238 resultados para theoretical Chemistry


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The intention of this work is to explain theoretically that democracy logically exists in China, despite the statements to the contrary by China’s ruling party. We will have to look at several recent developments in social and political theory to fully understand my point. The first involves recent findings in the historical analysis of democracy from thinkers like Keane (2009), Isakhan and Stockwell (2011). The second deals with cosmopolitan theory and 2nd modernity, or from the works of David Held (2003), Ulrich Beck and Edgar Grande (2010) respectively. Finally, the third is a recent work of mine titled “Democratic Theory and Theoretical Physics” (2010).

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In this paper, two ideal formation models of serrated chips, the symmetric formation model and the unilateral right-angle formation model, have been established for the first time. Based on the ideal models and related adiabatic shear theory of serrated chip formation, the theoretical relationship among average tooth pitch, average tooth height and chip thickness are obtained. Further, the theoretical relation of the passivation coefficient of chip's sawtooth and the chip thickness compression ratio is deduced as well. The comparison between these theoretical prediction curves and experimental data shows good agreement, which well validates the robustness of the ideal chip formation models and the correctness of the theoretical deducing analysis. The proposed ideal models may have provided a simple but effective theoretical basis for succeeding research on serrated chip morphology. Finally, the influences of most principal cutting factors on serrated chip formation are discussed on the basis of a series of finite element simulation results for practical advices of controlling serrated chips in engineering application.

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A series of porphyrins substituted in one or two meso-positions by diphenylphosphine oxide groups has been prepared by the palladium catalysed reaction of diphenylphosphine or its oxide with the corresponding bromoporphyrins. Compounds {MDPP-[P(O)Ph2]n} (M = H2, Ni, Zn; H2DPP = 5,15-diphenylporphyrin; n = 1, 2) were isolated in yields of 60-95%. The reaction is believed to proceed via the conventional oxidative addition, phosphination and reductive elimination steps, as the stoichiometric reaction of η1-palladio(II) porphyrin [PdBr(H2DPP)(dppe)] (H2DPP = 5,15-diphenylporphyrin; dppe = 1,2-bis(diphenylphosphino)ethane) with diphenylphosphine oxide also results in the desired mono-porphyrinylphosphine oxide [H2DPP-P(O)Ph2]. Attempts to isolate the tertiary phosphines failed due to their extreme air-sensitivity. Variable temperature 1H NMR studies of [H2DPP-P(O)Ph2] revealed an intrinsic lack of symmetry, while fluorescence spectroscopy showed that the phosphine oxide group does not behave as a "heavy atom" quencher. The electron withdrawing effect of the phosphine oxide group was confirmed by voltammetry. The ligands were characterised by multinuclear NMR and UV-visible spectroscopy as well as mass spectrometry. Single crystal X-ray crystallography showed that the bis(phosphine oxide) nickel(II) complex {[NiDPP-[P(O)Ph2]2} is monomeric in the solid state, with a ruffled porphyrin core and the two P=O fragments on the same side of the average plane of the molecule. On the other hand, the corresponding zinc(II) complex formed infinite chains through coordination of one Ph2PO substituent to the neighbouring zinc porphyrin through an almost linear P=O---Zn unit, leaving the other Ph2PO group facing into a parallel channel filled with disordered water molecules. These new phosphine oxides are attractive ligands for supramolecular porphyrin chemistry.

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This paper attempts to develop a theoretical acceptance model for measuring Web personalization success. Key factors impacting Web personalization acceptance are identified from a detailed literature review. The final model is then cast in a structural equation modeling (SEM) framework comprising nineteen manifest variables, which are grouped into three focal behaviors of Web users. These variables could provide a framework for better understanding of numerous factors that contribute to the success measures of Web personalization technology. Especially, those concerning the quality of personalized features and how personalized information through personalized Website can be delivered to the user. The interrelationship between success constructs is also explained. Empirical validations of this theoretical model are expected on future research.

