Palladium-Catalyzed Oxidative Synthesis of Highly Functionalized Ortholactones

A palladium-catalyzed oxidative reaction is reported which converts dihydropyrans to their corresponding ortholactone. The products are formed in good to excellent yields with a very high level of chemoselectivity and functional group tolerance. Mechanistic studies confirm that the reaction proceeds by a Wacker-type mechanism.

Potentially Voting across the Divide in Deeply Divided Places: Ethnic Catch-All Voting in Consociational Northern Ireland

I elaborate a model of cross-bloc party support in deeply divided places. The model expects that the variation in the level of electoral support that citizens in Community A have for parties in Community B is a function of citizens' evaluations of the relative ability of parties in Community B to represent the interests of all communities. This 'ethnic catch-all' model of cross-bloc party support is tested in the context of consociational Northern Ireland, using data from a representative survey conducted directly after the 2010 Westminster general election. The findings are asymmetric: the model explains Protestant support for nationalist parties but not Catholic support for unionist parties. The findings, and their implications, are discussed.

Holding parties responsible at election time: Multi-level, multi-party government and electoral accountability

This paper highlights the crucial role played by party-specific responsibility attributions in performance-based voting. Three models of electoral accountability, which make distinct assumptions regarding citizens' ability to attribute responsibility to distinct governing parties, are tested in the challenging Northern Ireland context - an exemplar case of multi-level multi-party government in which expectations of performance based voting are low. The paper demonstrates the operation of party-attribution based electoral accountability, using data from the 2011 Northern Ireland Assembly Election Study. However, the findings are asymmetric: accountability operates in the Protestant/unionist bloc but not in the Catholic/nationalist bloc. This asymmetry may be explained by the absence of clear ethno-national ideological distinctions between the unionist parties (hence providing political space for performance based accountability to operate) but the continued relevance in the nationalist bloc of ethno-national difference (which limits the scope for performance politics). The implications of the findings for our understanding of the role of party-specific responsibility attribution in performance based models of voting, and for our evaluation of the quality of democracy in post-conflict consociational polities, are discussed. 

Boys' underachievement, educational aspirations and constructions of locality

Over recent years the moral panic that has surrounded 'boys' underachievement' has tended to encourage crude and essentialist comparisons between all boys and all girls and to eclipse the continuing and more profound effects on educational achievement exerted by social class and 'race'/ethnicity. While there are differences in educational achievement between working class boys and girls, these differences are relatively minor when comparing the overall achievement levels of working class children with those from higher, professional social class backgrounds. This paper argues that a need exists therefore for researchers to fully contextualise the gender differences that exist in educational achievement within the over-riding contexts provided by social class and 'race'/ethnicity. The paper provides an example of how this can be done through a case study of 11-year-old children from a Catholic, working class area in Belfast. The paper shows how the children's general educational aspirations are significantly mediated by their experiences of the local area in which they live. However, the way in which the children come to experience and construct a sense of locality differs between the boys and girls and this, it is argued, helps to explain the more positive educational aspirations held by some of the girls compared to the boys. The paper concludes by considering the relevance of locality for understanding its effects on educational aspirations among other working class and/or minority ethnic communities.

CHROMIUM(II)-MEDIATED CONVERSION OF ALPHA,BETA-UNSATURATED ALDEHYDES TO CYCLOPROPANOLS

Chromium(II) chloride converts alpha,beta-unsaturated aldehydes to the corresponding cyclopropanols.

Enhancing design space exploration by extending CPU/GPU specifications onto FPGAs

