12 resultados para high-performance frontal analysis

em Brock University, Canada


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The use of certain perfonnance enhancing substances and methods has been defined as a major ethical breach by parties involved in the governance of highperfonnance sport. As a result, elite athletes worldwide are subject to rules and regulations set out in international and national anti-doping policies. Existing literature on the development of policies such as the World Anti-Doping Code and The Canadian antiDoping Program suggests a sport system in which athletes are rarely meaningfully involved in policy development (Houlihan, 2004a). Additionally, it is suggested that this lack of involvement is reflective of a similar lack of involvement in other areas of governance concerning athletes' lives. The purpose ofthis thesis is to examine the history and current state of athletes' involvement in the anti-doping policy process in Canada's high-perfonnance sport system. It includes discussion and analysis of recently conducted interviews with those involved in the policy process as well as an analysis of relevant documents, including anti-doping policies. The findings demonstrate that Canadian athletes have not been significantly involved in the creation of recently developed antidoping policies and that a re-evaluation of current policies is necessary to more fully recognize the reality of athletes' lives in Canada's high-perfonnance sport system and their rights within that system.

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Several automated reversed-phase HPLC methods have been developed to determine trace concentrations of carbamate pesticides (which are of concern in Ontario environmental samples) in water by utilizing two solid sorbent extraction techniques. One of the methods is known as on-line pre-concentration'. This technique involves passing 100 milliliters of sample water through a 3 cm pre-column, packed with 5 micron ODS sorbent, at flow rates varying from 5-10 mUmin. By the use of a valve apparatus, the HPLC system is then switched to a gradient mobile phase program consisting of acetonitrile and water. The analytes, Propoxur, Carbofuran, Carbaryl, Propham, Captan, Chloropropham, Barban, and Butylate, which are pre-concentrated on the pre-column, are eluted and separated on a 25 cm C-8 analytical column and determined by UV absorption at 220 nm. The total analytical time is 60 minutes, and the pre-column can be used repeatedly for the analysis of as many as thirty samples. The method is highly sensitive as 100 percent of the analytes present in the sample can be injected into the HPLC. No breakthrough of any of the analytes was observed and the minimum detectable concentrations range from 10 to 480 ng/L. The developed method is totally automated for the analysis of one sample. When the above mobile phase is modified with a buffer solution, Aminocarb, Benomyl, and its degradation product, MBC, can also be detected along with the above pesticides with baseline resolution for all of the analytes. The method can also be easily modified to determine Benomyl and MBC both as solute and as particulate matter. By using a commercially available solid phase extraction cartridge, in lieu of a pre-column, for the extraction and concentration of analytes, a completely automated method has been developed with the aid of the Waters Millilab Workstation. Sample water is loaded at 10 mL/min through a cartridge and the concentrated analytes are eluted from the sorbent with acetonitrile. The resulting eluate is blown-down under nitrogen, made up to volume with water, and injected into the HPLC. The total analytical time is 90 minutes. Fifty percent of the analytes present in the sample can be injected into the HPLC, and recoveries for the above eight pesticides ranged from 84 to 93 percent. The minimum detectable concentrations range from 20 to 960 ng/L. The developed method is totally automated for the analysis of up to thirty consecutive samples. The method has proven to be applicable to both purer water samples as well as untreated lake water samples.

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With the 2010 Vancouver Winter Olympic Games quickly approaching, there has been a heightened interest in the performance of Canadian athletes at international competitions (Duffy, 2007; Fidlin, 2005; Longley, 2006). Two significant documents outline Canada's goal to become the number one sporting nation at the 2010 Olympic Games, and improve Canada's performance at the 2008 Olympic Games: Own the Podium and Road to Excellence (Priestner Allinger & Allinger, 2004; Road to Excellence, 2006). These two documents represent heightened interest in the performance of our elite athletes, in conjunction with Canada's hosting status of the Vancouver 2010 Winter Olympic Games. The requirements to train and compete at the international level have become more demanding both in terms of financial resources and time commitment. The need to financially assist athletes with their training and competition costs has been an important topic of debate over the past decades (Beamish & Borowy, 1987; Gatehouse, 2004; Macintosh, 1996; Munro, 1970; Owens, 2004). Two sources of fiinding for high performance athletes in Canada are the Athlete Assistance Program (AAP) provided by the Federal Government and the Canadian Olympic Excellence Fund provided by the Canadian Olympic Committee. The importance of these fiinds for athletes has been discussed in various forums (Ekos, 1992, 1997, 2005; Priestner Allinger & Allinger, 2004; Thibault «& Babiak, 2005). However, alternative sources of funds for high performance athletes have never been the object of research. As such the purpose of this study was to describe a group of athlete applicants from the time period of November 2004 to April 2006, and to contextualize these applications within the development of the Charitable Fund for Athletes.

