TIME-RESOLVED ABSORPTION, INFRARED, AND RESONANCE RAMAN-SPECTRA OF THE COMPLEXES [RU(X)(R)(CO)(2)(ALPHA-DIIMINE)] (X=HALIDE R=ALKYL) - INFLUENCE OF X ON THE CHARGE-TRANSFER CHARACTER OF THE LOWEST EXCITED-STATE

Nanosecond time-resolved absorption (TA), resonance Raman (TR(3)), and infrared (TRIR) spectra are reported for several complexes [Ru(X)(R)(CO)(2)(alpha-diimine)] (X = Cl, Br, I; R = Me, Et; alpha-diimine = N,N'-diisopropyl-1,4-diaza-1,3-butadiene (iPr-DAB), pyridine-2-carbaldehyde-N-isopropylimine (iPr-PyCa), 2,2'-bipyridine (bpy)). This is the first instance in which the TA, TR(3), and TRIR techniques have been used to probe excited states in the same series of complexes. The TA spectra of the iodide complexes show a transient absorption between 550 and 700 nm, which does not depend on the solvent but shifts to lower energy in the order iPr-DAB > bpy > iPr-PyCa. This band is assigned to an intraligand transition. For the corresponding chloride and bromide complexes this band occurs at higher energy, most probably because of a change of character of the lowest excited state from XLCT to MLCT. The TRIR spectra show an increase in v(CO) (and k(CO)) on promotion to the excited state; however, the shifts Delta v(CO) show a decrease in the order Cl- > Br- > I-. The TR(3) spectra of the excited complexes [Ru(X)(R)(Co)(2)(iPr-DAB)] show v(s)(CN) of the iPr-DAB ligand 50-80 cm(-1) lower in frequency than for the complexes in their ground state. This frequency shift decreases in the order Cl- > Br- > I-, indicating a decrease of CT character of the lowest excited state in this order. However, going from X = Br to I, the effect on Delta v(CO) is much larger than the decrease of Delta v(s)(CN). This different effect on the CO- and CN-stretching frequencies is assigned to a gradual change in character of the lowest excited state from MLCT to XLCT when Cl- is replaced by Br- and I-. This result confirms a similar conclusion derived from previous resonance Raman and emission experiments on these complexes.

Probing The effects of Experimental Conditions on the Character of Drug-Polymer Phase Diagrams Constructed Using Flory-Huggins Theory

Purpose: Amorphous drug-polymer solid dispersions have been found to result in improved drug dissolution rates when compared to their crystalline counterparts. However, when the drug exists in the amorphous form it will possess a higher Gibb’s free energy than its associated crystalline state and can recrystallize. Drug-polymer phase diagrams constructed through the application of the Flory Huggins (F-H) theory contain a wealth of information regarding thermodynamic and kinetic stability of the amorphous drug-polymer system. This study was aimed to evaluate the effects of various experimental conditions on the solubility and miscibility detections of drug-polymer binary system. Methods: Felodipine (FD)-Polyvinylpyrrolidone (PVP) K15 (PVPK15) and FD-Polyvinylpyrrolidone/vinyl acetate (PVP/VA64) were the selected systems for this research. Physical mixtures with different drug loadings were mixed and ball milled. These samples were then processed using Differential Scanning Calorimetry (DSC) and measurements of melting point (Tend) and glass transition (Tg) were detected using heating rates of 0.5, 1.0 and 5.0°C/min. Results: The melting point depression data was then used to calculate the F-H interaction parameter (χ) and extrapolated to lower temperatures to complete the liquid–solid transition curves. The theoretical binodal and spinodal curves were also constructed which were used to identify regions within the phase diagram. The effects of polymer selection, DSC heating rate, time above parent polymer Tg and polymer molecular weight were investigated by identifying amorphous drug miscibility limits at pharmaceutically relevant temperatures. Conclusion: The potential implications of these findings when applied to a non-ambient processing method such as Hot Melt Extrusion (HME) are also discussed.

The conserved Helix C region in the superfamily of interferon-a/interleukin-10-related cytokines corresponds to a high-affinity binding site for the HSP70 chaperone DnaK.