The design cycle for complex special-purpose computing systems is extremely costly and time-consuming. It involves a multiparametric design space exploration for optimization, followed by design verification. Designers of special purpose VLSI implementations often need to explore parameters, such as optimal bitwidth and data representation, through time-consuming Monte Carlo simulations. A prominent example of this simulation-based exploration process is the design of decoders for error correcting systems, such as the Low-Density Parity-Check (LDPC) codes adopted by modern communication standards, which involves thousands of Monte Carlo runs for each design point. Currently, high-performance computing offers a wide set of acceleration options that range from multicore CPUs to Graphics Processing Units (GPUs) and Field Programmable Gate Arrays (FPGAs). The exploitation of diverse target architectures is typically associated with developing multiple code versions, often using distinct programming paradigms. In this context, we evaluate the concept of retargeting a single OpenCL program to multiple platforms, thereby significantly reducing design time. A single OpenCL-based parallel kernel is used without modifications or code tuning on multicore CPUs, GPUs, and FPGAs. We use SOpenCL (Silicon to OpenCL), a tool that automatically converts OpenCL kernels to RTL in order to introduce FPGAs as a potential platform to efficiently execute simulations coded in OpenCL. We use LDPC decoding simulations as a case study. Experimental results were obtained by testing a variety of regular and irregular LDPC codes that range from short/medium (e.g., 8,000 bit) to long length (e.g., 64,800 bit) DVB-S2 codes. We observe that, depending on the design parameters to be simulated, on the dimension and phase of the design, the GPU or FPGA may suit different purposes more conveniently, thus providing different acceleration factors over conventional multicore CPUs.

Religion, pragmatic fundamentalism and the transformation of the Northern Ireland conflict

Since 11 September 2001, the religious dimension of conflict has been the focus of increasing attention. In The Clash of Civilizations, Huntington has identified the West in religious-cultural terms, as Christian with a dominant democratic culture emphasizing tolerance, moderation and consensus. The persistence of conflict in Northern Ireland among 'White' Protestant and Catholic Christians undermines this simplistic argument and demands a more subtle understanding of the role of religion and fundamentalism in contemporary conflict. Modernization theory - which is echoed among some theorists of globalization - had predicted the declining importance of religion as the world became industrialized and increasingly interconnected. This is echoed by those who argue that the Northern Ireland conflict is 'ethno-national' and dismiss the role of religion. On the other hand, others have claimed that the conflict is religious and stress the role of Protestant fundamentalism. This article draws on new evidence from Northern Ireland of the complex and subtle ways in which religion impacts on the conflict there, incorporating insights about the pragmatism of fundamentalist Protestants and how religious actors are contributing to conflict transformation. This analysis leads to three broader conclusions about understanding conflicts with religious dimensions. First, the complexity of religion must be understood, and this includes a willingness to recognize the adaptability of fundamentalisms to particular contexts. Second, engaging with fundamentalists and taking their grievances seriously opens up possibilities for conflict transformation. Third, governments and religious actors within civil society can play complementary roles in constructing alternative (religious) ideologies and structures as part of a process of transformation. In a world in which the impact of religion is persistent, engaging with the religious dimension is a vital part of a broader-based strategy for dealing with conflict. © 2008 Journal of Peace Research.

Catholicism and Fascism in Interwar Ireland

The interwar era saw the collapse of liberal democracy and the rise of anti-democratic authoritarian movements and states throughout much of Europe. Parliamentary or liberal democracy proved especially vulnerable in countries with large Catholic populations and ‘successor states’ – those states that achieved independence following the Great War. Despite meeting both criteria, the democratic structures of the Irish Free State – established in 1922 following a revolutionary struggle against British rule – proved remarkably resilient: indeed, it was arguably the only successor state to remain fully democratic by 1939 This outcome appears all the more striking given the formation of the state amidst a civil war, a form of conflict that frequently prevented the successful emergence of democracy. This is an article about the dog that didn’t bark: why did the kind of authoritarian political movements that flourished in many other parts of interwar Europe attract negligible support in the Irish Free State, and what does this have to tell us about the relationship between Catholicism and authoritarian politics? It begins by surveying the Irish Catholic Church’s attitudes to far-right politics in Continental Europe, and assessing how ‘official’ Catholic attitudes shaped popular perceptions of fascism and clerical authoritarianism within Ireland. It then explores the extent to which Ireland’s only significant fascistic movement – the Blueshirts – was influenced by, and sought to exploit, Catholicism. It concludes by questioning whether the immense influence of the Catholic Church and Catholic values within Irish political culture and society facilitated or hindered the cause of authoritarian politics in Ireland.