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This work includes two major parts. The first part of the work concentrated on the studies of the application of the highperfonnance liquid chromatography-particle beam interface-mass spectrometry system of some pesticides. Factors that have effects on the detection sensitivity were studied. The linearity ranges and detection limits of ten pesticides are also given in this work. The second part of the work concentrated on the studies of the reduction phenomena of nitro compounds in the HPLC-PB-MS system. Direct probe mass spectrometry and gas chromatography-mass spectrometry techniques were also used in the work. Factors that have effects on the reduction of the nitro compounds were studied, and the possible explanation is proposed. The final part of this work included the studies of reduction behavior of some other compounds in the HPLC-PB-MS system, included in them are: quinones, sulfoxides, and sulfones.

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The sugar beet cyst nematode, Heterodera schachtii, is a major agricultural pest. The disruption of the mating behaviour of this plant parasite in the field may provide a means of biological control, and a subsequent increase in crop yield. The H. schachtii female sex pheromone, which attracts homospecific males, was collected in an aqueous medium and isolated using high performance liquid chromatography. Characterization of the male-attractive material revealed that it was heat stable and water soluble. The aqueous medium conditioned by female H. schachtii was found to be biologically active and stimulated male behaviour in a concentration dependent manner. The activity of the crude pheromone was specific to males of H. schachtii and did not attract second stage juveniles. Results indicated that vanillic acid, a putative nematode pheromone, is not an active component of the H. schachtii sex pheromone. Male H. schachtii exhibited stylet thrusting, a poorly understood behaviour of the male, upon exposure to the female sex pheromone. This behaviour appeared to be associated with mate-finding and was used as a novel indicator of biological activity in bioassays. Serotonin, thought to be involved in the neural control of copulatory behaviour in nematodes, stimulated stylet thrusting. However, the relationship between stylet thrusting induced by the sex pheromone and stylet thrusting induced by serotonin is not clear. Extracellular electrical activity was recorded fi-om the anterior region of H. schachtii males during stylet thrusting, and appeared to be associated with this behaviour. The isolation of the female sex pheromone of H. schachtii may, ultimately, lead to the structural identification and synthesis of the active substance for use in a novel biological control strategy.

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Catharanthlls rosellS (L.) G Don is a commercially significant flower species and in addition is the only source of the monoterpenoid indole alkaloids (MIA) vinblastine and vincristine, which are key pharmaceutical compounds that are used to combat a number of different cancers. Therefore, procurement of the antineoplastic agents is difficult but essential procedure. Alternatively, CatharanthllS tissue cultures have been investigated as a source of these agents; however they do not produce vindoline, which is an obligate precursor to vinblastine and vincristine. The interest in developing high MIA cultivars of Catharantlws rosellS has prompted metabolic profiling studies to determine the variability of MIA accumulation of existing flowering cultivars, with particular focus on the vindoline component ofthe pathway. Metabolic profiling studies that used high performance liquid chromatography of MIAs from seedlings and young leaf extracts from 50 different flowering cultivars showed that, except for a single low vindoline cultivar (Vinca Mediterranean DP Orchid), they all accumulate similar levels of MIAs. Further enzymatic studies with extracts from young leaves and from developing seedlings showed that the low vindoline cultivar has a IO-fold lower tabersonine-16-hydroxylase activity than those of CatharanthllS rosellS cv Little Delicata. Additionally, studies aimed at metabolic engineering ofvindoline bios}l1thesis in Catharanthus rosellS hairy root cultures have been performed by expressing the last step in vindoline biosynthesis [Dcacetylvindoline-4-0- acetyltransferase (DAT)]. Enzymatic profiling studies with transformed hairy roots have confirmed that over-expressing DAT leads to lines with high levels of O-acetyltransferase activity when compared to non-expressing hairy roots. One particular DA T over111 expressing hairy root culture (line 7) contained 200 times the OAT activity than leaves of control lines. Additional MIA analyses revealed that DAT over-expressing hairy roots have an altered alkaloid profile with significant variation in the accumulation of h6rhammericine. Further analysis of transformed hairy root line 7 suggests a correlation between the expression of OAT activity and h6rhammericine accumulation with root maturation. These studies show that metabolic and selective enzymatic profiling can enhance our ability to search for relevant MIA pathway mutants and that genetic engineering with appropriate pathway genes shows promise as a tool to modify the MIA profile of Catharanthus roseus.

