The synthesis and electronic structure of a novel [NiS4Fe2(CO)(6)] radical cluster: Implications for the active site of the [NiFe] hydrogenases

A novel [Ni'S-4'Fe-2(CO)(6)] cluster (1: 'S-4'=(CH3C6H3S2)(2)(CH2)(3)) has been synthesised, structurally characterised and has been shown to undergo a chemically reversible reduction process at -1.31 V versus Fc(+)/Fc to generate the EPR-active monoanion 1(-). Multifrequency Q-, X- and S-band EPR spectra of Ni-61-enriched 1(-) show a well-resolved quartet hyperfine splitting in the low-field region due to the interaction with a single Ni-61 (I = 3/2) nucleus. Simulations of the EPR spectra require the introduction of a single angle of non-coincidence between g, and A(1), and g(3) and A(3) to reproduce all of the features in the S- and X-band spectra. This behaviour provides a rare example of the detection and measurement of non-coincidence effects from frozen-solution EPR spectra without the need for single-crystal measurements, and in which the S-band experiment is sensitive to the non-coincidence. An analysis of the EPR spectra of 1(-) reveals a 24% Ni contribution to the SOMO in 1(-), supporting a delocalisation of the spin-density across the NiFe2 cluster. This observation is supported by IR spectroscopic results which show that the CO stretching frequencies, v(CO), shift to lower frequency by about 70 cm(-1) when 1 is reduced to 1(-). Density functional calculations provide a framework for the interpretation of the spectroscopic properties of 1(-) and suggest that the SOMO is delocalised over the whole cluster, but with little S-centre participation. This electronic structure contrasts with that of the Ni-A, -B, -C and -L forms of [NiFe] hydrogenase in which there is considerable S participation in the SOMO.

Magnetic and electronic structure of TICo2S2

An extensive investigation of the ferromagnetic compound TlCo2S2 has resulted in new information on the electronic and magnetic structure. Electronic structure calculations showed that magnetic ordering is energetically favorable with a clear driving force for ferromagnetic coupling within the cobalt layers. TlCo2S2 is metallic and the conductivity is due to holes in the valence band. XPS single crystal measurements did not show evidence of mixed oxidation states of cobalt. Neutron powder diffraction resulted in a ferromagnetic structure with the magnetic moment in the ab-plane. The derived magnetic moment of the cobalt atom is 0.65(2) mu(B) at 10 K and is in very good agreement with the value, mu(sat) = 0.65(1) mu(B) at 10 K, inferred from the magnetic hysteresis curve. (C) 2004 Elsevier Inc. All rights reserved.

Early Cinema and Oklahoma

This article provides the first history of early cinema in the territory and (from 1907) US state of Oklahoma. It covers the origins and proliferation of fiction and nonfiction filmmaking, paying particular attention to the various films produced at the 101 Ranch and the Pawnee Bill Ranch. It also covers the beginnings of newsreel footage in the state. The article also delves into the issues of film exhibition in Oklahoma, ranging from the earliest film screenings to the nickelodeon era, and also provides a history of efforts towards censorship in the pre-1915 era.

Structural and electronic properties of Ce overlayers and low-dimensional Pt-Ce alloys on Pt{111}

The structural, thermal, chemisorptive, and electronic properties of Ce on Pt{111} are studied by photoemission, Auger spectroscopy, scanning tunnel microscope (STM), and low-energy electron diffraction (LEED). Stranski-Krastanov-like growth of low-density Ce layers is accompanied by substantial valence charge transfer from Ce to Pt: in line with this, the measured dipole moment and polarizability of adsorbed Ce at low coverages are 7.2 x 10(-30) C m and similar to 1.3x10(-29) m(3), respectively. Pt-Ce intermixing commences at similar to 400 K and with increasing temperature a sequence of five different ordered surface alloys evolves. The symmetry, periodicities, and rotational epitaxy observed by LEED are in good accord with the STM data which reveal the true complexity of the system. The Various bimetallic surface phases are based on growth of crystalline Pt5Ce, a hexagonal layer structure consisting of alternating layers of Pt2Ce and Kagome nets of Pt atoms. This characteristic ABAB layered arrangement of the surface alloys is clearly imaged, and chemisorption data permit a distinction to be made between the more reactive Pt2Ce layer and the less reactive Pt Kagome net. Either type of layer can appear at the surface as the terminating structure, thicker films exhibiting unit mesh parameters characteristic of the bulk alloy.

