4 resultados para ORIGINS

em Brock University, Canada


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This research identified and examined the responses of 19 physically active seniors to determine why they were physically active. The participants were physically active seniors, from the Niagara region who participated in physical activity 2, or more times per week. The purpose to this research was to determine what specific experiences or characteristics those seniors' possessed which motivated them to follow an exercise regime in later life. Three focus group interviews were conducted and participants responded to a set of predetermined questions. Responses to the interview questions were transcribed and analysed by comparing words and participant responses. This method of analysis is known as ethnographic summary. Themes, concepts, and experiences that emerged from the focus group interviews were also recorded according to systematic coding by way of content analysis. From this study, factors that predispose, enable, reinforce and prevent seniors from participating in exercise have been identified. Nine recommendations for improving seniors quality of life have also emerged from the study. Additionally, the findings from the study illustrate that those responsible for planning programs for seniors need to consider senior's wants and needs. Finally, the study also has educational implications. All participants in the study experienced a positive introduction to daily phyiscal activity through their school setting. Participants of the study believed, that their positive experiences at school, directly influenced their lifelong involvement in exercise.

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The Green Party of Canada, as a vital aspect of the Canadian green movement, and its connection to international green organizations can be examined primarily through the examp l es of both the Canadian Greens and the Green party of Ontario , by using original party documents and literature, information gained through Green party meetings and discussions with members, and commentary by Green theorists where app licable. As well, the influence on the Canadian green movement by the German Green Party is out lined , again mainly through party literature, documents and critiques of the party's experiences. This study reveals several existing and potential problems fo r t he Green Party in Canada, and the political fut ure of the Canadian green movement in general. Some, such as the real i ties of the Canadian political system are external to the movement, and may be overcome with adjustments in goals and methods, and a realization of the changing attitude towards environmental issues in a political context . On the other hand, internal party disfunctions in both organization and direction, caused mainly by the indefinite parameters of green ideology, threaten to expl oi t t he al ready problematic aspects evident in t he Green Party . Aside from its somewhat slow beginnings, the Green Party in Canada has developed into a strong grassroots social movement, not however from its political visibility but from the steady growth in the popul ari ty of ecological pol i t ics in Canada . Due to the seeming enormity of the obstacles facing the Greens in their effort 4 to achieve electoral success, it is doubtful that Parliamentary representation will be achieved without a major re-orientation of party organization and methods. UI timately the strength of the Green Party in Canada will be based upon its ability to survive as a significant movement, and its willingness to continue to challenge political thought and practice.

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Diatoms are renowned for their robust ability to perform NPQ (Non-Photochemical Quenching of chlorophyll fluorescence) as a dissipative response to heightened light stress on photosystem II, plausibly explaining their dominance over other algal groups in turbulent light environs. Their NPQ mechanism has been principally attributed to a xanthophyll cycle involving the lumenal pH regulated reversible de-epoxidation of diadinoxanthin. The principal goal of this dissertation is to reveal the physiological and physical origins and consequences of the NPQ response in diatoms during short-term transitions to excessive irradiation. The investigation involves diatom species from different originating light environs to highlight the diversity of diatom NPQ and to facilitate the detection of core mechanisms common among the diatoms as a group. A chiefly spectroscopic approach was used to investigate NPQ in diatom cells. Prime methodologies include: the real time monitoring of PSII excitation and de-excitation pathways via PAM fluorometry and pigment interconversion via transient absorbance measurements, the collection of cryogenic absorbance spectra to measure pigment energy levels, and the collection of cryogenic fluorescence spectra and room temperature picosecond time resolved fluorescence decay spectra to study excitation energy transfer and dissipation. Chemical inhibitors that target the trans-thylakoid pH gradient, the enzyme responsible for diadinoxanthin de-epoxidation, and photosynthetic electron flow were additionally used to experimentally manipulate the NPQ response. Multifaceted analyses of the NPQ responses from two previously un-photosynthetically characterised species, Nitzschia curvilineata and Navicula sp., were used to identify an excitation pressure relief ‘strategy’ for each species. Three key areas of NPQ were examined: (i) the NPQ activation/deactivation processes, (ii) how NPQ affects the collection, dissipation, and usage of absorbed light energy, and (iii) the interdependence of NPQ and photosynthetic electron flow. It was found that Nitzschia cells regulate excitation pressure via performing a high amplitude, reversible antenna based quenching which is dependent on the de-epoxidation of diadinoxanthin. In Navicula cells excitation pressure could be effectively regulated solely within the PSII reaction centre, whilst antenna based, diadinoxanthin de-epoxidation dependent quenching was implicated to be used as a supplemental, long-lasting source of excitation energy dissipation. These strategies for excitation balance were discussed in the context of resource partitioning under these species’ originating light climates. A more detailed investigation of the NPQ response in Nitzschia was used to develop a comprehensive model describing the mechanism for antenna centred non-photochemical quenching in this species. The experimental evidence was strongly supportive of a mechanism whereby: an acidic lumen triggers the diadinoxanthin de-epoxidation and protonation mediated aggregation of light harvesting complexes leading to the formation of quencher chlorophyll a-chlorophyll a dimers with short-lived excited states; quenching relaxes when a rise in lumen pH triggers the dispersal of light harvesting complex aggregates via deprotonation events and the input of diadinoxanthin. This model may also be applicable for describing antenna based NPQ in other diatom species.

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The exact mechanistic understanding of various organocatalytic systems in asymmetric reactions such as Henry and aza-Henry transformations is important for developing and designing new synthetic organocatalysts. The focus of this dissertation will be on the use of density functional theory (DFT) for studying the asymmetric aza-Henry reaction. The first part of the thesis is a detailed mechanistic investigation of a poorly understood chiral bis(amidine) (BAM) Brønsted acid catalyzed aza-Henry reaction between nitromethane and N-Boc phenylaldimine. The catalyst, in addition to acting as a Brønsted base, serves to simultaneously activate both the electrophile and the nucleophile through dual H-bonding during C-C bond formation and is thus essential for both reaction rate and selectivity. Analysis of the H-bonding interactions revealed that there was a strong preference for the formation of a homonuclear positive charge-assisted H-bond, which in turn governed the relative orientation of substrate binding. Attracted by this well-defined mechanistic investigation, the other important aspect of my PhD research addressed a detailed theoretical analysis accounting for the observed selectivity in diastereoselective versions of this reaction. A detailed inspection of the stereodetermining C-C bond forming transition states for monoalkylated nitronate addition to a range of electronically different aldimines, revealed that the origins of stereoselectivity were controlled by a delicate balance of different factors such as steric, orbital interactions, and the extent of distortion in the catalyst and substrates. The structural analysis of different substituted transition states established an interesting dependency on matching the shape and size of the catalyst (host molecule) and substrates (guest molecules) upon binding, both being key factors governing selectivity, in essence, offering an analogy to positive cooperative binding effect of catalytic enzymes and substrates in Nature. In addition, both intra-molecular (intra-host) and inter-molecular (host-guest, guest-guest) stabilizing interactions play a key role to the high π-facial selectivity. The application of dispersion-corrected functionals (i.e., ωB97X-D and B3LYP-D3) was essential for accurately modeling these stabilizing interactions, indicating the importance of dispersion effects in enantioselectivity. As a brief prelude to more extensive future studies, the influence of a triflate counterion on both reactivity and selectivity in this reaction was also addressed.