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The effects of sample solvent composition and the injection volume, on the chromatographic peak profiles of two carbamate derivatives, methyl 2-benzimidazolecarbamate (MBC) and 3-butyl-2,4-dioxo[1,2-a]-s-triazinobenzimidazole (STB), were studied using reverse phase high performance liquid chromatograph. The study examined the effects of acetonitrile percentage in the sample solvent from 5 to 50%, effects of methanol percentage from 5 to 50%, effects of pH increase from 4.42 to 9.10, and effect of increasing buffer concentration from ° to 0.12M. The effects were studied at constant and increasing injection mass and at four injection volumes of 10, 50, 100 and 200 uL. The study demonstrated that the amount and the type of the organic solvents, the pH, and the buffer strength of the sample solution can have a pronounced effect on the peak heights, peak widths, and retention times of compounds analysed. MBC, which is capable of intramolecular hydrogen bonding and has no tendency to ionize, showed a predictable increase .in band broadening and a decrease in retention times at higher eluting strengths of the sample solvent. STB, which has a tendency to ionize or to strongly interact with the sample solvent, was influenced in various ways by the changes in ths sample solvent composition. The sample solvent effects became more pronounced as the injection volume increased and as the percentage of organic solvent in the sample solution became greater. The peak height increases for STB at increasing buffer concentrations became much more pronounced at higher analyte concentrations. It was shown that the widely accepted procedure of dissolving samples in the mobile phase does not yield the most efficient chromatograms. For that reason samples should be dissolved in the solutions with higher aqueous content than that of the mobile phase whenever possible. The results strongly recommend that all the samples and standards, regardless whether the standards are external or internal, be analysed at a constant sample composition and a constant injection volume.

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A high performance liquid chromatographic method employing two columns connected in series and separated~y·a.switching valve has been developed for the analysis of the insecticide/ nematicide oxamyl (methyl-N' ,N'-dimethyl-N-[(methylcarbamoyl) oxy]-l-thiooxarnimidate) and two of its metabolites. A variation of this method involving two reverse phase columns was employed to monitor the persistence and translocation of oxamyl in treated peach seedlings. It was possible to simultaneously analyse for oxamyl and its corresponding oxime (methyl-N',N'-dimethyl-N-hydroxy-l-thiooxamimidate}, a major metabolite of oxamyl in plants, without prior cleanup of the samples. The method allowed detection of 0.058 pg oxamyl and 0.035 p.g oxime. On treated peach leaves oxamyl was found to dissipate rapidly during the first two-week period, followed by a period of slow decomposition. Movement of oxamyl or its oxime did not occur in detectable quantities to untreated leaves or to the root or soil. A second variation of the method which employed a size exclusion column as·the first column and a reverse phase column as the second was used to monitor the degradation of oxamyl in treated, planted corn seeds and was suitable for simultaneous analysis of oxamyl, its oxime and dimethylcyanoformamide (DMCF), a metabolite of oxamyl. The method allowed detection of 0.02 pg oxamyl, 0.02 p.g oxime and 0.005 pg DMCF. Oxamyl was found to persist for a period of 5 - 6 weeks, which is long enough to permit oxamyl seedtreatment to be considered as a potential means of protecting young corn plants from nematode attack. Decomposition was found to be more rapid in unsterilized soil than in sterililized soil. DMCF was found to have a nematostatic effect at high concentrations ( 2,OOOpprn), but at lower concentrations no effect on nematode mobility was observed. Oxamyl, on the other hand, was found to reduce the mobility of nematodes at concentrations down to 4 ppm.

