Synthetic and mechanistic aspects of the reactions of α-diazosulfoxides

The research described in this thesis focuses, principally, on synthesis of stable α-diazosulfoxides and investigation of their reactivity under various reaction conditions (transition-metal catalysed, photochemical, thermal and microwave) with a particular emphasis on the reactive intermediates and mechanistic aspects of the reaction pathways involved. In agreement with previous studies carried out on these compounds, the key reaction pathway of α-diazosulfoxides was found to be hetero-Wolff rearrangement to give α-oxosulfine intermediates. However, a competing reaction pathway involving oxygen migration from sulfur to oxygen was also observed. Critically, isomerisation of α-oxosulfine stereoisomers was observed directly by 1H NMR spectroscopy in this work and this observation accounts for the stereochemical outcomes of the various cycloaddition reactions, whether carried out with in situ trapping or with preformed solutions of sulfines. Furthermore, matrix isolation experiments have shown that electrocyclisation of α-oxosulfines to oxathiiranes takes place and this verifies the proposed mechanisms for enol and disulfide formation. The introductory chapter includes a brief literature review of the synthesis and reactivity of α-diazosulfoxides prior to the commencement of research in this field by the Maguire group. The Wolff rearrangement is also discussed and the characteristic reactions of a number of reactive intermediates (sulfines, sulfenes and oxathiiranes) are outlined. The use of microwave-assisted organic synthesis is also examined, specifically, in the context of α-diazocarbonyl compounds as substrates. The second chapter describes the synthesis of stable monocyclic and bicyclic lactone derivatives of α-diazosulfoxides from sulfide precursors according to established experimental procedures. Approaches to precursors of ketone and sulfimide derivatives of α-diazosulfoxides are also described. The third chapter examines the reactivity of α-diazosulfoxides under thermal, microwave, rhodium(II)-catalysed and photochemical conditions. Comparison of the results obtained under thermal and microwave conditions indicates that there was no evidence for any effect, other than thermal, induced by microwave irradiation. The results of catalyst studies involving several rhodium(II) carboxylate and rhodium(II) carboxamidate catalysts are outlined. Under photochemical conditions, sulfur extrusion is a significant reaction pathway while under thermal or transition metal catalysed conditions, oxygen extrusion is observed. One of the most important observations in this work was the direct spectroscopic observation (by 1H NMR) of interconversion of the E and Z-oxosulfines. Trapping of the α-oxosulfine intermediates as cycloadducts by reaction with 2,3-dimethyl-1,3-butadiene proved useful both synthetically and mechanistically. As the stereochemistry of the α-oxosulfine is retained in the cycloadducts, this provided an ideal method for characterisation of this key feature. In the case of one α-oxosulfine, a novel [2+2] cycloaddition was observed. Preliminary experiments to investigate the reactivity of an α-diazosulfone under rhodium(II) catalysis and microwave irradiation are also described. The fourth chapter describes matrix isolation experiments which were carried out in Rühr Universität, Bochum in collaboration with Prof. Wolfram Sander. These experiments provide direct spectroscopic evidence of an α-oxosulfine intermediate formed by hetero-Wolff rearrangement of an α-diazosulfoxide and subsequent cyclisation of the sulfine to an oxathiirane was also observed. Furthermore, it was possible to identify which stereoisomer of the α-oxosulfine was present in the matrix. A preliminary laser flash photolysis experiment is also discussed. The experimental details, including all spectral and analytical data, are reported at the end of each chapter. The structural interpretation of 1H NMR spectra of the cycloadducts, described in Chapter 3, is discussed in Appendix I.

Explorations in a meaning making system: Kerry as an entrepreneurial platform and the equine sector as a cluster

This Portfolio is about the changes that can be supported and achieved through transformational education that impacts on personal, professional and organisational levels. Having lived through an era of tremendous change over the second half of the twentieth century and into the twenty-first the author has a great drawing board to contemplate in the context of professional career experience as an engineer. The ability to engage in ‘subject-object’ separation is the means by which Kegan (1994, 2009) explains that transformation takes place and the Essays in this Portfolio aim to support and bring about such change. Exploration of aspects of ‘Kerry’ is the material selected to both challenge support change in the way of knowing from being subject to certain information and knowledge that to being able to consider it more objectively. The task of being able to distance judgement about the economy and economic development of Kerry was facilitated by various readings around of a number of key thinkers including Kegan, Drucker, Porter and Penrose. The central themes of Kerry or the potential for economic development are built into each Essay. Essay One focuses on reflections of Kerry life - on Kerry people within and without Kerry - and events as they affected understandings of how people related to and worked with one another. These reflections formed the basis for transformational goals identified which required a shift from an engineering mindset to encompass an economics-based view. In Essay Two knowledge of economic concepts is developed by exploring the writings of Drucker, Penrose, and Porter with pertinence to considering economic development generally, and for Kerry in particular in the form of an ‘entrepreneurial platform’. The concepts and theories were the basis of explorations presented in Essays Three and Four. Essay Three focuses on Kerry’s potential for economic development give its current economic profile and includes results from interviews with selected businesses. Essay Four is an exercise in the application of Porter’s ‘Cluster’ concept to the equine sector.

