decreasing. Two forces, hospital downsizing and advancing technology, are identified as the major contributors to the shift in acute care delivery. The effects that these changes are having on the clinical nursing practice of registered nurses working in AAC settings are not known. Given that AAC settings are rapidly expanding, it can be anticipated that the delivery of nursing care will continue to be compressed into a shorter time frame. Therefore, the following qualitative research question was formulated: What are the problems and issues related to clinical nursing practice in acute ambulatory settings? The purpose of this study was to explore the problems and issues associated with change and clinical nursing practice including the educational needs of nurses working in MC settings. Specific objectives of the study included the following: (a) to explore the problems and issues related to nursing practice in select AAC settings; (b) to explore the similarities and differences in perspectives related to role expectation between nurse managers, nurse educators, and staff nurses; and (c) to develop a conceptual framework that will guide the construction of an instrument needed for further research. This study used semistructured individual interviews and focus group sessions to collect data from the three categories of registered nurses. More specifically, data were collected from one nurse manager, two charge nurses, two nurse educators and fifteen staff nurses, working in three different MC settings of a major teaching hospital. Collected data were separately analyzed by the researcher and an external rater following grounded theory methodology. By using open and axial coding, the problems and issues identified by nurses were grouped into several major and minor themes. In final analysis, by using selective coding, the four core themes (intensification, moderation, frustration, and adaptation) were extracted. Each core theme was presented and discussed in relation to hospital downsizing and advancing technology. The relationships among the four core themes were discussed and depicted in a model termed the "Impact and Consequence Model on Nursing Practice in MC Settings." Implications for further research are discussed and research hypotheses, based on the research findings, are presented.

Petrography, geochemistry and structure of the Timmins area, Ontario

Regional structural analysis of the Timmins area indicates four major periods of tectonic deformation. The DI deformation is characterized by a series of isoclinal FI folds which are outlined in the study area by bedding, pillow tops and variolitic flows. The D2 deformation developed the Porcupine Syncline and refolded the Fl folds about a NE. axis. A pervasive S2 foliation developed during low grade (greenschist) regional metamorphism associated with the D2 deformation. The S2 foliation developed south of the Destor-Porcupine Break. The third phase of tectonic D3 deformation is recognized by the development of a S3 sub-horizontal crenulation cleavage which developed on the plane of the S2 foliation. No meso scopic folds are associated with this deformation. The 8 3 crenulation cleavage is observed south of the Destor-Porcupine Break. The D4 tectonic deformation is recorded as a subvertical S4 crenulation cleavage which developed on the plane of the S2 foliation and also offsets the S3 crenulation cleavage. Macroscopic F4 folds have refolded the F2 axial plane. No metamorphic recrystallization is associated with this deformation. The S4 crenulation cleavage is observed south of the Destor-Porcupine Break. Petrographic evidence indicates that the Timmins area has been subjected to pervasive regional low grade (greenschist) metamorphism which has recrystallized the original mineralogy. South of the study are~ the Donut Lake ultramafic lavas have been subjected to contact medium grade (amphibolite facies) metamorphism associated with the intrusion of the Peterlong Lake Complex. The Archean volcanic rocks of the Timmins area have been subdivided into komatiitic, tholeiitic and calcalkaline suites based on Zr, Ti0 2 and Ni. The three elements were used because of their r e lative immobility during subsequent metamorphic events. Geochemical observations in the Timmins area indicates that the composition of the Goose Lake and Donut Lake Formations are a series of peridotitic, pyroxenitic and basaltic komatiites. The Lower Schumacher Formation is a sequence of basaltic komatiites while the upper part of the Lower Schumacher Formation is an intercalated sequence of basaltic komatiites and low Ti0 2 tholeiites. The variolitic flows are felsic tholeiites in composition and geochemical evidenc e sugg ests that they developed as a n immiscible splitting of a tholeiitic magma. The Upper Schumacher Formation is a sequence of tholeiitic rocks dis p laying a mild iron enrichment. The Krist and Boomerang Formations are the felsic calc-alkaline rocks of the study area which are characteristically pyroclastic. The Redstone Fo rmation is dominantly a calc-alkali ne sequence of volcani c rocks whose minor mafic end me mbers exposed in 1t.he study hav e basaltic komatiitic compositions. Geochemical evidence sugges ts that the Keewatin-type se dimentary rocks have a composition similar to a quartz diorite or a granodiorite. Fi e l d obs ervations and petrographic evidence suggests that they were derived fr om a distal source and now repr esent i n part a turbidite sequence. The Timiskaming-type sedimentary rocks approach the c omp osi t ion of the felsic calc-alkaline rocks of the study area . The basal conglomerate in the study are a sugge s ts that th e uni t was derived fr om a proximal source. Petrographic and ge ochemical evidence suggests that the peridotitic and pyroxenitic komatiites originated as a 35-55% partial melt within the mantle, in excess of 100 Km. depth. The melt ros e as a diapir with the subsequent effusion of the ultramafic lavas, The basaltic komatiites and tholeiitic rocks originated in the mantle from lesser degrees of partial melting and fractionated in low pressure chambers. Geochemical evidence suggests a "genetic link" between the basaltic komatiites and tholeiites, The calc-alkaline rocks developed as a result of the increa.se In PO in the magma chamber. The felsic calcalkaline rocks are a late stage effusion possibly the last major volcanic eruptions in the area.

