6 resultados para Three-photon processes

em CORA - Cork Open Research Archive - University College Cork - Ireland


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This paper examines the international diffusion of one business practice, project management, through the prism of prior literature and data on the diffusion of ISO 9000. The study took an inductive approach, building theory through the iterative collection and analysis of quantitative and qualitative data. The findings problematise the central position accorded to the S-curve model and neo-institutional theory in explaining technology diffusion. The research posits three distinct processes driving the diffusion process: utility, institutional isomorphism, and competitive isomorphism, with the latter consisting of three primary mechanisms: competitive imitation, trendslators and fashion retailers. Contrary to prior literature, national, quasi-professional associations are found to be central to the diffusion process and play a key role in advocating and containing management technologies.

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This thesis describes the optimisation of chemoenzymatic methods in asymmetric synthesis. Modern synthetic organic chemistry has experienced an enormous growth in biocatalytic methodologies; enzymatic transformations and whole cell bioconversions have become generally accepted synthetic tools for asymmetric synthesis. Biocatalysts are exceptional catalysts, combining broad substrate scope with high regio-, enantio- and chemoselectivities enabling the resolution of organic substrates with superb efficiency and selectivity. In this study three biocatalytic applications in enantioselective synthesis were explored and perhaps the most significant outcome of this work is the excellent enantioselectivity achieved through optimisation of reaction conditions improving the synthetic utility of the biotransformations. In the first chapter a summary of literature discussing the stereochemical control of baker’s yeast (Saccharomyces Cerevisae) mediated reduction of ketones by the introduction of sulfur moieties is presented, and sets the work of Chapter 2 in context. The focus of the second chapter was the synthesis and biocatalytic resolution of (±)-trans-2-benzenesulfonyl-3-n-butylcyclopentanone. For the first time the practical limitations of this resolution have been addressed providing synthetically useful quantities of enantiopure synthons for application in the total synthesis of both enantiomers of 4-methyloctanoic acid, the aggregation pheromone of the rhinoceros beetles of the genus Oryctes. The unique aspect of this enantioselective synthesis was the overall regio- and enantioselective introduction of the methyl group to the octanoic acid chain. This work is part of an ongoing research programme in our group focussed on baker’s yeast mediated kinetic resolution of 2-keto sulfones. The third chapter describes hydrolase-catalysed kinetic resolutions leading to a series of 3-aryl alkanoic acids. Hydrolysis of the ethyl esters with a series of hydrolases was undertaken to identify biocatalysts that yield the corresponding acids in highly enantioenriched form. Contrary to literature reports where a complete disappearance of efficiency and, accordingly enantioselection, was described upon kinetic resolution of sterically demanding 3-arylalkanoic acids, the highest reported enantiopurities of these acids was achieved (up to >98% ee) in this study through optimisation of reaction conditions. Steric and electronic effects on the efficiency and enantioselectivity of the biocatalytic transformation were also explored. Furthermore, a novel approach to determine the absolute stereochemistry of the enantiopure 3-aryl alkanoic acids was investigated through combination of co-crystallisation and X-ray diffraction linked with chiral HPLC analysis. The fourth chapter was focused on the development of a biocatalytic protocol for the asymmetric Henry reaction. Efficient kinetic resolution in hydrolase-mediated transesterification of cis- and trans- β-nitrocyclohexanol derivatives was achieved. Combination of a base-catalysed intramolecular Henry reaction coupled with the hydrolase-mediated kinetic resolution with the view to selective acetylation of a single stereoisomer was investigated. While dynamic kinetic resolution in the intramolecular Henry was not achieved, significant progress in each of the individual elements was made and significantly the feasibility of this process has been demonstrated. The final chapter contains the full experimental details, including spectroscopic and analytical data of all compounds synthesised in this project, while details of chiral HPLC analysis are included in the appendix. The data for the crystal structures are contained in the attached CD.

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Ecosystem goods and services provided by estuarine and near coastal regions are being increasingly recognised for their immense value, as is the biodiversity in these areas and these near coastal communities have been identified as sentinels of climate change also. Population structure and reproductive biology of two bivalve molluscs, Cerastoderma edule and, Mytilus edulis were assessed at two study sites over a 16-month study period. Following an anomalously harsh winter, advancement of spawning time was observed in both species. Throughout Ireland and Europe the cockle has experienced mass surfacings in geographically distinct regions, and a concurrent study of cockles was undertaken to explore this phenomenon. Surfaced and buried cockles were collected on a monthly basis and their health compared. Age was highlighted as a source of variation between dying and healthy animals with a parasite threshold being reached possibly around age three. Local factors dominated when looking at the cause of surfacing at each site. The health of mussels was explored too on a temporal and seasonal basis in an attempt to assess what constitutes a healthy organism. In essence external drivers can tip the balance between “acceptable” levels of infection where the mussel can still function physiologically and “unacceptable” where prevalence and intensity of infection can result in physiological impairment at the individual and population level. Synecological studies of intertidal ecosystems are lacking, so all bivalves encountered during the sampling were assessed in terms of population structure, reproduction, and health. It became clear, that some parasites might specialize on one host species while others are not so specific in host choice. Furthermore the population genetics of the cockle, its parasite Meiogymnophallus minutus, and its hyperparasite Unikaryon legeri were examined too. A small nucleotide polymorphism was detected upon comparison of Ireland and Morocco.