Contemporary subject: human rights and democracy

The aim of this paper is to show that only in a society where human rights are honored and democracy is vigorous, the process of subjectivation be possible. It is a critical sociology research. The article is presented in two parts, the first, subject and subjectivity in contemporary times, analyze the obstacles that individuals have for subjective process, and the second, subject and human rights and subject and democracy we argue about the need for human rights and democracy for the process of subjectivation.

‘Ghosts in the Head and Ghost Towns in the Field: Ethnography and the Experience of Presence and Absence’

This article is about an anthropologist coming to terms with the field and fieldwork. In 1995, I left – was evacuated from – my fieldsite as a volcanic eruption started just as my period of fieldwork drew to a close. These eruptions dramatically and instantaneously altered life on the island of Montserrat, a British colony in the Caribbean. While Montserrat the land, and Montserratians the people, migrated and moved on with their lives, Montserrat and Montserratians were preserved in my mind and in my anthropological writings as from “back home.” Revisiting Montserrat several years into the volcano crisis, I drove through the villages and roads leading to the former capital of the island, where I had worked from. My route to this modern-day Pompeii threw up a stark contrast between absence and presence, the imagined past and the experienced present. This is understood, in part, by examining the literary work of two other travelers through Montserrat, Henry Coleridge and Pete McCarthy, both of whom have a very different experience of the place and the people.

Genetic programming based formulation for fresh and hardened properties of self-compacting concrete containing pulverised fuel ash

Self-compacting concrete (SCC) flows into place and around obstructions under its own weight to fill the formwork completely and self-compact without any segregation and blocking. Elimination of the need for compaction leads to better quality concrete and substantial improvement of working conditions. This investigation aimed to show possible applicability of genetic programming (GP) to model and formulate the fresh and hardened properties of self-compacting concrete (SCC) containing pulverised fuel ash (PFA) based on experimental data. Twenty-six mixes were made with 0.38 to 0.72 water-to-binder ratio (W/B), 183–317 kg/m³ of cement content, 29–261 kg/m³ of PFA, and 0 to 1% of superplasticizer, by mass of powder. Parameters of SCC mixes modelled by genetic programming were the slump flow, JRing combined to the Orimet, JRing combined to cone, and the compressive strength at 7, 28 and 90 days. GP is constructed of training and testing data using the experimental results obtained in this study. The results of genetic programming models are compared with experimental results and are found to be quite accurate. GP has showed a strong potential as a feasible tool for modelling the fresh properties and the compressive strength of SCC containing PFA and produced analytical prediction of these properties as a function as the mix ingredients. Results showed that the GP model thus developed is not only capable of accurately predicting the slump flow, JRing combined to the Orimet, JRing combined to cone, and the compressive strength used in the training process, but it can also effectively predict the above properties for new mixes designed within the practical range with the variation of mix ingredients.

‘Doing it with men’: feminist research practice and patriarchal inheritance practices in Welsh family farming

Internationally, the gender relations of the family farming ‘way of life’ have beenshown to be stubbornly persistent in their adherence to patriarchal inheritancepractices. This article demonstrates how such ‘agri-cultural’ practices are situated bothwithin the subjective sphere of farming individuals’ and within global agri-economics,bringing new challenges to patrilineal farm survival. It is suggested here that the recenttendency for post-structuralist theorisation in rural studies has underestimated theexistence and impact of patrilineal patterns in family farming. Such patterns mean thatwomen are shown to largely occupy relational gender identities as the ‘helper’, whilstmen are strongly identified as the ‘farmer’. Drawing on repeated life-history interviewsconducted with farming men and women from Powys, Mid Wales, the aim of thisarticle is to generate debate as to the extent to which men can be brought into feministresearch practice in order to reveal patriarchy to a greater degree. The article begins bysituating the near-exclusion of men from feminist research practice within theoreticaldevelopments in feminist geography. This discussion also assists in deriving issues ofresearch methods, positionality and interpretive power which focus the integration ofempirical material in the methodological reflections provided in section three. In sectiontwo, the rationale for the epistemological stance taken in the research is provided. Thearticle provides an example of the successful integration of men into a feminist researchframe, suggests avenues for theoretical development and identifies future researchdirections which can be informed by ‘doing it with men’.

Keywords: epistemology; family farming; feminist res

Beyond the shadow space: architecture as a professional and creative process; during and post-conflict.

