7 resultados para Wireless electrochemical promotion of catalysis

em Brock University, Canada


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Although it is generally accepted that Rydberg orbitals are very large and diffuse, and that electron promotion to a Rydberg orbital is not too different from ionization of the molecule, analysis of the two types of transitions proves otherwise. The photoelectron spectrum of the 2B2 (n) ion has very little vibrational structure attached to the origin band; on the other hand, several of the Rydberg transitions which involve the promotion of the n(bZ) electron exhibit a great deal of vibrational activity. In particular, the members of the n=3 Rydberg\ series interact with and perturb each other through pseudo-Jahn-Teller vibronic coupling. The vacuum ultraviolet spectrum contains a number of features which are difficult to explain, and two unusually sharp bands can only be identified as representing some form of electron promotion in formaldehyde.

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This research was focussed on the effects of light, solvent and substituents in the molybdenum-catalyzed oxidation of phenylmethyl sulfides with t-Bu02H and on the effect of light in the molybdenum-catalyzed epoxidation of l-octene with t-Bu02H. It was shown that the Mo(CO)6-catalyzed oxidation of phenylmethyl sulfide with t-Bu02H~ at 35°C, proceeds 278 times faster underUV light than under laboratory lighting, whereas the Mo02(acac)2-catalyzed oxidation proceeds only 1.7 times faster under UV light than under normal laboratory lighting. The difference between the activities of both catalysts was explained by the formation of the catalytically active species, Mo(VI). The formation of the Mo(VI) species, from Mo(CO)6 was observed from the IR spectrum of Mo(CO)6 in the carbonyl region. The Mo(CO)6-catalyzed epoxidation of l-octene with t-Bu02H showed that the reaction proceeded 4.6 times faster under UV light than in the dark or under normal laboratory lighting; the rates of epoxidations were found to be the same in the dark and under normal laboratory lighting. The kinetics of the epoxidations of l-octene with t-Bu02H, catalyzed by Mo02(acac)2 were found to be complicated; after fast initial rates, the epoxidation rates decreased with time. The effect of phenylmethyl sulfide on the Mo(CO)6-catalyzed epoxidation of l-octene waS studied. It was shown that instead of phenylmethyl sulfide, phenylmethyl sulfone, which formed rapidly at 85°C, lowered the reaction rate. The epoxidation of l-octene was found to be 2.5 times faster in benzene than in ethanol. The substituent effect on the Mo02(acac)2-catalyzed oxidations of p-OH, p-CHgO, P-CH3' p-H, p-Cl, p-Br, p-CHgCO, p-HCO and P-N02 substituted phenylmethyl sulfides were studied. The oxidations followed second order kinetics for each case; first order dependency on catalyst concentration was also observed in the oxidation of p-CHgOPhSMeand PhSMe. It was found that electron-donating groups on the para position of phenylmethyl sulfide increased the rate of reaction, while electronwithdrawing groups caused the reaction rate to decrease. The reaction constants 0 were determined by using 0, 0- and 0* constants. The rate effects were paralleled by the activation energies for oxidation. The decomposition of t-Bu02H in the presence of M.o (CO)6, Mo02 (acac)2 and VO(acac)2 was studied. The rates of decomposition were found to be very small compared to the oxidation rates at high concentration of catalysis. The relative rates of the Mo02(acac)2-catalyzed oxidation of p-N02PhSMe by t-Bu02H in the presence of either p-CH30PhSMe or PhSMe clearly show that PhSMe and p-CHgOPhSMe act as co-catalysts in the oxidation of p-N02PhSMe. Benzene, mesity1ene and cyclohexane were used to determine the effect of solvent in the Mo02 (acac)2 and Mo(CO)6-catalyzed oxidation of phenylmethyl sulfide. The results showed that in the absence of hydroxylic solvent, a second molecule of t-Bu02H was involved in the transition state. The complexation of the solvent with the catalyst could not be explained.The oxidations of diphenyl sulfoxide catalyzed by VO(acac)2, Mo(CO)6 and Mo02(acac)2 showed that VO(acac)2 catalyzed the oxidation faster than Mo(CO)6 and Mo02 (acac)2_ Moreover, the Mo(CO)6-catalyzed oxidation of diphenyl sulfoxide proceeded under UV light at 35°C.