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The enculturation of Irish traditional musicians involves informal, non-formal, and sometimes formal learning processes in a number of different settings, including traditional music sessions, workshops, festivals, and classes. Irish traditional musicians also learn directly from family, peers, and mentors and by using various forms of technology. Each experience contributes to the enculturation process in meaningful and complementary ways. The ethnographic research discussed in this dissertation suggests that within Irish traditional music culture, enculturation occurs most effectively when learners experience a multitude of learning practices. A variety of experiences insures that novices receive multiple opportunities for engagement and learning. If a learner finds one learning practice ineffective, there are other avenues of enculturation. This thesis explores the musical enculturation of Irish traditional musicians. It focuses on the process of becoming a musician by drawing on methodologies and theories from ethnomusicology, education, and Irish traditional music studies. Data was gathered through multiple ethnographic methodologies. Fieldwork based on participant-observation was carried out in a variety of learning contexts, including traditional music sessions, festivals, workshops, and weekly classes. Additionally, interviews with twenty accomplished Irish traditional musicians provide diverse narratives and firsthand insight into musical development and enculturation. These and other methodologies are discussed in Chapter 1. The three main chapters of the thesis explore various common learning experiences. Chapter 2 explores how Irish traditional musicians learn during social and musical interactions between peers, mentors, and family members, and focuses on live music-making which occurs in private homes, sessions, and concerts. These informal and non-formal learning experiences primarily take place outside of organizations and institutions. The interview data suggests these learning experiences are perhaps the most pervasive and influential in terms of musical enculturation. Chapter 3 discusses learning experience in more organized settings, such as traditional music classes, workshops, summer schools, and festivals. The role of organizations such as Comhaltas Ceoltóirí Éireann and pipers’ clubs are discussed from the point of view of the learner. Many of the learning experiences explored in this chapter are informal, non-formal, and sometimes formal in nature, depending on the philosophy of the organization, institution, and individual teacher. The interview data and field observations indicate that learning in these contexts is common and plays a significant role in enculturation, particularly for traditional musicians who were born during and after the 1970s. Chapter 4 explores the ways Irish traditional musicians use technology, including written sources, phonography, videography, websites, and emerging technologies, during the enculturation process. Each type of technology presents different educational implications, and traditional musicians use these technologies in diverse ways and some more than others. For this, and other reasons, technology plays a complex role during the process of musical enculturation. Drawing on themes which emerge during Chapter 2, 3, and 4, the final chapter of this dissertation explores overarching patterns of enculturation within Irish traditional music culture. This ethnographic work suggests that longevity of participation and engagement in multiple learning and performance opportunities foster the enculturation of Irish traditional musicians. Through numerous and prolonged participation in music-making, novices become accustomed to and learn musical, social, and cultural behaviours. The final chapter also explores interconnections between learning experiences and also proposes directions for future research.

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This thesis focuses on the complex relationship between representations of the human body and the formal processes of mise-en-scène in three consecutive films by the writer-director Paul Schrader: American Gigolo (1980), Cat People (1982) and Mishima: A Life in Four Chapters (1985). While Schrader’s work has typically been critiqued under the broad category of masculinity in crisis (and often as a subset of the films of his more famous long-time collaborator, Martin Scorsese), I focus on a fiveyear early period of his filmography when he sought to explore his key themes of bodily crisis, fragmentation and alienation through an unusually intense focus upon the expressive potential of film form, specifically via the combined elements of colour, lighting, camerawork and production design. By approaching these three films as corporeal character studies of troubled figures whose emotional and psychosexual neurosis is experienced in and through the body, I will locate Schrader’s filmmaking process and style within the thematic and aesthetic contexts of both his own early film criticism and the European and Japanese art cinemas that he claims as his primary influence. In doing so, I will establish Schrader’s position as a director whose literary and theological background differentiated him from his peers of the postclassical Hollywood generation, and who thus continually sought to develop his own visual literacy through his relationship with the camera and his collaborations with more overtly style-oriented film artists. But instead of merely focusing on mise-en-scène to gain a formalist appreciation of these films, I mobilise stylistic analysis as a new critical approach towards the problematic discourses of identity and embodiment that have haunted Schrader’s career from the beginning. In particular, I argue that paying closer attention to Schrader’s formal choices sheds new light on how these films – which he approached as exercises in style – repeatedly deal with the volatile and unavoidably body-oriented categories of race, gender and sexuality. In the process, I argue that a formalist attentiveness to mise-en-scène can also provide valuable cultural insights into Schrader’s oeuvre.

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Background: Diagnostic decision-making is made through a combination of Systems 1 (intuition or pattern-recognition) and Systems 2 (analytic) thinking. The purpose of this study was to use the Cognitive Reflection Test (CRT) to evaluate and compare the level of Systems 1 and 2 thinking among medical students in pre-clinical and clinical programs. Methods: The CRT is a three-question test designed to measure the ability of respondents to activate metacognitive processes and switch to System 2 (analytic) thinking where System 1 (intuitive) thinking would lead them astray. Each CRT question has a correct analytical (System 2) answer and an incorrect intuitive (System 1) answer. A group of medical students in Years 2 & 3 (pre-clinical) and Years 4 (in clinical practice) of a 5-year medical degree were studied. Results: Ten percent (13/128) of students had the intuitive answers to the three questions (suggesting they generally relied on System 1 thinking) while almost half (44%) answered all three correctly (indicating full analytical, System 2 thinking). Only 3-13% had incorrect answers (i.e. that were neither the analytical nor the intuitive responses). Non-native English speaking students (n = 11) had a lower mean number of correct answers compared to native English speakers (n = 117: 1.0 s 2.12 respectfully: p < 0.01). As students progressed through questions 1 to 3, the percentage of correct System 2 answers increased and the percentage of intuitive answers decreased in both the pre-clinical and clinical students. Conclusions: Up to half of the medical students demonstrated full or partial reliance on System 1 (intuitive) thinking in response to these analytical questions. While their CRT performance has no claims to make as to their future expertise as clinicians, the test may be used in helping students to understand the importance of awareness and regulation of their thinking processes in clinical practice.