HSP70 chaperones mediate protein folding by ATP-dependent interaction with short linear peptide segments that are exposed on unfolded proteins. The mode of action of the Escherichia coli homolog DnaK is representative of all HSP70 chaperones, including the endoplasmic reticulum variant BiP/GRP78. DnaK has been shown to be effective in assisting refolding of a wide variety of prokaryotic and eukaryotic proteins, including the -helical homodimeric secretory cytokine interferon- (IFN-). We screened solid-phase peptide libraries from human and mouse IFN- to identify DnaK-binding sites. Conserved DnaK-binding sites were identified in the N-terminal half of helix B and in the C-terminal half of helix C, both of which are located at the IFN- dimer interface. Soluble peptides derived from helices B and C bound DnaK with high affinity in competition assays. No DnaK-binding sites were found in the loops connecting the -helices. The helix C DnaK-binding site appears to be conserved in most members of the superfamily of interleukin (IL)-10-related cytokines that comprises, apart from IL-10 and IFN-, a series of recently discovered small secretory proteins, including IL-19, IL-20, IL-22/IL-TIF, IL-24/MDA-7 (melanoma differentiation-associated gene), IL-26/AK155, and a number of viral IL-10 homologs. These cytokines belong to a relatively small group of homodimeric proteins with highly interdigitated interfaces that exhibit the strongly hydrophobic character of the interior core of a single-chain folded domain. We propose that binding of DnaK to helix C in the superfamily of IL-10-related cytokines may constitute the hallmark of a novel conserved regulatory mechanism in which HSP70-like chaperones assist in the formation of a hydrophobic dimeric "folding" interface.

Risk versus National Pride. Conflicting discourses over the construction of a High Voltage Power Station in the Athens Metropolitan Area for demands of the 2004 Olympics

This paper first explores the conflictual discourses employed by government agencies, citizens’ initiatives, and environmental organizations over the construction of a High Voltage Power Station (KYT) for demands of the 2004 Olympic Games, as presented in media reports and movement literature over a period of one year. Having in mind recent criticisms targeting the lack of empirical evidence in Ulrich Beck’s risk theorization, this exploration is of distinct importance. Secondly, it takes into account that both the defensive character of societal action and mistrust to expert authorities have been confirmed as prevalent characteristics of both the Greek and the general risk social context. The paper attempts to re-evaluate and/or complement existing perspectives of societal activism in general and environmental mobilizations in particular within the confines of the Greek social context. As a tentative conclusion, it is suggested that the risk perspective offers a novel prism for the examination of societal activism without confining it to the characteristics of individual national contexts.

Rambling in the Field of Modern Identity: Some Speculations on Irish Traditional Music

This article argues that Irish “traditional” music is modern in its form and history, and explores the ramifications of this thesis for understanding of the peculiarities of Irish modernity and identity. The article exhaustively surveys the historiography of Irish traditional music and uniquely interprets this literature in relation to competing conceptions of identity and modernity articulated by Taylor, Appiah and Žižek. It also interprets Irish traditional music in relation to conceptions of Irish modernity articulated in a wide range of disciplines within Irish studies. Reflecting on the author’s lifelong engagement with traditional music performance, the article argues that the resilience of traditional music within the broader culture is connected to the peculiar character of Irish modernity, and that it suffers from problems of aesthetic exhaustion shared by much modern art in the contemporary conjuncture.

The Regulation of Public Space in Northern Ireland

The Parades Commission of Northern Ireland was established to regulate the use of public space in the region. Its formal design includes both a role in mediating between groups over how spaces are used and an adjudicative role when agreement between competing groups cannot be reached. We argue that the Parades Commission has only been effective to the degree that its character as a bureaucracy has quelled violence surrounding parades. The Commission's goal of conciliation cannot be attained without a more consistent, transparent and inclusive approach to applying law.

“Hegemony Protected by the Armour of Coercion”: Dashiell Hammett’s Red Harvest and the State

This article argues that Dashiell Hammett's 1929 novel Red Harvest is best understood in the context of the consolidation and expansion of the US state following the First World War and the Russian Revolution. It also argues that Hammett's novel constitutes a highly significant articulation of theoretical debates about the nature of political authority and state power in the modern era and speaks about the transition of one state formation to another. Insofar as Red Harvest explores the way in which the state's coercive and ethical character are bound up together, this article argues that Hammett's novel draws upon an understanding of political authority and state power primarily derived from Gramsci, via Marx. Gramsci insists that control cannot be maintained through force alone (and his conception of hegemony, in turn, suggests a power bloc that can become fragmented and disunited in a war of position). In the same way, Red Harvest traces the transformation of the “economic-corporate” state into the expanded or “ethical” State but crucially any ethical dimension, as Gramsci notes, is always beholden to the needs of the capitalist economy. As such, the apparently arbitrary bloodshed in the novel is conceived as a relatively minor realignment in the ranks of the capitalist classes – certainly less serious than the miners' strike that prefigures the novel. What makes this realignment significant is that it calls attention to the state both as repressive and as a site of conflict and compromise. Here, the work performed by the Continental Op and by the crime novel in general – simultaneously buttressing and, to some extent, contesting the power of the state – needs to be understood as part of the process by which the state is consistently enacting hegemony (albeit protected by the armour of coercion). The article concludes by pointing out that while Gramsci is perhaps too willing to dwell upon the state's expanded reach, Red Harvest is more interested in examining possible “cracks and fissures” in the state formation, even if the critique it ultimately offers goes nowhere and yields nothing.