Textual characteristics of coarse sediments in selected streams of the Niagara Peninsula, Ontario

The streams flowing through the Niagara Escarpment are paved by coarse carbonate and sandstone sediments which have originated from the escarpment units and can be traced downstream from their source. Fifty-nine sediment samples were taken from five streams, over distances of 3,000 to 10,000 feet (915 to 3050 m), to determine downstream changes in sediment composition, textural characteristics and sorting. In addition, fluorometric velocity measurements were used in conjunction with measured -discharge and flow records to estimate the frequency of sediment movement. The frequency of sediments of a given lithology changes downstream in direct response to the outcrop position of the formations in the channels. Clasts derived from a single stratigraphic unit usually reach a maximum frequency within the first 1,000 feet (305 m) of transport. Sediments derived from formations at the top of waterfalls reach a modal frequency farther downstream than material originating at the base of waterfalls. Downstream variations in sediment size over the lengths of the study reaches reflect the changes in channel morphology and lithologic composition of the sediment samples. Linear regression analyses indicate that there is a decrease in the axial lengths between the intial and final samples and that the long axis decreases in length more rapidly than the intermediate, while the short axis remains almost constant. Carbonate sediments from coarse-grained, fossiliferous units - iii - are more variable in size than fine-grained dolostones and sandstones. The average sphericity for carbonates and sandstones increases from 0.65 to 0.67, while maximum projection sphericity remains nearly constant with an average value of 0.52. Pebble roundness increases more rapidly than either of the sphericity parameters and the sediments change from subrounded to rounded. The Hjulstrom diagram indicates that the velocities required to initiate transport of sediments with an average intermediate diameter of 10 cm range from 200 cm/s to 300 cm/s (6.6 ft./sec. to 9.8 ft./sec.). From the modal velocitydischarge relations, the flows corresponding to these velocities are greater than 3,500 cfs (99 m3s). These discharges occur less than 0.01 p~r cent (0.4 days) of the time and correspond to a discharge occurring during the spring flood.

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.