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Variations in different types of genomes have been found to be responsible for a large degree of physical diversity such as appearance and susceptibility to disease. Identification of genomic variations is difficult and can be facilitated through computational analysis of DNA sequences. Newly available technologies are able to sequence billions of DNA base pairs relatively quickly. These sequences can be used to identify variations within their specific genome but must be mapped to a reference sequence first. In order to align these sequences to a reference sequence, we require mapping algorithms that make use of approximate string matching and string indexing methods. To date, few mapping algorithms have been tailored to handle the massive amounts of output generated by newly available sequencing technologies. In otrder to handle this large amount of data, we modified the popular mapping software BWA to run in parallel using OpenMPI. Parallel BWA matches the efficiency of multithreaded BWA functions while providing efficient parallelism for BWA functions that do not currently support multithreading. Parallel BWA shows significant wall time speedup in comparison to multithreaded BWA on high-performance computing clusters, and will thus facilitate the analysis of genome sequencing data.

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This qualitative case study explored how the structural power imbalance in high performance sport influenced the bargaining process and resulting commercial rights and obligations of a single Canadian national sport organization’s (NSO1) Athlete Agreement. Principles comprising the doctrine of unconscionability, specifically the identification of a power imbalance between contracting parties, and the exploration of how that power imbalance influenced the terms of the contract, provided a framework to analyze factors influencing the commercial contents of NSO1’s Athlete Agreement. The results of this analysis revealed that despite the overarching influence of the inherent structural power imbalance on all aspects of NSO1 and its membership, an athletes’ level of commercial appeal can reach such heights as to balance the bargaining positions of both parties and subsequently influence the commercial contents of the Athlete Agreement.

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This study contributes to current research on voice behaviour by investigating several under-explored drivers that motivate employees’ expression of constructive ideas about work-related issues. It draws from the concept of psychological climate to examine how voice behaviour is influenced by employees’ (1) personal resources (tenacity and passion for work), (2) perceptions of social interdependence (task and outcome interdependence), and (3) supervisor leadership style (transformational and transactional). Using a multi-source research design, surveys were administered to 226 employees and to 24 supervisors at a Canadian-based not-for-profit organization. The hypotheses are tested with hierarchical regression analysis. The results indicate that employees are more likely to engage in voice behaviour to the extent that they exhibit higher levels of passion for work. Further, their voice behaviour is lower to the extent that their supervisor adopts a transformational leadership style characterized by high performance expectations or a transactional leadership style based on contingent rewards and contingent punishment behaviours. The study reveals that there are no significant effects of tenacity, social interdependence, and behaviour-focused transformational leadership on voice. The findings have significant implications for organizations that seek to encourage employee behaviours that help improve current work practices or undo harmful situations.

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The purpose of this study was to understand the experiences of Canada’s high performance athletes who have benefitted from Own the Podium (OTP)-recommended funding and support leading up to an Olympic or Paralympic Games. OTP, a nonprofit agency, is responsible for determining the overall investment strategy for high performance sport in Canada through recommendations to support national sport organizations (NSOs) with the aim to improve Canadian performances at the Olympic and Paralympic Games. For this study, data were collected through in-depth interviews with eleven Canadian high performance athletes (i.e., single-sport Summer/Winter Olympians and Paralympians and recently retired athletes). Analysis of the data resulted in twelve overarching themes; resources, pressure, missing gap, results, targeting, stress, expectations, boost in confidence, OTP relationship, OTP name, pre/post OTP, and lost funding. Overall, results from this exploratory research indicate that athletes generally had a favourable perception regarding OTP-recommended funding and support.