795 resultados para Transposition into the contemporary


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Reactions of 5,6- and 4,5-epoxycholestane derivatives with strong bases were investigated. Epoxidation of 3a-acetoxycholest-5-ene also gave a new compound along with the anticipated epoxides. Interconversions of the latter were observed. Some possible mechanisms of its formation and rearrangements have been pIioposed. No reaction was observed with any of the 5,6- and 4,5-steroidal epoxides employed in the present study, using potassium tertiary butoxide under refluxing conditions. n-Butyllithium reacted only with 5,6-epoxycholestanes bearing a ketal moiety at the C3 carbon. Opening of the ketal group was observed with n-butyllithium in the case of a ~-epoxide. The reaction was also investigated in the absence of epoxide functionality. A possible mechanism for the opening of ketal group has been proposed. Lithium diethylamide (LDEA) was found effective in rearranging 5,6- and 4,5-epoxides to their ~orresponding allylic alcohols. These rearrangements presumably proceed via syn-eliminations, however the possibility of a corresponding anti-elimination has not been eliminated. A substituent effect of various functional groups (R = H, OH, OCH2CH20) at C3 has-been observed on product distribution in the LDEApromoted rearrangements of the corresponding epoxides. No reaction of these epoxides was observed with lithium diisopropylamide (LDA) • In the second part of the project, several attempts were made towards the sYRthesis of deoxycorticoste~one~17,2l,2l~d3' a compound desirable for the 2l-dehydroxylation studies of deoxycorticosterone. Several routes were investigated, and some deuterium labelled pregnane derivatives were prepared in this regard. Microbial 21-hydroxylation of progesteronel7,21,21,2l- d4 by ~ niger led to loss of deuterium from C21 of the product. An effort was made to hydroxylate progesterone microbially under neutral condtions.

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Factors involved in the determination of PAHs (16 priority PAHs as an example) and PCBs (10 PCB congeners, representing 10 isomeric groups) by capillary gas chromatography coupled with mass spectrometry (GC/MS, for PAHs) and electron capture detection (GC/ECD , for PCBs) were studied, with emphasis on the effect of solvent. Having various volatilities and different polarities, solvent studied included dichloromethane, acetonitrile, hexan e, cyclohexane, isooctane, octane, nonane, dodecane, benzene, toluene, p-xylene, o-xylene, and mesitylene. Temperatures of the capillary column, the injection port, the GC/MS interface, the flow rates of carrier gas and make-up gas, and the injection volume were optimized by one factor at a time method or simplex optimization method. Under the optimized conditions, both peak height and peak area of 16 PAHs, especially the late-eluting PAHs, were significantly enhanced (1 to 500 times) by using relatively higher boiling point solvents such as p-xylene and nonane, compared with commonly used solvents like benzene and isooctane. With the improved sensitivity, detection limits of between 4.4 pg for naphthalene and 30.8 pg for benzo[g,h,i]perylene were obtained when p-xylene was used as an injection solvent. Effect of solvent on peak shape and peak intensity were found to be greatly dependent on temperature parameters, especially the initial temperature of the capillary column. The relationship between initial temperature and shape of peaks from 16 PAHs and 10 PCBs were studied and compared when toluene, p-xylene, isooctane, and nonane were used as injection solvents. If a too low initial temperature was used, fronting or split of peaks was observed. On the other hand, peak tailing occurred at a too high initial column temperature. The optimum initial temperature, at which both peak fronting and tailing were avoided and symmetrical peaks were obtained, depended on both solvents and the stationary phase of the column used. On a methyl silicone column, the alkane solvents provided wider optimum ranges of initial temperature than aromatic solvents did, for achieving well-shaped symmetrical GC peaks. On a 5% diphenyl: 1% vinyl: 94% dimethyl polysiloxane column, when the aromatic solvents were used, the optimum initial temperature ranges for solutes to form symmetrical peaks were improved to a similar degree as those when the alkanes were used as injection solvents. A mechanism, based on the properties of and possible interactions among the analyte, the injection solvent, and the stationary phase of the capillary column, was proposed to explain these observations. The effect of initial temperature on peak height and peak area of the 16 PAHs and the 10 PCBs was also studied. The optimum initial temperature was found to be dependent on the physical properties of the solvent used and the amount of the solvent injected. Generally, from the boiling point of the solvent to 10 0C above its boiling point was an optimum range of initial temperature at which cthe highest peak height and peak area were obtained.