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The Women's Literary Club of St. Catharines was founded in 1892 by a local author, Emma Harvey (Mrs. J.G.) Currie (1829-1913) and held its last official meeting on February 19, 1994. The Club developed, flourished and eventually waned. After more than one hundred successful years, the last members deposited the Club's archives at Brock University for the benefit of researchers, scholars and the larger community. The ‘object of the Club’ was established as “the promotion of literary pursuits.” The Club was a non-profit social organization composed of predominantly white, upper middle class women from the St. Catharines and surrounding areas. Club meetings were traditionally held fortnightly from March to December each year. The last meeting of the year was a celebration of their Club anniversary. The early meetings of the Club include papers presented and music performed by Club members. The literary pursuits that would dominate the agendas for the entire life of the Club reflected an interest in selected authors, national and local history, classical history, musical performances and current cultural and newsworthy events. For example in 1893 a typical meeting agendas would contain papers on Henry Wadsworth Longfellow, Hawaii, Brook Farm, Miss Louisa May Alcott and “Education of Women 100 years Ago.” Within the first year of the Club’s existence, detailed minute books became the norm and an annual agenda or program developed. The WLC collection contains a near complete set of meeting minutes from 1892 until 1995 and a comprehensive collection of yearly programs from 1983-1967 which members took great care to publish each year. Mrs. Currie brought together a group of women with a shared interest in literature and history, who wanted to pursue that interest in a formal and structured manner. She was well educated and influenced at an early age by her tutor and mentor William Kirby, local historian, writer and newspaper editor from Niagara-on-the-Lake. While Currie’s private education influenced her love of literature and history, the Club movement of the 1890’s offered a more public forum for her to share knowledge and learning with other women. Mrs. Currie was the wife of St. Catharines lawyer, James G. Currie, who also served as a Member of Parliament for the county of Lincoln. Mrs. W.H. McClive, who was also married to a St. Catharines lawyer, worked closely with Currie and they began research into the possibility of a literary Club in St. Catharines. Currie corresponded with a variety of literary Clubs across North America before she and Mrs.McClive tagged onto the momentum of the Club movement and published “A Clarion call for Women of St. Catharines To Form a Literary Club” in the local paper The St. Catharines Evening Journal. in 1892 and asked like Clubs to publish the news of their new Club. The early years of the WLC set the foundation of how the Club meetings and events would unfold for the next 80 plus years. Photos and minutes from the first ten years reveal an excitement and interest in organized Club outings. One particular event, an annual pilgrimage to the homestead of Laura Secord, became a yearly celebration for the Club. Club President, Mrs. Currie’s own personal work on Laura Secord amplified the Club’s interest in the ‘heroine of 1812’ and she allocated the profits from her publication on Secord in order to create a commemorative plaque/monument in the name of Laura Secord. The Club celebrated this event with a regular pilgrimage to this site. The connection felt by Club members and this memorial would continue until the Club’s last meetings. The majority of members in the early years were of the upper middle classes in the growing city of St. Catharines. Many of the charter members were the wives of merchants, business men, lawyers, doctors, even a hatter. Furthermore, the position of president was most often held by a woman with a comprehensive list of interests. This is particularly the case in Isabel Brighty McComb (1876-1941). Brighty who became a member in 1903, became Club president in 1932 and stayed in her post until her death in 1941. Similar to Mrs. Currie, Brighty was a local historian and published 2 booklets on local history. Her obituary indicates her position in the community as an author and involved community member committed to lifetime memberships in the Imperial Order of Daughters of Empire, I.O.D.E., the National Organization of Women, N.O.W. and the United Empire Loyalist Society, as well as the WLC. She was a locally known ‘teacher of elocution’ and a devoted researcher of Upper Canadian history. In a Club scrapbook dedicated to her, the biographical sketch illustrates the professionalism surrounding Brighty. There is very little personal history mentioned and the focus is on her literary works, her published essay, booklets and poetry. This professional focus, evident in both her obituary and the scrapbook, illustrate the diversity of these women, especially in their roles outside of the home. The WLC collection contains a vast array of essay, lectures clippings and scrapbooks from past meetings. Organized predominantly by topic or author, the folders and scrapbooks offer a substantial amount of research opportunity in the literary history of Canada. The dates, scope of topics and authors covered offer historians an exciting opportunity to examine the consumption of particular literary trends, artists and topics within the context of a midsized industrial city in English Canada. This is especially important because the agenda adhered to by the Club was bent on promoting, discussing and reviewing predominantly Canadian material. By connecting when and what these women were studying, scholars many gain a better understanding of the broader consumption and appreciation of literary and social trends of Canadian women outside of publishing and institutional records. Furthermore, because the agendas were set by and for these women, outside of the constructs of an institutionalized canon or agenda, they offer a fresh and on the ground examination of literary consumption over an extensive length of time.