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Daylighting in tropical and sub-tropical climates presents a unique challenge that is generally not well understood by designers. In a sub-tropical region such as Brisbane, Australia the majority of the year comprises of sunny clear skies with few overcast days and as a consequence windows can easily become sources of overheating and glare. The main strategy in dealing with this issue is extensive shading on windows. However, this in turn prevents daylight penetration into buildings often causing an interior to appear gloomy and dark even though there is more than sufficient daylight available. As a result electric lighting is the main source of light, even during the day. Innovative daylight devices which redirect light from windows offer a potential solution to this issue. These devices can potentially improve daylighting in buildings by increasing the illumination within the environment decreasing the high contrast between the window and work regions and deflecting potentially glare causing sunlight away from the observer. However, the performance of such innovative daylighting devices are generally quantified under overcast skies (i.e. daylight factors) or skies without sun, which are typical of European climates and are misleading when considering these devices for tropical or sub-tropical climates. This study sought to compare four innovative window daylighting devices in RADIANCE; light shelves, laser cut panels, micro-light guides and light redirecting blinds. These devices were simulated in RADIANCE under sub-tropical skies (for Brisbane) within the test case of a typical CBD office space. For each device the quantity of light redirected and its distribution within the space was used as the basis for comparison. In addition, glare analysis on each device was conducted using Weinold and Christoffersons evalglare. The analysis was conducted for selected hours for a day in each season. The majority of buildings that humans will occupy in their lifetime are already constructed, and extensive remodelling of most of these buildings is unlikely. Therefore the most effective way to improve daylighting in the near future will be through the alteration existing window spaces. Thus it will be important to understand the performance of daylighting systems with respect to the climate it is to be used in. This type of analysis is important to determine the applicability of a daylighting strategy so that designers can achieve energy efficiency as well the health benefits of natural daylight.

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Australian queer (GLBTIQ) university student media is an important site of cultural and political self-representation. These groups exist within university student unions and the unions provide them with space, financial support and resources. Community media is a significant site for the development of queer identity, community and a key part of queer politics. This paper reviews my research into queer community media which is grounded in a Queer Theoretical perspective of identity performativity. Cover argues that Queer Theoretical approaches that study media products fail to consider the material contexts which contribute to their construction. I use an ethnographic approach combined with discourse analysis in order to reveal queer student activists’ media representations of queer, and the production contexts which shape them. My research contributes to queer media scholarship by using a methodology to address the gap that Cover identifies.