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Accuracy at identifying or detecting a second-target (T2) is reduced if presented within approximately 500 ms of the first target (TI) - an attentional blink (AB). Affect has previously been shown to influence the magnitude of the AB such that positive affect (PA) is associated with smaller ABs. To account for these findings, Olivers and Nieuwenhuis (2005) proposed an overinvestment hypothesis where P A was said to reduce overinvestment of attentional resources in TI and distractors, leaving more resources for T2. In the present study, P3, CNV, and average activation on distracter-only trials were used to measure attentional investment. The goal was to investigate whether these electrophysiological measures mediated the relationship between self-reported affect and the AB. Results demonstrated that investment of attentional resources was not associated with self-reported affect, or AB magnitude. However, self-report measures of affect, personality and electrophysiological measures of investment did follow some predictions derived from the overinvestment hypothesis.

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The purpos e of this phenomenological research is to explore the meaning of a YMCA-sponsored after-school recreation program in the lives of four adolescent boys. Listening to youth voice is impor t ant to the ability of othe r s to design, implement and evaluate high-quality programs tha t facilitate learning opportunities tha t a r e meaningful to participants. Within the context of interviews, task-based activities we r e used to ga the r data. Guided by Creswell's analytic spiral (1998), data wa s analyzed according to van Manen's (1990) thematic analysis and Caeilli's (2000) creative narrative analysis. It wa s found tha t this after-school progr am provided the s e adolescents with the opportunity to escape from the i r monotonous after-school activities and the instability of the i r home and school environments. Also, they we r e connected wi th positive peers, caring adults and the wide r community, opportunities tha t we r e limited in othe r aspects of the i r lives. Methodological issues a r e also discussed.

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Full Title: Letter from George W. Campbell, esq., late Secretary of the Treasury, to the Chairman of the Committee appointed to inquire into the causes and particulars of the invasion of the City of Washington, and the neighboring town of Alexandria, in the month of August last Laid before the House by the Chairman of the said Committee, and ordered to be printed January 2, 1815. 13th Congress, 3rd Session. House. Doc. 38. Printed by Roger C. Weightman

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Full Title: Letters from the Secretary of War to the Committee of Ways and Means, in relation to the number of Militia called into the public service in 1813, to a provision for paying the bounties and premiums to soldiers lately authorized, and to the strength of the army March, 3, 1814. Read, and ordered to be printed. U.S. 13th Congress 2nd Session, 1813-1814. House.

