Structural carpentry in medieval Ireland: continuity and change

The study of medieval carpentry is probably one of the most neglected aspects of archaeological research in Ireland. The principal difficulty is the nature of the evidence, in that timber, unless the conditions are right, rarely leaves a trace above ground. The problem is further exacerbated by the fact that not a single medieval timber-framed building has survived in Ireland. Nevertheless, in recent years, in addition to the medieval roof of Dunsoghley, which up to quite recently was thought to be the only surviving roof structure in Ireland, a further eight medieval roof structures have been identified. Furthermore, an extensive corpus of early medieval mills, with evidence for advanced Roman carpentry techniques, has been excavated, while evidence for Viking houses, on what is probably the largest extant Viking settlement in Europe, have also been recovered. Although post and wattle structures dominate the archaeological record of the Viking period, nevertheless, it will be shown that the Roman tradition of carpentry, evidenced in the early medieval mills from the early seventh century, continued in use in the wider Gaelic community. And it is one of the pivotal points of this study, that with the takeover of Dublin by the Gaelic Irish in the late tenth century, this Roman carpentry tradition was gradually assimilated into the carpentry tradition of the Viking towns, which were now largely inhabited by a mixed population of Hiberno-Norse. Evidence for this Gaelic influence can be seen not only in the gradual replacement of the Viking post and wattle house by timber houses with load-bearing walls, but more importantly by the evidence for waterfront structures founded on baseplates with mortise and tenoned uprights on the pre-Norman waterfront in Cork. Furthermore, it will be shown, that the carpentry techniques used to build the Wood Quay revetments, shortly after the Anglo-Norman conquest in AD 1170, supports this contention.

An exploration of leadership in Irish post-primary education

The purpose of this study is to explore the nature and how of leadership in Irish post-primary schools. It considers school leadership within the context of contemporary Distributed Leadership theory. Associated concepts such as Distributed Cognition and Activity Theory are used to frame the study. From a distributed perspective, it is now widely accepted that other agents (e.g. teachers) have a leadership role, as part of collaborative, participative and supportive learning communities. Thus, this study considers how principals interact and build leadership capacity throughout the school. The study draws on two main sources of evidence. In analysing the implications of accountability agendas for school leadership, there is an exploration and focus on the conceptualisations of school leadership that are fore-grounded in 21 WSE reports. Elements of Critical Discourse Analysis are employed as an investigative tool to decipher how the construction of leadership practice is produced. The second prong of the study explores leadership in 3 case-study post-primary schools. Leadership is a complex phenomenon and not easy to describe. The findings clarify, however, that school leadership is a construct beyond the scope of the principal alone. While there is widespread support for a distributed model of leadership, the concept does not explicitly form part of the discourse in the case-study schools. It is also evident that any attempt to understand leadership practice must connect local interpretations with broader discourses. The understanding and practice of leadership is best understood in its sociohistorical context. The study reveals that, in the Irish post-primary school, the historical dimension is very influential, while the situational setting, involving a particular set of agents and agendas, strongly shapes thinking and practices. This study is novel as it synthesises two key sources of evidence. It is of great value in that it teases out the various historical and situational aspects to enhance understandings of school leadership in contemporary Ireland. It raises important questions for policy, practice and further research.

A microscopic study of structural and electronic properties of functionalized silicon surfaces based on first-principles