Traditions and transitions: teenagers’ perceptions of parading in Belfast

The purpose of this article is to explore and illuminate teenagers' experiences of, and attitudes to, parades in Belfast. The research draws on responses from 125 teenagers located in interface areas (areas where Catholics and Protestants live side by side but apart) to government supported attempts to rebrand Orangefest (traditional parade associated with Protestant/Unionist/Loyalist community) and St Patrick's Day (traditional parade associated with Catholic/Nationalist/Republican community) as all-inclusive community events. For the most part, young people access these parades in pre-existing, single identity peer groups and view these parades as either inclusive or exclusive calling into question the extent to which Belfast's city centre can be viewed as shared space.

‘Plugging the Gap’: Shared Education and the promotion of community relations through schools in Northern Ireland

Although there is no consensus amongst educationalists as to the role schools play as drivers of hostilities in divided societies, there is broad agreement that they can facilitate more positive intergroup relations. In Northern Ireland the promotion of school based inter-group contact has been offered as a means through which this can happen. Until 2007, the approach was twofold, reflected on the one hand in short-term contact opportunities for pupils in predominantly Catholic and Protestant schools, and on the other, in support for integrated schools which educate Catholics and Protestants together. In 2007 the Shared Education Programme was introduced to ‘bridge the gap’ between short-term opportunities for contact, and ‘full immersion’ integrated schools. Informed by contact theory, shared education offers curriculum based interaction between pupils attending all school types, aimed at promoting the type of contact likely to reduce negative social attitudes and ultimately contribute to social harmony. In this paper, we examine the impact of shared education thus far. Our analysis suggests that whilst shared education is generally effective in promoting positive assessments of other group members, there is a danger that programme impact may be inhibited by the foregrounding of educational over reconciliation priorities. Appreciating that the downplaying reconciliation objectives may have been necessary when the programme was established in order to maximize recruitment to it, we argue that if the full potential of shared education is to be realized, moving forward, it is important for schools to engage with issues of group differences.

Does social deprivation influence inter-group contact outcomes for pupils in Northern Ireland?

The education system in Northern Ireland is characterized by division, with
around 95% of the pupil population attending predominantly co-religionist
schools. In a society that is transitioning from a thirty year conflict that has been
framed by hostilities between the main Catholic and Protestant communities, reconciliation
interventions in education have sought to promote the value of intergroup
contact between pupils attending separate schools. Some qualitative research
suggests that such initiatives are more likely to have positive outcomes for
pupils from more middle class backgrounds than those from more disadvantaged
communitiesand areas that experienced high levels of conflict related incidents and deaths during the pre-ceasefire years. Drawing on contact theory and empirical evidence from a large scale quantitative study, we seek to examine this theory. Using free school meals as a proxy for social class, our findings are consistent in finding that there is a differential impact of contact for those from less affluent backgrounds, and we conclude by arguing that this should be reflected in policy responses.

Reva Siegel and the Role of Religion in Constructing the Meaning of ‘Human Dignity

The “religious understanding” of dignity is a topic of considerable complexity and is the subject of extensive scholarship. In this paper, I consider understandings of dignity that are currently under discussion in Roman Catholic circles, not least because Catholic discussions of dignity are often seen as influential in public policy and legal interpretation, directly and indirectly. I shall focus on one relatively neglected issue in legal scholarship: how scholars go about the task of identifying what a particular religion’s understanding of human dignity involves.
To illustrate the methodological problems that such an enterprise raises, I shall take one attempt by a scholar writing in the field of secular legal scholarship to describe Catholic understandings of dignity in the context of abortion and same-sex marriage. The discussion is that of Reva Siegel, an academic lawyer at Yale University; her recent analysis of differing understandings of dignity illustrates some of the issues that arise when the secular scholarly community addresses religious understandings of dignity.