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Niagara Peninsula of Ontario is the largest viticultural area in Canada. Although it is considered to be a cool and wet region, in the last decade many water stress events occurred during the growing seasons with negative effects on grape and wine quality. This study was initiated to understand and develop the best strategies for water management in vineyards and those that might contribute to grape maturity advancement. The irrigation trials investigated the impact of time of initiation (fruit set, lag phase and veraison), water replacement level based on theoretical loss through crop evapotranspiration (ETc; 100,50 and 25%) and different irrigation strategies [partial root zone drying (PRD) versus regulated deficit irrigation (RD!)] on grape composition and wine sensory profiles. The irrigation experiments were conducted in a commercial vineyard (Lambert Vineyards Inc.) located in Niagara-on-the-Lake, Ontario, from 2005 through 2009. The two experiments that tested the combination of different water regimes and irrigation time initiation were set up in a randomized block design as follows: Baco noir - three replicates x 10 treatments [(25%, 50% and 100% of ETc) x (initiation at fruit set, lag phase and veraison) + control]; Chardonnay - three replicates x seven treatments [(25%, 50% and 100% of ETc) x (initiation at fruit set and veraison) + control]. The experiments that tested different irrigation strategies were set up on two cultivars as follows: Sauvignon blanc - four replicates x four treatments [control, fully irrigated (100% ETc), PRD (100% ETc) and RDI (25% ETc)]; Cabemet Sauvignon - four replicates x five treatments [control, fully irrigated (100% ETc), PRD (100% ETc), RDI (50% ETc) and RDI (25% ETc)]. The controls in each experiment were nonirrigated. The irrigation treatments were compared for many variables related to soil water status, vine physiology, berry composition, wine sensory profile, and hormone composition [(abscisic acid (ABA) and its catabolites]. Soil moisture profile was mostly affected by irrigation treatments between 20 and 60 em depth depending on the grapevine cultivar and the regime of water applied. Overall soil moisture was consistently higher throughout the season in 100 and 50% ETc compare to the control. Transpiration rates and leaf temperature as well as shoot growth rate were the most sensitive variables to soil water status. Drip irrigation associated with RDI treatments (50% ETc and 25% ETc) had the most beneficial effects on vine physiology, fruit composition and wine varietal typicity, mainly by maintaining a balance between vegetative and reproductive parts of the vine. Neither the control nor the 100 ETc had overall a positive effect on grape composition and wine sensory typicity. The time of irrigation initiation affected the vine physiology and grape quality, the most positive effect was found in treatments initiated at lag phase and veraison. RDI treatments were overall more consistent in their positive effect on grape composition and wine varietal typicity comparing to PRD treatment. The greatest difference between non-irrigated and irrigated vines in most of the variables studied was found in 2007, the driest and hottest season of the experimental period. Soil water status had a greater and more consistent effect on red grapevine cultivars rather than on white winegrape cultivars. To understand the relationships among soil and plant water status, plant physiology and the hormonal profiles associated with it, abscisic acid (ABA) and its catabolites [phaseic acid (PA), dihydrophaseic acid (DPA), 7-hydroxy-ABA (TOH-ABA), 8' -hydroxy-ABA, neophaseic acid and abscisic acid glucose ester (ABA-GE)] were analyzed in leaves and berries from the Baco noir and Chardonnay irrigation trials over two growing seasons. ABA and some of its catabolites accurately described the water status in the vines. Endogenous ABA and some of its catabolites were strongly affected in Baco noir and Chardonnay by both the water regime (i.e. ET level) and timing of irrigation initiation. Chardonnay grapevines produced less ABA in both leaves and berries compared to Baco noir, which indicated that ABA synthesis is also cultivar dependant. ABA-GE was the main catabolite in treatments with high water deficits, while PA and DPA were higher in treatments with high water status, suggesting that the vine produced more ABA-GE under water deficits to maintain rapid control of the stomata. These differences between irrigation treatments with respect to ABA and catabolites were particularly noticeable in the dry 2007 season. Two trials using exogenous ABA investigated the effect of different concentrations of ABA and organs targeted for spraying, on grape maturation and berry composition of Cabemet Sauvignon grapevines, in two cool and wet seasons (2008-2009). The fIrst experiment consisted of three replicates x three treatments [(150 and 300 mg/L, both applications only on clusters) + untreated control] while the second experiment consisted in three replicates x four treatments [(full canopy, only clusters, and only leaves sprayed with 300 ppm ABA) + untreated control]. Exogenous ABA was effective in hastening veraison, and improving the composition of Cabemet Sauvignon. Ability of ABA to control the timing of grape berry maturation was dependant on both solution concentration and the target organ. ABA affected not only fruit composition but also yield components. Berries treated with ABA had lower weight and higher skin dry mass, which constitutes qualitative aspects desired in the wine grapes. Temporal advancement of ripening through hormonal control can lead to earlier fruit maturation, which is a distinct advantage in cooler areas or areas with a high risk of early frost occurrence. Exogenous ABA could provide considerable benefits to wine industry in terms of grape composition, wine style and schedule activities in the winery, particularly in wet and cool years. These trials provide the ftrst comprehensive data in eastern North America on the response of important hybrid and Vitis vinifera winegrape cultivars to irrigation management. Results from this study additionally might be a forward step in understanding the ABA metabolism, and its relationship with water status. Future research should be focused on ftnding the ABA threshold required to trigger the ripening process, and how this process could be controlled in cool climates.

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It is estimated that over 4.4 million people are living in Canada with a reported disability. Due to a number of risk factors associated with potential health concerns and sedentary lifestyles, it is important for people with physical disabilities to lead an active lifestyle. Recreation and leisure pursuits are a great outlet for this to take place. However, in order to gain the long terms benefits of these pursuits one must be committed to an activity. With the use of a collaborative interview method, with the Sport Commitment Model serving as the guiding framework, this study sought to find the underlying factors for continued participation for people with physical disabilities in wheelchair basketball. Through utilizing an interpretive approach it was found that enjoyment, social support, perceived ability and to some extent involvement opportunities, were the main contributors to overall commitment. Criticisms and suggestions for future research are also provided.