Surface modification of silicon with organic monolayers tethered to the surface by different linkers is an important process in realizing future (opto-)electronic devices. Understanding the role played by the nature of the linking group and the chain length on the adsorption structures and electronic properties of these assemblies is vital to advance this technology. This Thesis is a study of such properties and contributes in particular to a microscopic understanding of induced changes in the work function of experimentally studied functionalized silicon surfaces. Using first-principles density functional theory (DFT), at the first step, we provide predictions for chemical trends in the work function of hydrogenated silicon (111) surfaces modified with various terminations. For nonpolar terminating atomic species such as F, Cl, Br, and I, the change in the work function is directly proportional to the amount of charge transferred from the surface, thus relating to the difference in electronegativity of the adsorbate and silicon atoms. The change is a monotonic function of coverage in this case, and the work function increases with increasing electronegativity. Polar species such as −TeH, −SeH, −SH, −OH, −NH2, −CH3, and −BH2 do not follow this trend due to the interaction of their dipole with the induced electric field at the surface. In this case, the magnitude and sign of the surface dipole moment need to be considered in addition to the bond dipole to generally describe the change in work function. Compared to hydrogenated surfaces, there is slight increase in the work function of H:Si(111)-XH, where X = Te, Se, and S, whereas reduction is observed for surfaces covered with −OH, −CH3, and −NH2. Next, we study the hydrogen passivated Si(111) surface modified with alkyl chains of the general formula H:Si–(CH2)n–CH2 and H:Si–X–(CH2)n–CH3, where X = NH, O, S and n = (0, 1, 3, 5, 7, 9, 11), at half coverage. For (X)–Hexyl and (X)–Dodecyl functionalization, we also examined various coverages up to full monolayer grafting in order to validate the result of half covered surface and the linker effect on the coverage. We find that it is necessary to take into account the van der Waals interaction between the alkyl chains. The strongest binding is for the oxygen linker, followed by S, N, and C, irrespective of chain length. The result revealed that the sequence of the stability is independent of coverage; however, linkers other than carbon can shift the optimum coverage considerably and allow further packing density. For all linkers apart from sulfur, structural properties, in particular, surface-linker-chain angles, saturate to a single value once n > 3. For sulfur, we identify three regimes, namely, n = 0–3, n = 5–7, and n = 9–11, each with its own characteristic adsorption structures. Where possible, our computational results are shown to be consistent with the available experimental data and show how the fundamental structural properties of modified Si surfaces can be controlled by the choice of linking group and chain length. Later we continue by examining the work function tuning of H:Si(111) over a range of 1.73 eV through adsorption of alkyl monolayers with general formula -[Xhead-group]-(CnH2n)-[Xtail-group], X = O(H), S(H), NH(2). The work function is practically converged at 4 carbons (8 for oxygen), for head-group functionalization. For tail-group functionalization and with both head- and tail-groups, there is an odd-even effect in the behavior of the work function, with peak-to-peak amplitudes of up to 1.7 eV in the oscillations. This behavior is explained through the orientation of the terminal-group's dipole. The shift in the work function is largest for NH2-linked and smallest for SH-linked chains and is rationalized in terms of interface dipoles. Our study reveals that the choice of the head- and/or tail-groups effectively changes the impact of the alkyl chain length on the work function tuning using self-assembled monolayers and this is an important advance in utilizing hybrid functionalized Si surfaces. Bringing together the understanding gained from studying single type functionalization of H:Si(111) with different alkyl chains and bearing in mind how to utilize head-group, tail-group or both as well as monolayer coverage, in the final part of this Thesis we study functionalized H:Si(111) with binary SAMs. Aiming at enhancing work function adjustment together with SAM stability and coverage we choose a range of terminations and linker-chains denoted as –X–(Alkyl) with X = CH3, O(H), S(H), NH(2) and investigate the stability and work function of various binary components grafted onto H:Si(111) surface. Using binary functionalization with -[NH(2)/O(H)/S(H)]-[Hexyl/Dodecyl] we show that work function can be tuned within the interval of 3.65-4.94 eV and furthermore, enhance the SAM’s stability. Although direct Si-C grafted SAMs are less favourable compared to their counterparts with O, N or S linkage, regardless of the ratio, binary functionalized alkyl monolayers with X-alkyl (X = NH, O) is always more stable than single type alkyl functionalization with the same coverage. Our results indicate that it is possible to go beyond the optimum coverage of pure alkyl functionalized SAMs (50%) by adding a linker with the correct choice of the linker. This is very important since dense packed monolayers have fewer defects and deliver higher efficiency. Our results indicate that binary anchoring can modify the charge injection and therefore bond stability while preserving the interface electronic structure.

From the demise of theory to its resurgence. A retrospective on the postmodern turn to rethink the 'desire for narrative' and the sublime untimeliness of emancipation

Cultural Marxist Theory, commonly known as theory, enjoyed a moment of extraordinary success in the 1970s, when the works of leading post-war French philosophers were published in English. After relocating to Anglophone academia, however, theory disavowed its original concerns and lost its ambition to understand the world as a whole, becoming the play of heterogeneities associated with postcolonialism, multiculturalism and identity politics, commonly referred to as postmodern theory. This turn, which took place during a period that seemed to have spelt the death of Marxism, the 1990s, induced many of its supporters to engage in an ongoing funeral wake designating the merits of theory and dreaming its resurgence. According to them, had theory been resurrected in historical circumstances completely different from those which had led to its rise, it would have never reacquired the significance that had originally connoted it. This thesis demonstrates how theory has survived its demise and entirely regained its prominence in our socio-political context marked by the effects of the latest crisis of capitalism and by the global threat of terrorisms rooted in messianic eschatologies. In its current form theory does no longer need to show allegiance to certain intellectual stances or political groupings in order to produce important reformulations of the projects it once gave life to. Though less overtly radical and epistemologically bounded, theory remains a necessary form of enquiry justified by the political commitment which originated it in the first place. Its voice continues to speak to us about justice ‘where it is not yet, not yet there, where it is no longer’ (Derrida, 1993, XVIII).