Effect of monovalent cations on the kinetics of hypoxic conformational change of mitochondrial complex i

Mitochondrial complex I is a large, membrane-bound enzyme central to energy metabolism, and its dysfunction is implicated in cardiovascular and neurodegenerative diseases. An interesting feature of mammalian complex I is the so-called A/D transition, when the idle enzyme spontaneously converts from the active (A) to the de-active, dormant (D) form. The A/D transition plays an important role in tissue response to ischemia and rate of the conversion can be a crucial factor determining outcome of ischemia/reperfusion. Here, we describe the effects of alkali cations on the rate of the D-to-A transition to define whether A/D conversion may be regulated by sodium.At neutral pH (7–7.5) sodium resulted in a clear increase of rates of activation (D-to-A conversion) while other cations had minor effects. The stimulating effect of sodium in this pH range was not caused by an increase in ionic strength. EIPA, an inhibitor of Na+/H+antiporters, decreased the rate of D-to-A conversion and sodium partially eliminated this effect of EIPA. At higher pH (> 8.0), acceleration of the D-to-A conversion by sodium was abolished, and all tested cations decreased the rate of activation, probably due to the effect of ionic strength.The implications of this finding for the mechanism of complex I energy transduction and possible physiological importance of sodium stimulation of the D-to-A conversion at pathophysiological conditions in vivo are discussed.

Investigations Into the Performance of a Turbogenerated Biogas Engine During Speed Transients

Turbogenerating is a form of turbocompounding whereby a Turbogenerator is placed in the exhaust stream of an internal combustion engine. The Turbogenerator converts a portion of the expelled energy in the exhaust gas into electricity which can then be used to supplement the crankshaft power. Previous investigations have shown how the addition of a Turbogenerator can increase the system efficiency by up to 9%. However, these investigations pertain to the engine system operating at one fixed engine speed. The purpose of this paper is to investigate how the system and in particular the Turbogenerator operate during engine speed transients. On turbocharged engines, turbocharger lag is an issue. With the addition of a Turbogenerator, these issues can be somewhat alleviated. This is done by altering the speed at which the Turbogenerator operates during the engine’s speed transient. During the transients, the Turbogenerator can be thought to act in a similar manner to a variable geometry turbine where its speed can cause a change in the turbocharger turbine’s pressure ratio. This paper shows that by adding a Turbogenerator to a turbocharged engine the transient performance can be enhanced. This enhancement is shown by comparing the turbogenerated engine to a similar turbocharged engine. When comparing the two engines, it can be seen that the addition of a Turbogenerator can reduce the time taken to reach full power by up to 7% whilst at the same time, improve overall efficiency by 7.1% during the engine speed transient.

Hypoxia response element-driven cytosine deaminase/5-fluorocytosine gene therapy system:a highly effective approach to overcome the dynamics of tumour hypoxia and enhance the radiosensitivity of prostate cancer cells in vitro

BACKGROUND: We proposed to exploit hypoxia-inducible factor (HIF)-1alpha overexpression in prostate tumours and use this transcriptional machinery to control the expression of the suicide gene cytosine deaminase (CD) through binding of HIF-1alpha to arrangements of hypoxia response elements. CD is a prodrug activation enzyme, which converts inactive 5-fluorocytosine to active 5-fluorouracil (5-FU), allowing selective killing of vector containing cells.

METHODS: We developed a pair of vectors, containing either five or eight copies of the hypoxia response element (HRE) isolated from the vascular endothelial growth factor (pH5VCD) or glycolytic enzyme glyceraldehyde-3-phosphate dehydrogenase (pH8GCD) gene, respectively. The kinetics of the hypoxic induction of the vectors and sensitization effects were evaluated in 22Rv1 and DU145 cells in vitro.

RESULTS: The CD protein as selectively detected in lysates of transiently transfected 22Rv1 and DU145 cells following hypoxic exposure. This is the first evidence of GAPDH HREs being used to control a suicide gene therapy strategy. Detectable CD levels were sustained upon reoxygenation and prolonged hypoxic exposures. Hypoxia-induced chemoresistance to 5-FU was overcome in both cell lines treated with this suicide gene therapy approach. Hypoxic transfectants were sensitized to prodrug concentrations that were ten-fold lower than those that are clinically relevant. Moreover, the surviving fraction of reoxygenated transfectants could be further reduced with the concomitant delivery of clinically relevant single radiation doses.

CONCLUSIONS: This strategy thus has the potential to sensitize the hypoxic compartment of prostate tumours and improve the outcome of current therapies.