Post-Conflict Performance, Film and Visual Arts:Cities of Memory

This book examines how contemporary theatre, performance, film and the visual arts respond to the post-conflict condition. The contents of the volume focus on a range of post-conflict cities, encouraging interdisciplinary discussion on the role of the arts and its relation to issues of testimony, witnessing, forgetting, representation, healing, reconciliation, agency, and metaphor. Contributors include: Thomas Elsaesser, Jane Taylor, Marvin Carlson, Rob Stone, Laurel Borisenko, Katarzyna Puzon, Miriam Paeslack, Emma Grey, Paula Blair, Zoran Poposki, Marija Todorova, Elena Carduro, and Paul Devlin.

‘Connected communities, “answerability” and the arts: a case study'

This co-authored essay outlines and analyses the AHRC 'Creative Interruptions' Project, 'Where do I belong?', a theatre-as-research project conducted with Afghan refugees in London under the guidance of PI Sarita Malik, Brunel University London.

Development and testing of an intermediate temperature glass sealant for use in mixed ionic and electronic conducting membrane reactors

High temperature ceramic membranes have interesting possibilities for application in areas of new and developing technologies such as hydrocarbon combustion with carbon dioxide capture and electrochemical promotion of catalysis (EPOC). However, membrane module sealing remains a significant technical challenge. In this work a borosilicate glass sealant (50SiO₂·25B₂O₃·25Na₂O, mol%) was developed to fit the requirements of sealing an air separation membrane system at intermediate temperatures (300-600 °C). The seal was assessed by testing the leak rates under a range of conditions. The parameters tested included the effect of flowrate on the leak rate, the heating and cooling rates of the reactor and the range of temperatures under which the system could operate. Tests for durability and reliability were also performed. It was found that the most favourable reactor configuration employed a reactor with the ceramic pellet placed underneath the inner chamber alumina tube (inverted configuration), using a quartz wool support to keep the membrane in place prior to sealing. Using this configuration the new glass-based seal was found to be a more suitable sealant than traditional alternatives; it produced lower leak rates at all desirable flowrates, with the potential for rapid heating and cooling and multiple cycling, allowing for prolonged usage. © 2010 Elsevier B.V. All rights reserved.

Civic engagement and the arts and humanities: a UK perspective

Higher education in the UK is in a state of flux and this is having particular impact on the humanities. On the one hand the pressure to support a STEM agenda is seen by some as forcing higher education down a narrow economic agenda, while government requirements for assessing the social and economic impact of research has raised concerns about excessive utilitarianism and a downgrading of ‘disinterested enquiry’. This paper argues that these concerns may be misplaced. The research impact agenda has the potential to promote more socially engaged research and more democratic engagement in the creation and dissemination of knowledge. In the US concerns about the democratic role of higher education more often seem to focus on the student experience. By contrast, in the UK concerns about citizenship education and democratic participation more often focus on high school students, perhaps because university students are more likely to have a formal role in institutional governance. The paper concludes that the papers in this forum have a very American feel, but the issues they address resonate on a much wider scale.

Two Trilogies:On Stewart Parker and Tom Murphy

This chapter discusses the relations between Irish cinema and the other arts- chiefly, literature, theatre, painting, and photography. It provides a critical overview of the main scholarly approaches to those forms of adaptation and citation that have tended to dominate Irish film production. It argues that factors such as the historic marginalization of non-literary modernist art in Ireland, a deep cultural resistance to intellectual and politically-engaged filmmaking, and a commercially-driven attachment to formulaic narrative structures, are among the reasons why Ireland has generally failed to produce a distinctive and successful cinema. The chapter concludes by discussing some films that have resisted this trend by offering their audiences a more creative approach to -- or poetics of -- adaptation that has more in common with the visual -- rather than literary -- arts in Ireland.

Voyage(s) to Sarajevo: Jean-Luc Godard and the Image of War

This essay discusses Jean-Luc Godard’s artistic response to the Bosnian War (1992-95), and its representations in the Western mass media. For Godard, the reluctance of Europe’s advanced liberal democracies to intervene meaningfully in Bosnia – their insistence that 'humanitarianism' rather than protective intervention was the order of the day – was tantamount to supporting Serbian fascism, and – a fortiori – regressing to a policy of appeasement reminiscent of the days of the Munich Agreement. Although Godard's stance set him against some of his former compatriots on the left, speculating on his ideological motivations is beside the point. Rather, it is is in his filmmaking, in his vision of cinema, and how it relates to other histories of the image, that Godard’s sensibility can be most keenly felt and understood. As the essay points out, even his recent contribution to Jean-Michel Frodon's compilation film, Bridges of Sarajevo/Les ponts de Sarajevo (2014, 114 mn.), persists in posing questions about how the past continues to shape the present, and how Sarajevo and its contemporary history still delineates the identity of Europe.