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Optimum Wellness involves the development, refinement and practice of lifestyle choices which resonate with personally meaningful frames of reference. Personal transformations are the means by which our frames of reference are refined across the lifespan. It is through critical reflection, supportive relationships and meaning making of our experiences that we construct and reconstruct our life paths. When individuals are able to be what they are destined to be or reach their higher purpose, then they are able to contribute to the world in positive and meaningful ways. Transformative education facilitates the changes in perspective that enable one to contemplate and travel a path in life that leads to self-actualisation. This thesis argues for an integrated theoretical framework for optimum Wellness Education. It establishes a learner centred approach to Wellness education in the form of an integrated instructional design framework derived from both Wellness and Transformative education constructs. Students’ approaches to learning and their study strategies in a Wellness education context serve to highlight convergences in the manner in which students can experience perspective transformation. As they learn to critically reflect, pursue relationships and adapt their frames of reference to sustain their pursuit of both learning and Wellness goals, strengthening the nexus between instrumental and transformative learning is a strategically important goal for educators. The aim of this exploratory research study was to examine those facets that serve to optimise the learning experiences of students in a Wellness course. This was accomplished through three research issues: 1) What are the relationships between Wellness, approaches to learning and academic success? 2) How are students approaching learning in an undergraduate Wellness subject? Why are students approaching their learning in the ways they do? 3) What sorts of transformations are students experiencing in their Wellness? How can transformative education be formulated in the context of an undergraduate Wellness subject? Subsequent to a thorough review of the literature pertaining to Wellness education, a mixed method embedded case study design was formulated to explore the research issues. This thesis examines the interrelationships between student, content and context in a one semester university undergraduate unit (a coherent set of learning activities which is assigned a unit code and a credit point value). The experiences of a cohort of 285 undergraduate students in a Wellness course formed the unit of study and seven individual students from a total of sixteen volunteers whose profiles could be constructed from complete data sets were selected for analysis as embedded cases. The introductory level course required participants to engage in a personal project involving a behaviour modification plan for a self-selected, single dimension of Wellness. Students were given access to the Standard Edition Testwell Survey to assess and report their Wellness as a part of their personal projects. To identify relationships among the constructs of Self-Regulated Learning (SRL), Wellness and Student Approaches to Learning (SAL) a blend of quantitative and qualitative methods to collect and analyse data was formulated. Surveys were the primary instruments for acquiring quantitative data. Sources included the Wellness data from Testwell surveys, SAL data from R-SPQ surveys, SRL data from MSLQ surveys and student self-evaluation data from an end of semester survey. Students’ final grades and GPA scores were used as indicators of academic performance. The sources of qualitative data included subject documentation, structured interview transcripts and open-ended responses to survey items. Subsequent to a pilot study in which survey reliability and validity were tested in context, amendments to processes for and instruments of data collection were made. Students who adopted meaning oriented (deep/achieving) approaches tended to assess their Wellness at a higher level, seek effective learning strategies and perform better in formal study. Posttest data in the main study revealed that there were significant positive statistical relationships between academic performance and total wellness scores (rs=.297, n=205, p<.01). Deep (rs=.343, n=137, p<.01) and achieving (rs=.286, n=123, p<.01) approaches to learning also significantly correlated with Wellness whilst surface approaches had negative correlations that were not significant. SRL strategies including metacognitive selfregulation, effort, help-seeking and critical thinking were increasingly correlated with Wellness. Qualitative findings suggest that while all students adopt similar patterns of day to day activities for example attending classes, taking notes, working on assignments the level of care with which these activities is undertaken varies considerably. The dominant motivational trigger for students in this cohort was the personal relevance and associated benefits of the material being learned and practiced. Students were inclined to set goals that had a positive impact on affect and used “sense of happiness” to evaluate their achievement status. Students who had a higher drive to succeed and/or understand tended to have or seek a wider range of strategies. Their goal orientations were generally learning rather than performance based and barriers presented a challenge which could be overcome as opposed to a blockage which prevented progress. Findings from an empirical analysis of the Testwell data suggest that a single third order Wellness construct exists. A revision of the instrument is necessary in order to juxtapose it with the chosen six dimensional Wellness model that forms the foundation construct in the course. Further, redevelopment should be sensitive to the Australian context and culture including choice of language, examples and scenarios used in item construction. This study concludes with an heuristic for use in Wellness education. Guided by principles of Transformative education theory and behaviour change theory, and informed by this representative case study the “CARING” heuristic is proposed as an instructional design tool for Wellness educators seeking to foster transformative learning. Based upon this study, recommendations were made for university educators to provide authentic and personal experiences in Wellness curricula. Emphasis must focus on involving students and teachers in a partnership for implementing Wellness programs both in the curriculum and co-curricularly. The implications of this research for practice are predicated on the willingness of academics to embrace transformative learning at a personal level and a professional one. To explore students’ profiles in detail is not practical however teaching students how to guide us in supporting them through the “pain” of learning is a skill which would benefit them and optimise the learning and teaching process. At a theoretical level, this research contributes to an ecological theory of Wellness education as transformational change. By signposting the wider contexts in which learning takes place, it seeks to encourage changing paradigms to ones which harness the energy of each successive contextual layer in which students live. Future research which amplifies the qualities of individuals and groups who are “Well” and seeks the refinement and development of instruments to measure Wellness constructs would be desirable for both theoretical and applied knowledge bases. Mixed method Wellness research derived and conducted by teams that incorporate expertise from multiple disciplines such as psychology, anthropology, education, and medicine would enable creative and multi-perspective programs of investigation to be designed and implemented. Congruences and inconsistencies in health promotion and education would provide valuable material for strengthening the nexus between transformational learning and behaviour change theories. Future development of and research on the effectiveness of the CARING heuristic would be valuable in advancing the understanding of pedagogies which advance rather than impede learning as a transformative process. Exploring pedagogical models that marry with transformative education may render solutions to the vexing challenge of teaching and learning in diverse contexts.