Introduction

Much has been written about the impact of conflict on the physical nature of cities; most obviously perhaps the damage, destruction, defensive construction and spatial reconfigurations that evolve in times of conflict. Set within the context of Belfast, Northern Ireland, this paper will focus on three areas. First, a closer reading of the long-term physical impact of conflict, in particular, the spatial forms and practices that persist conceptually and culturally, and/or resist re-conceptualisation. Secondly, the effect of conflict on the nature of architectural practice itself, considering whether issues such as appointment and procurement impacted on architectural expectation and the context of operation. Thirdly, the effect of conflict on people, in particular in relation to creativity and hence the psyche of practice itself. This section will also identify the conditions that undermine or support design quality and creativity not only within times of conflict but also as society evolves out of the shadow space. 1
Twelve years on from the Peace Agreement,2 it may seem remarkable from an external perspective that Northern Ireland still needs to be reflecting on its troubled past. But the immediate post-conflict phase offered the communities of Northern Ireland place and time to experience ‘normal life’, begin to reconcile themselves to the hurt they experienced and start to reconfigure their relationships to one another. Indeed, it has often been expressed that probing the issues too much, at too early a phase, might in fact ‘Open old wounds without resolving anything’ and/or ‘Destabilise the already fragile political system.’3 This tendency not to deliberate or be too probing is therefore understandable and might be the reason why, for example, Northern Ireland's first Architecture and Built Environment policy, published in June, 2006, contains only one routine reference to ‘the Troubles’.

Clearly, however, there is a time in the development of a healthy, functioning society, when in order effectively to plan its future, it must also carry out a closer reading and deeper understanding of its past. As Maya Angelou puts it, ‘History, despite its wrenching pain/ Cannot be unlived, and if faced/ With courage, need not be lived again.’4

Increasingly, those within the creative arts sector and the built environment professions are showing interest in carrying out that closer reading, teasing out issues around conflict. This was led in part by the recent publication of the Troubles Archive by the Arts Council of Northern Ireland.5 Those involved in the academic or professional development of future generations of architects are also concerned about the relevance of a post-conflict condition. As a profession, if architects purport to be concerned with context, then the almost tangible socio-political circumstances and legacy of Northern Ireland does inevitably require direct eye contact. This paper therefore aims to bring the relationship between conflict and architectural practice in Northern Ireland into sharp focus, not to constrain or dull creative practice but to heighten its potential.

Security governance in transition: The compartmentalising, crowding out and corralling of policing and security in Northern Ireland

The article suggests that while the report of the Independent Commission on Policing (ICP) provides a police reform blueprint for Northern Ireland and elsewhere, it can also be seen as an attempt to engage more elliptically with contemporary debates in security governance vis-a-vis the increasingly fragmented nature of late-modern policing and the role of the state. A decade into the reform process in Northern Ireland and in spite of the networked approach postulated by the ICP, the public police continue to enjoy a pre-eminent place and little evidence exists of any significant weakening of state steering and rowing of security. The discussion proposes a tentative typology explaining the continued colonization of security spaces by the State using constituent attendant processes of compartmentalizing, crowding out and corralling.

Radical Change, Accounting and Public Sector Reforms: A Comparison of Italian and Canadian Municipalities

NPM has been generally regarded as an administrative reform for which resilience and consequences have been mainly investigated at a country level. Although accounting played a central role in NPM reforms over the last decades, how accounting change actually took place, and through what organizational dynamics, has been under-investigated. This paper adopts a new perspective, archetype theory, and looks into how intra-organizational dynamics (values, interests, power, capabilities) combine with reform processes to influence the outcome of accounting change. Evidence from Italian (disruptive process) and Canadian (sedimented process) municipalities shows that radical change is associated with specific configurations of intra-organizational dynamics.

Gender mainstreaming and the Common Agricultural Policy

While there are many case studies looking at gender mainstreaming in national contexts, this article offers a pan-European perspective to examine how a stated commitment to gender equality at this meta-level works in practice. The European Union’s (EU) stated commitment to gender mainstreaming the Common Agricultural Policy (CAP) is critically reviewed. The article reviews theoretical literature on gender mainstreaming, considers the position of women in agriculture across Europe, and examines efforts by the EU to gender mainstream the CAP. It argues that at best, gender mainstreaming focuses on the symptoms of gender inequality in agriculture rather than the causes. Because of this, gender mainstreaming cannot be transformative in this context. Little thought has been given to the practical difficulties of actually gender mainstreaming a policy such as the CAP. The EU’s priority for the CAP focuses on the mainstream business goal of a viable agricultural industry and does not pay any heed to gender inequalities in agriculture. In short, the stated commitment to gender mainstreaming is empty rhetoric

The Casual Buttress:Certainty and Contingency in the Study of the Vernacular

Impromptu accretions such as the buttresses in Robin Walkers photograph are moments that are familiar in the architecture of the everyday. Indeed the buttress is a very common occurrence with these cottages in particular, their mud walls being poor at resisting concentrated lateral loading. While not always required the buttress emerges when requirements to create spaces to support inhabitation are at odds with the external form and construction of the buildings. These points of disjunction are resolved in an additive fashion externally. The location varies from structure to structure, occasionally the buttress is be used as a point of connection for further structures, becoming subsumed in outbuildings or walls. This preponderance to variety means that it is omitted from the reductive drawings of type that classify these buildings and yet it occurs in enough for it to have a fundamental and transformative relationship to the generality of cottages.
What is of interest is not so much what these structures hold in common, but rather what differentiates them. It is their capacity for variety within a defined range which allows them at once to speak at once of broader social structures and of a specific place and person.
Using the above observation this paper treats of the failure of architectural typological studies of the vernacular to derive anything other than formal exemplars, and posits an alternative approach based on a focus on the technical construction of such buildings.