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There is an emerging awareness that children with poor motor abilities are at particular risk for overweight. This cross-sectional study examined the influence of physical activity behaviour on the relationship between motor proficiency and body composition. Participants were 1287 (646 males, 641 females) Grade 6 students in the Physical Health Activity Study project. Height, weight, waist girth, and motor proficiency (Bruininks-Oseretsky Test of Motor Performance BOTMP-SF) were assessed. Physical activity behaviours were also evaluated with a multifaceted approach and reported for school-based, non-school based physical activity, free-time play, and sedentary activities (Participation Questionnaire), and leisure time exercise (Godin-Shephard Leisure Time Exercise Questionnaire GS). Overweight was defined by BMI scores: boys :::20.6-21.2 and <25.1-26.0; girls: ::: 20.7-21.7and <25.4-26.7 and obesity was defined as: boys:::: 25.1-26.0; girls: :::25.4-26.7. Children were classified as case group (CG,::; 10% on BOTMP-SF), borderline case group (BC, > 10% to ::; 20% on BOTMP-SF) or non-case group. Analyses of variance (ANOVAs) uncovered a significant difference in overweight and obesity between the case group and non-case group. Normal-weight children reported higher participation in organized school-sports (intra-mural and inter-school teams). The CG reported significantly lower participation in school sports teams and lower GS results, with a trend towards lower participation in all active pursuits. They also reported a significantly higher duration of television watching and book reading. There were no significant differences between motor proficiency groups by gender, age, nonschool sports, or free-time activity. Multivariate ordinal logistic regression analysis showed that the case group was 10.9 times more likely to be overweight/obese than their peers. No single aspect of physical activity was able to explain the difference in odds ratios for the motor proficiency groups. However, for the entire cohort, children who participated in more organized school sports were less likely to be overweight/obese. These findings confirm that children with low motor proficiency are at significant risk of developing overweight. It is evident that these children have generally attenuated activity levels and heightened levels of sedentary pursuits. School-based activities appear particularly limited, and are the one area where children have near autonomy in their decision to pursue active opportunities. The promotion of school-based programs, specifically intramural sports may be an important aspect in increasing children's overall activity levels. It is also essential to consider the needs of those children with low motor proficiency when designing activity promotion programs. Future research should further explore motor proficiency and overweight/obesity.

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Grounded in Basic Psychological Needs Theory (Deci & Ryan, 2002), the present investigation examined whether psychological need satisfaction mediated the relationship between moderate-to-vigorous physical activity (MVPA) and well-being. Adopting a longitudinal design participants (N= 147) completed questionnaires assessing MVPA, well-being and perceived psychological need satisfaction in exercise contexts on three occasions separated by three weeks. A pattern of small-to-moderate correlations were noted between MVPA and indices of well-being (r12's ranged from .16 to .29). Multiple mediation analysis indicated that perceived psychological need satisfaction mediated the relationship between MVPA and well-being with perceived competence emerging as a unique mediator. Serial mediation analyses indicated the importance of ongoing psychological need satisfaction to well-being. Contexts that afford individuals the opportunity to engage in MVPA, as well as supports their need for competence, would be most advantageous for the promotion of psychological well-being.

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Traditional employment options for persons with developmental disabilities are lacking. Employment options available for persons with developmental disabilities are reflective of the medical and social model perspectives of disability; with segregated and supported employment reinforcing the idea that persons with developmental disabilities are incapable and competitive employment missing the necessary accommodations for persons to be successful. This study examined social enterprises as an alternative employment option that can balance both medical and social model perspectives by accommodating for weaknesses or limitations and recognizing the strengths and capabilities of persons with developmental disabilities in the workplace. Moreover, this study is part of a broader case study which is examining the nature and impacts of a social enterprise, known as Common Ground Co-operative (CGC), which supports five social purpose businesses that are owned and operated by persons with developmental disabilities. This study is part of the Social Business and Marginalized Social Groups Community-University Research Alliance. To date, a case study has been written describing the nature and impacts of CGC and its related businesses from the perspectives of the Partners, board members, funders and staff (Owen, Readhead, Bishop, Hope & Campbell, in press & Readhead, 2012). The current study used a descriptive case study approach to provide a detailed account of the perceptions and opinions of CGC staff members who support each of the Partners in the five related businesses. Staff members were chosen for the focus of this study because of the integral role that they play in the successful outcomes of the persons they support. This study was conducted in two phases. In the first phase five staff members were interviewed. During this stage of interviews, several themes were presented which needed to be examined in further detail, specifically staff stress and burnout and duty of care for business Partners versus the promotion of their autonomy. A second phase of interviews was then conducted with one individual participant and a focus group of seven. During both interview phases, Staff participants described an employment model that creates a non-judgemental environment for the business Partners that promotes their strengths, accommodates for their limitations, provides educational opportunities and places the responsibility for the businesses on the persons with developmental disabilities cultivating equality and promoting independence. Staff described the nature of their role including risk factors for stress, the protective factors that buffer stress, and the challenges associated with balancing many role demands. Issues related to the replication of this social enterprise model are described.

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This research study explored a support system for children with learning disabilities. The Learning Disabilities Association of Niagara Region (LDANR) recently expanded its Better Emotional and Social Times (B.E.S.T.) program to incorporate an innovative, character education initiative called the “Who is NOBODY?” program. The objective of this qualitative case study was two-fold. First, the study aimed to support the LDANR in assessing the efficacy of the “Who is NOBODY?” program, providing the LDANR with empirical support for their programs. Second, the study enabled a more in-depth understanding of how to best support children with LD in regards to their social and emotional well-being. The study explored the “Who is NOBODY?” program through three lenses: design, implementation, and experiences of participating children. Three primary themes emerged from these three data lenses: positive character traits, prosocial behaviour, and strong self-efficacy – leading to the promotion of strong character development and self-esteem. Taken together, the “Who is NOBODY?” program was shown to be a successful remediation program for supporting vulnerable children with LD.