Structural manifestation of the delocalization error of density functional approximations: C(4N+2) rings and C(20) bowl, cage, and ring isomers.

The ground state structure of C(4N+2) rings is believed to exhibit a geometric transition from angle alternation (N < or = 2) to bond alternation (N > 2). All previous density functional theory (DFT) studies on these molecules have failed to reproduce this behavior by predicting either that the transition occurs at too large a ring size, or that the transition leads to a higher symmetry cumulene. Employing the recently proposed perspective of delocalization error within DFT we rationalize this failure of common density functional approximations (DFAs) and present calculations with the rCAM-B3LYP exchange-correlation functional that show an angle-to-bond-alternation transition between C(10) and C(14). The behavior exemplified here manifests itself more generally as the well known tendency of DFAs to bias toward delocalized electron distributions as favored by Huckel aromaticity, of which the C(4N+2) rings provide a quintessential example. Additional examples are the relative energies of the C(20) bowl, cage, and ring isomers; we show that the results from functionals with minimal delocalization error are in good agreement with CCSD(T) results, in contrast to other commonly used DFAs. An unbiased DFT treatment of electron delocalization is a key for reliable prediction of relative stability and hence the structures of complex molecules where many structure stabilization mechanisms exist.

C. G. Jung and literary theory: the challenge from fiction

C.G. Jung and Literary Theory remedies a significant omission in literary studies by doing for Jung and poststructuralist literary theories what has been done extensively for Freud, Lacan and post-Freudian psychoanalysis. This work represents a complete departure from traditional Jungian literary criticism. Instead, radically new Jungian literary theories are developed of deconstruction, feminist theory, gender and psyche, the body and sexuality, spirituality, postcolonialism, historicism and reader-response. As well as linking Jung to the work of Derrida, Kristeva and Irigaray, the book traces contentious occult, cultural and political narratives in Jung's career. It contains a chapter on Jung and fascism in a literary context. [From the Publisher]

Can density functional theory (DFT) be used as an aid to a deeper understanding of tandem mass spectrometric fragmentation pathways?

Prediction of tandem mass spectrometric (MS/MS) fragmentation for non-peptidic molecules based on structure is of immense interest to the mass spectrometrist. If a reliable approach to MS/MS prediction could be achieved its impact within the pharmaceutical industry could be immense. Many publications have stressed that the fragmentation of a molecular ion or protonated molecule is a complex process that depends on many parameters, making prediction difficult. Commercial prediction software relies on a collection of general heuristic rules of fragmentation, which involve cleaving every bond in the structure to produce a list of 'expected' masses which can be compared with the experimental data. These approaches do not take into account the thermodynamic or molecular orbital effects that impact on the molecule at the point of protonation which could influence the potential sites of bond cleavage based on the structural motif. A series of compounds have been studied by examining the experimentally derived high-resolution MS/MS data and comparing it with the in silico modelling of the neutral and protonated structures. The effect that protonation at specific sites can have on the bond lengths has also been determined. We have calculated the thermodynamically most stable protonated species and have observed how that information can help predict the cleavage site for that ion. The data have shown that this use of in silico techniques could be a possible way to predict MS/MS spectra. Copyright (C) 2009 John Wiley & Sons, Ltd.

State power matters: power, the state and political struggle in the post-war American novel

This article is concerned with resituating the state at the centre of the analytical stage and, concomitantly, with drawing attention to the dangers of losing sight of the state as a locus of power. It seeks to uncover the relationship between two related lines of critical inquiry: Marxist and Foucauldian theories of the state; and the attempts by three postwar American novelist (Ken Kesey, William Burroughs and E.L. Doctorow) to determine the nature and extent of this power and to consider under what conditions political struggle might be possible. It argues that such a move is needed because recent critical analysis has been too preoccupied by corporeal micropolitics and global macropolitics, and that the postwar American novel can help us in this move because it is centrally concerned with the repressive potentiality of the US state. It maintains that the resuscitation of Marxist state theories in early 1970s and a debate between Poulantzas and Foucault is intriguingly foreshadowed and even critiqued by these novels. Consequently, it concludes that these novels constitute an unrecognized pre-history of what would become one of the key intellectual debates of the late twentieth century: an engagement between Marxist and post-structuralist conceptions of the power and resistance.