Synthesis and utilization of guanidine catalysts for applications directed towards the preparation of butenolide and modified amino acid derivatives

Development of guanidine catalysts is explored through direct iminium chloride and amine coupling, alongside a 2-chloro-l,3-dimethyl-IH-imidazol-:-3-ium chloride (DMC) induced thiourea cyclization. Synthesized achiral catalyst N-(5Hdibenzo[ d,t][1,3]diazepin-6(7H)-ylidene)-3,5-bis(trifluoromethyl) aniline proved unsuccessful towards O-acyl migrations, however successfully catalyzed the vinylogous aldol reaction between dicbloro furanone and benzaldehyde. Incorporating chirality into the guanidine catalyst utilizing a (R)-phenylalaninol auxiliary, generating (R)-2-((5Hdibenzo[ d,t] [1,3 ]diazepin-6(7H)-ylidene ) amino )-3 -phenylpropan-l-ol, demonstrated enantioselectivity for a variety of adducts. Highest enantiomeric excess (ee) was afforded between dibromofuranone and p-chlorobenzaldehyde, affording the syn conformation in 96% ee and the anti in 54% ee, with an overall yield of30%. Attempts to increase asymmetric induction were focused on incorporation of axial chirality to the (R)phenylalaninol catalyst using binaphthyl diamine. Incorporation of (S)-binaphthyl exhibited destructive selectivity, whereas incorporation of (R)-binaphthyl demonstrated no effects on enantioselectivity. Current studies are being directed towards identifying the catalytic properties of asymmetric induction with further studies are being aimed towards increasing enantioselectivity by increasing backbone steric bulk.

Elucidation of the Retinoid Signalling Pathway Involved in Axon Guidance in Lymnaea stagnalis and Xenopus laevis

The vitamin A metabolite, retinoic acid (RA), is known to play a crucial role in several developmental processes including axial patterning and differentiation. More recently, RA has been implicated in the regenerative process acting through its classical signaling pathway, the nuclear receptors, retinoic acid receptor (RAR) and retinoid X receptor (RXR), to mediate gene transcription. Moreover, RA has been shown to act as a guidance molecule for growth cones of regenerating motorneurons of the pond snail, Lymnaea stagnalis. Our lab has recently shown that RA can induce this morphological response independent of nuclear transcription, however, the role of the retinoid receptors in RA-induced chemoattraction is still unknown. Here, I show that the retinoid receptors, RXR and RAR, may mediate the growth cones response to the metabolically active retinoic acid isomers, all-trans and 9-cis RA, in Lymnaea stagnalis. Data presented here show that both an RXR and RAR antagonist can block growth cone turning in response to application of both isomers. Because no prior investigations have shown growth cone turning of individual vertebrate neurons, I aimed to show that both retinoic acid isomers were capable of inducing growth cone turning of embryonic spinal cord neurons in the frog, Xenopus laevis. For the first time in Xenopus, I showed that both all-trans and 9-cis RA were able to induce significantly more neurite outgrowth from cultured embryonic spinal cord neurons and induce positive growth cone turning of individual growth cones. In addition, I showed that the presence of the RXR antagonist, HX531, blocked 9-cis RA-induced growth cone turning and the RARβ antagonist, LE135, blocked all-trans RA-induced growth cone turning in this species. Evidence provided here shows for the first time, conservation of retinoic acid-induced growth cone turning in a vertebrate model system. In addition, these data show that the receptors involved in this morphological response may be the same in vertebrates and invertebrates.

Understanding Workplace Essential Skills: A Student's Perspective

An instrumental case study was conducted to explore the perspective of recent graduates from a Greater Toronto Area community college experience in relation to Workplace Essential Skills (WES). Five participants who graduated from a business school within the last 4 years were interviewed twice over a 4-month period to gain a deeper understanding of this relationship. This qualitative approach used semi-structured interviews to elicit stories about their experiences, their relationships in school, and the development of skills that were useful in the workplace. The analysis of data involved the 3-step coding process of open, axial, and selective coding consistent with the approach used by Neuman (2006). The analysis revealed that the overall experience of attending college contributed to the learning that took place. The participants gave greater significance to the life experience in learning WES and the networks associated with learning than the formal aspects of education. It is also important to acknowledge that the research identified a significant opportunity for educators’ to positively impact the learning experience.

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.