Influence of the Graphical Levels of Detail of a Virtual Thrower on the Perception of the Movement

Virtual reality has a number of advantages for analyzing sports interactions such as the standardization of experimental conditions, stereoscopic vision, and complete control of animated humanoid movement. Nevertheless, in order to be useful for sports applications, accurate perception of simulated movement in the virtual sports environment is essential. This perception depends on parameters of the synthetic character such as the number of degrees of freedom of its skeleton or the levels of detail (LOD) of its graphical representation. This study focuses on the influence of this latter parameter on the perception of the movement. In order to evaluate it, this study analyzes the judgments of immersed handball goalkeepers that play against a graphically modified virtual thrower. Five graphical representations of the throwing action were defined: a textured reference level (L0), a nontextured level (L1), a wire-frame level (L2), a moving point light display (MLD) level with a normal-sized ball (L3), and a MLD level where the ball is represented by a point of light (L4). The results show that judgments made by goalkeepers in the L4 condition are significantly less accurate than in all the other conditions (p

The Liedertheater of Wenzel and Mensching: Subversive Use of the Agitprop and Clowning Tradition in the GDR

The East German poet-clowns Hans-Eckardt Wenzel and Steffen Mensching rose to prominence during the GDR's (German Democratic Republic; Deutsche Demokratische Republik, DDR) Peaceful Revolution of autumn 1989 with their cabaret production Letztes aus der Da Da eR. A film adaptation of the production was made by Jörg Foth in 1990, which was finally released on DVD with English subtitles in the United Kingdom and North America in 2009 (Latest from the Da-Da-R). In light of this long-overdue interest in Wenzel & Mensching, this article will attempt to put the work of the duo in historical and aesthetic context. Their use of character, masks, music, and philosophy combined to create the distinctly grotesque world that constituted their Liedertheater performances.

Exploitation of inherited weakness in fire-damaged building sandstone: the ‘fatiguing’ of ‘shocked’ stone

The problem of the long-term impact of historical fire on masonry is not clearly understood. Much research focuses on the damage that is caused by fire in isolation, and omits to investigate the subsequent exploitation of weaknesses inherited from fire events. Fire can, for example, cause significant physical, chemical and mineralogical change to sandstone, which may then be exploited by background environmental factors such as salt and freeze–thaw weathering. To explore this experimentally, blocks of Peakmoor Sandstone were subjected to a real fire (as well as lime rendering/removal and frost cycle pre-treatments), and their subsequent response to salt weathering cycles was monitored by weight loss and visual assessment of the pattern of surface damage. Results illustrate that the post-fire deterioration of sandstone is strongly conditioned by fracture networks and soot cover inherited from the fire. The exploitation of fractures can lead to spalling during salt weathering cycles — this takes place as granular dissagregation steadily widens cracks and salts concentrate and crystallise in areas of inherited weakness. Soot cover can have a profound effect on subsequent performance. It reduces surface permeability and can be hydrophobic in character, limiting salt ingress and suppressing decay in the short term. However, as salt crystals concentrate under the soot crust, detachment of this layer can occur, exposing fire-damaged stone beneath. Understanding the subsequent exploitation of stone exposed to fire damage by background environmental factors (for example, salt weathering/ temperature cycling) is key to the post-fire management of stone decay.

The Right to Self-Defence in National and International Law: The Role of the Imminence Requirement

This article explores the doctrine of self-defence within the context of the challenges directed at the imminence requirement, from the perspective of both national and international law. The article will attempt to illustrate that the requirement of imminence underlines the political character of the self-defence doctrine wherein private force may only be resorted to in the absence of institutional protection. This study will argue that the imminence rule can not merely be regarded as a "proxy" for establishing necessity; rather, the elements of imminence, necessity, and proportionality are inextricably connected to ensure that defensive force is only resorted to when national or international authorities are not in a position to prevent an illegal aggression, and that the defensive lethal force is not abused.