Pachymedusa dacnicolor tryptophyllin-1 (PdT-1): structural characterization, pharmacological activity and cloning of precursor cDNA.

Tryptophyllins are a heterogenous group of amphibian skin peptides originally identified in skin extracts of Neotropical leaf frogs, Phyllomedusa sp., by chemical means. Until now, biosynthetic precursor structure and biological activity remain unreported. Here we describe the isolation of a novel, post-translationally modified tryptophyllin, Lys-Pro-Hyp-Ala-Trp-Val-Pro.amide (PdT-1), from the skin secretion of the Mexican leaf frog, Pachymedusa dacnicolor. Using a 3'- and 5'-RACE strategy and an in vitro skin cDNA library, the PdT-1-encoding precursor was cloned and found to consist of an open-reading frame of 62 amino acids with a single copy of PdT-1 located towards the C-terminus. A synthetic replicate of PdT-1 was found to be a potent myoactive agent, relaxing mammalian arterial smooth muscle and contracting small intestinal smooth muscle at nanomolar concentrations. PdT-1 is thus the first amphibian skin tryptophyllin to be pharmacologically characterized and the first whose precursor cDNA has been cloned.

Interactions of 1-Methylimidazole with UO2(CH3CO2)2 and UO2(NO3)2: Structural, Spectroscopic and Theoretical Evidence for Imidazole Binding to the Uranyl Ion

The first definitive high-resolution single-crystal X-ray structure for the coordination of the 1-methylimidazole (Meimid) ligand to UO2(Ac)2 (Ac = CH3CO2) is reported. The crystal structure evidence is confirmed by IR, Raman, and UV-vis spectroscopic data. Direct participation of the nitrogen atom of the Meimid ligand in binding to the uranium center is confirmed. Structural analysis at the DFT (B3LYP) level of theory showed a conformational difference of the Meimid ligand in the free gas-phase complex versus the solid state due to small energetic differences and crystal packing effects. Energetic analysis at the MP2 level in the gas phase supported stronger Meimid binding over H2O binding to both UO2(Ac)2 and UO2(NO3)2. In addition, self-consistent reaction field COSMO calculations were used to assess the aqueous phase energetics of combination and displacement reactions involving H2O and Meimid ligands to UO2R2 (R = Ac, NO3). For both UO2(NO3)2 and UO2(Ac)2, the displacement of H2O by Meimid was predicted to be energetically favorable, consistent with experimental results that suggest Meimid may bind uranyl at physiological pH. Also, log(Knitrate/KAc) calculations supported experimental evidence that the binding stoichiometry of the Meimid ligand is dependent upon the nature of the reactant uranyl complex. These results clearly demonstrate that imidazole binds to uranyl and suggest that binding of histidine residues to uranyl could occur under normal biological conditions.

Developing NGO competencies in post-disaster reconstruction: a theoretical framework

In the aftermath of recent natural disasters, NGOs have become increasingly involved in the permanent reconstruction of affected communities. These organizations, often operating well outside their expertise, encounter significant barriers as they implement reconstruction programmes. This paper presents the theoretical bedrock of a current research project, the overall goal of which is to design a competency-based framework model that can be used by NGOs in post-disaster reconstruction projects. Drawing on established theories of management, a unique perspective has been developed from which a competency-based reconstruction theory emerges. This theoretical framework brings together three distinct fields; Disaster Management, Strategic Management and Project Management, each vital to the success of the model. This theoretical study will incorporate a critical review of literature within each field. It is imperative that NGOs involved in post-disaster reconstruction familiarize themselves with concepts and strategies. It is hoped that the competence-based frame-work model that is produced on the basis of this theory will help define the standard of best practice to which future NGO projects might align themselves.

Philosophy, Social Hope and Democratic Criticism:Critical Theory for a Global Age

The attempt to connect philosophy and social hope has been one of the key distinguishing features of critical theory as a tradition of enquiry. This connection has been questioned forcefully from the perspective of a post-philosophical pragmatism, as articulated by Rorty. In this article I consider two strategies that have been adopted by critical theorists in seeking to reject Rorty's suggestion that we should abandon the attempt to ground social hope in philosophical reason. We consider argumentative strategies of the philosophical anthropologist and of the rational proceduralist. Once the exchanges between Rorty and these two strands of critical theory have been reconstructed and assessed, an alternative perspective emerges. It is argued that philosophical reasoning best helps to sustain social hope in a rapidly changing world when we consider it in terms of the practice of democratic criticism.