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Explanations of the role of analogies in learning science at a cognitive level are made in terms of creating bridges between new information and students’ prior knowledge. In this empirical study of learning with analogies in an 11th grade chemistry class, we explore an alternative explanation at the "social" level where analogy shapes classroom discourse. Students in the study developed analogies within small groups and with their teacher. These classroom interactions were monitored to identify changes in discourse that took place through these activities. Beginning from socio-cultural perspectives and hybridity, we investigated classroom discourse during analogical activities. From our analyses, we theorized a merged discourse that explains how the analog discourse becomes intertwined with the target discourse generating a transitional state where meanings, signs, symbols, and practices are in flux. Three categories were developed that capture how students intertwined the analog and target discourses—merged words, merged utterances/sentences, and merged practices.

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An increasing number of studies are highlighting the alarming proportion of motorists that drive after having consumed illicit drugs. However presently, little attention has focused on the factors that may facilitate drug driving from a criminogenic paradigm. This study evaluated the contribution of deterrence, defiance, and deviance theories on intentions to drug drive to determine factors that might facilitate or reduce this behaviour. A total of 922 individuals completed a questionnaire that assessed frequency of drug use and a variety of perceptions on deterrence, defiance, and deviance constructs. The analysis showed that the defiance constructs (i.e., experiencing feelings of shame and believing in the legitimacy of sanctioning authority) and the deviance constructs (i.e., moral attachment to the norm and having a criminal conviction) were predictive of drug driving intentions. The facets of deterrence theory were not found to be significant predictors. Ultimately, this study illustrates that a range of behavioural and perceptual factors have the capacity to influence decisions to drug drive. As a result, there appears the need to extend the focus of research endeavours beyond legal sanctions to examine other factors that may be utilised to both understand the aetiology of drug driving as well as increase the possibility of compliance with the corresponding legislation.

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Novel profluorescent nitroxides bearing a triazole linker between the coumarin fluorophore and an isoindoline nitroxide were prepared in good yields using the coppercatalyzed azide�alkyne 1,3-dipolar cycloaddition reaction (CuAAC). Nitroxides containing 7-hydroxy and 7-diethylamino substitution on their coumarin rings displayed significant fluorescence suppression, and upon reaction with methyl radicals, normal fluorescence emission was returned. The fluorescence emission for the 7-hydroxycoumarin nitroxide and its diamagnetic analogue was found to be strongly influenced by pH with maximal fluorescence emission achieved in basic solution. Solvent polarity was also shown to affect fluorescence emission. The significant difference in fluorescence output between the nitroxides and their corresponding diamagnetic analogues makes these compounds ideal tools for monitoring processes involving free-radical species.

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This important work describes recent theoretical advances in the study of artificial neural networks. It explores probabilistic models of supervised learning problems, and addresses the key statistical and computational questions. Chapters survey research on pattern classification with binary-output networks, including a discussion of the relevance of the Vapnik Chervonenkis dimension, and of estimates of the dimension for several neural network models. In addition, Anthony and Bartlett develop a model of classification by real-output networks, and demonstrate the usefulness of classification with a "large margin." The authors explain the role of scale-sensitive versions of the Vapnik Chervonenkis dimension in large margin classification, and in real prediction. Key chapters also discuss the computational complexity of neural network learning, describing a variety of hardness results, and outlining two efficient, constructive learning algorithms. The book is self-contained and accessible to researchers and graduate students in computer science, engineering, and mathematics