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Accuracy at reporting a second-target (T2) is reduced if it is presented within approximately 500 ms of the first target (T1) – an attentional blink (AB). Early models explained the AB in terms of attentional limitations creating a processing bottleneck such that T2 processing would be impaired while T1 processing was ongoing. Theoretical models of the AB have more recently been expanded to include the role of cognitive control. In this dissertation I propose that cognitive control, defined as the optimization of information processing in order to achieve goals, is maladapted to the dual-task conditions of the AB task in that cognitive control optimizes the T1 goal, due to its temporal proximity, at the cost of T2. I start with the concept that the role of cognitive control is to serve goals, and that how goals are conceived of and the degree of motivation associated with those goals will determine whether cognitive control will create the condition that cause the AB. This leads to the hypothesis that electrophysiological measures of cognitive control and the degree of attentional investment resulting from cognitive control modulate the AB and explain individual differences in the AB. In a series of four studies feedback-related N2 amplitude, (reflecting individual differences in the strength of cognitive control), and event-related and resting alpha frequency oscillatory activity (reflecting degree of attentional investment), are used to explain both intra- and inter-individual variability in performance on the AB task. Results supported the hypothesis that stronger cognitive control and greater attentional investment are associated with larger AB magnitudes. Attentional investment, as measured by alpha frequency oscillations, and cognitive control, as measured by the feedback-related N2, did not relate to each other as hypothesized. It is proposed that instead of a measure of attentional investment alone, alpha frequency oscillatory activity actually reflects control over information processing over time, in other words the timing of attention. With this conceptualization, various aspects of cognitive control, either related to the management of goals (feedback-related N2) or the management of attention over time to meet goals, explain variability in the AB.

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Abstract Past research has addressed the issue of male underachievement in literacy as an issue of global concern. This qualitative study focused on one subgroup of males which the literature highlighted as most at risk of educational underachievement in the Canadian educational landscape: male Caribbean immigrants to Canada. The research questions that framed the study sought to gain insight into the educational experiences of this group of learners so that ways through which their literacy achievement as measured by academic performance and classroom engagement could be projected. New literacy studies view literacy as socioculturally bound in social, institutional, and cultural relationships (Gee 1996). Literacy can therefore be thought of as an extension of self that Lankshear and Knobel (2006) assert is always connected to social identities. Central to the research questions as a result of this perspective was the discovery of the ideologies of reading held by the participants and their connections to literacy practice. Supplementary questions delved into socially valued literacy practices and ways in which learners saw themselves as Black males reflected in the Canadian educational framework. In this qualitative study with an interview design, data were collected through individual semistructured interviews with the 4 participants and through a focus group session with all the participants. The findings depicted that identity, interests, and ideologies of reading all influenced the literacy practices and engagement of Caribbean males. The findings documented are valuable as they provide a fresh perspective surrounding the educational experiences of the male Caribbean learner and can present insights which can lead to enhanced academic engagement and improved student achievement for this group of learners.

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This study sought to determine if and how the Ontario approach to integrating media education into the curriculum can be applied to Chinese education. The study used thematic analyses to identify the Ontario curriculum‘s attributes and approach to teaching media literacy, and to investigate relevant policies and national curriculum standards in Chinese compulsory education to reveal the status quo of Chinese media education. Finally, the study explored the feasibility of applying the Ontario media education model in China. Findings indicate that the Ontario model can be employed in the Chinese context, but only partly so, because current Chinese media education is limited by protectionism and restrictive policies corresponding to the use of media merely as research tools.

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A photograph for Business Niagara Magazine, featuring (from left to right) : John Howard, Vineland Estates Winery; William Lenko, Daniel Lenko Estate Winery; Gene Luczkiw, The Institute for Enterprise Education; Donald Ziraldo, Inniskillin Wines; Paul Speck, Henry of Pelham Family Estate; Joseph Pohorly, Joseph's Estate Wines. The photograph is dated Monday, January 19, 2004 and has a handwritten message that reads: "Donald. Thanks for making the industry what it is today! Cheers Gene"

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The maximum lifespan (MLSP) of endothermic vertebrates can range from as little as a year to over two centuries, yet the underlying phenotype of aging is very similar amongst this group of organisms. One organelle that may be important in the phenotype of aging is the mitochondrion. When damaged, this organelle is thought to contribute to many of the neurodegenerative diseases of aging. For this thesis, mitochondria from brain tissues of 7 mammalian and 2 avian species were isolated to assess whether the antioxidant glutathione system and major molecular chaperone, HSP60, is correlated to species MLSP. Furthermore, HSP60, and the major endoplasmic reticulum chaperone, GRP78, were measured under basal conditions, and following the introduction of an oxidative stress (hydrogen peroxide) in cultured mammalian myoblasts from 10 different species. My results indicate that the enzymes involved in the glutathione defense system are not correlated to species MLSP in brain mitochondria; however HSP60 levels are indeed higher in the longer-lived species. HSP60 levels are also higher at the basal level in cultured mammalian myoblasts and after 1 hour of hydrogen peroxide exposure. GRP78 induction is not correlated to species MLSP at the basal level or following hydrogen peroxide exposure. Therefore, these results suggest that HSP60 is a correlate of longevity in endothermic vertebrate species, but neither the glutathione antioxidant defense system, nor GRP78, correlates to species longevity.