Simultaneous bridge-localized and mixed-valence character in diruthenium radical cations featuring diethynylaromatic bridging ligands

A series of bimetallic ruthenium complexes [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)] featuring diethynylaromatic bridging ligands (Ar = 1,4-phenylene, 1,4-naphthylene, 9,10-anthrylene) have been prepared and some representative molecular structures determined. A combination of UV–vis–NIR and IR spectroelectrochemical methods and density functional theory (DFT) have been used to demonstrate that one-electron oxidation of compounds [{Ru(dppe)Cp*}2(μ-C≡CArC≡C)](HC≡CArC≡CH = 1,4-diethynylbenzene; 1,4-diethynyl-2,5-dimethoxybenzene; 1,4-diethynylnaphthalene; 9,10-diethynylanthracene) yields solutions containing radical cations that exhibit characteristics of both oxidation of the diethynylaromatic portion of the bridge, and a mixed-valence state. The simultaneous population of bridge-oxidized and mixed-valence states is likely related to a number of factors, including orientation of the plane of the aromatic portion of the bridging ligand with respect to the metal d-orbitals of appropriate π-symmetry.

Self, role and character: developing a professional identity as a drama teacher

The paper reports on research into what may have influenced trainees on four post-graduate teacher training courses in England to become specialist drama teachers rather than pursue careers in the world of professional entertainment. In doing so it raises questions regarding the value of considering teaching as a performing art. The paper goes on to explore how drama trainees regard an understanding of performance, and an ability to both use and demonstrate performance techniques, as integral to their role as subject specialists. The subsequent discussion examines how a drama teacher’s professional identity may be seen as being made up of the three inter-connected elements, self, role and character. Thus, while all teaching may be considered to involve some elements of performativity , this paper suggests that, for the drama specialist, an understanding of what constitutes ‘performance’ has a particular importance. One conclusion drawn from the research is that recognising the place of performance in their practice may result in experienced teachers of drama regarding themselves as artists whose art is teaching drama; another is that recognising the different ways in which adopting a role may involve performance could be of value to all teachers and teacher educators.

(Re)enchanting geography? The nature of being critical and the character of critique in human geography

Enchantment is a term frequently used by human geographers to express delight, wonder or that which cannot be simply explained. However, it is a concept that has yet to be subject to sustained critique, specifically how it can be used to progress geographic thought and praxis. This paper makes sense of, and space for, the unintelligibility of enchantment in order to encourage a less repressed, more cheerful way of engaging with the geographies of the world. We track back through our disciplinary heritage to explore how geographers have employed enchantment as a force through which the world inspires affective attachment. We review the terrain of the debate surrounding recent geographical engagements with enchantment, focusing on the nature of being critical and the character of critique in human geography, offering a new ‘enchanted’ stance to our geographical endeavours. We argue that the moment of enchantment has not passed with the current challenging climate; if anything, it is more pressing.

Late-Holocene changes in character and behaviour of land-terminating glaciers on James Ross Island, Antarctica

Virtually no information is available on the response of land-terminating Antarctic Peninsula glaciers to climate change on a centennial timescale. This paper analyses the topography, geomorphology and sedimentology of prominent moraines on James Ross Island, Antarctica, to determine geometric changes and to interpret glacier behaviour. The moraines are very likely due to a late-Holocene phase of advance and featured (1) shearing and thrusting within the snout, (2) shearing and deformation of basal sediment, (3) more supraglacial debris than at present and (4) short distances of sediment transport. Retreat of ∼100 m and thinning of 15–20 m has produced a loss of 0.1 km3 of ice. The pattern of surface lowering is asymmetric. These geometrical changes are suggested most simply to be due to a net negative mass balance caused by a drier climate. Comparisons of the moraines with the current glaciological surface structure of the glaciers permits speculation of a transition from a polythermal to a cold-based thermal regime. Small land-terminating glaciers in the northern Antarctic Peninsula region could be cooling despite a warming climate.

Bridge-localized HOMO-binding character of divinylanthracene-bridged dinuclear ruthenium carbonyl complexes: spectroscopic, spectroelectrochemical, and computational studies

The electronic properties of four divinylanthracene-bridged diruthenium carbonyl complexes [{RuCl(CO)(PMe3)3}2(μ[BOND]CH[DOUBLE BOND]CHArCH[DOUBLE BOND]CH)] (Ar=9,10-anthracene (1), 1,5-anthracene (2), 2,6-anthracene (3), 1,8-anthracene (4)) obtained by molecular spectroscopic methods (IR, UV/Vis/near-IR, and EPR spectroscopy) and DFT calculations are reported. IR spectroelectrochemical studies have revealed that these complexes are first oxidized at the noninnocent bridging ligand, which is in line with the very small ν(C[TRIPLE BOND]O) wavenumber shift that accompanies this process and also supported by DFT calculations. Because of poor conjugation in complex 1, except oxidized 1+, the electronic absorption spectra of complexes 2+, 3+, and 4+ all display the characteristic near-IR band envelopes that have been deconvoluted into three Gaussian sub-bands. Two of the sub-bands belong mainly to metal-to-ligand charge-transfer (MLCT) transitions according to results from time-dependent DFT calculations. EPR spectroscopy of chemically generated 1+–4+ proves largely ligand-centered spin density, again in accordance with IR spectra and DFT calculations results.

Impact of chronic neonicotinoid exposure on honeybee colony performance and queen supersedure

BACKGROUND: Honeybees provide economically and ecologically vital pollination services to crops and wild plants. During the last decade elevated colony losses have been documented in Europe and North America. Despite growing consensus on the involvement of multiple causal factors, the underlying interactions impacting on honeybee health and colony failure are not fully resolved. Parasites and pathogens are among the main candidates, but sublethal exposure to widespread agricultural pesticides may also affect bees. METHODOLOGY/PRINCIPAL FINDINGS: To investigate effects of sublethal dietary neonicotinoid exposure on honeybee colony performance, a fully crossed experimental design was implemented using 24 colonies, including sister-queens from two different strains, and experimental in-hive pollen feeding with or without environmentally relevant concentrations of thiamethoxam and clothianidin. Honeybee colonies chronically exposed to both neonicotinoids over two brood cycles exhibited decreased performance in the short-term resulting in declining numbers of adult bees (-28%) and brood (-13%), as well as a reduction in honey production (-29%) and pollen collections (-19%), but colonies recovered in the medium-term and overwintered successfully. However, significantly decelerated growth of neonicotinoid-exposed colonies during the following spring was associated with queen failure, revealing previously undocumented long-term impacts of neonicotinoids: queen supersedure was observed for 60% of the neonicotinoid-exposed colonies within a one year period, but not for control colonies. Linked to this, neonicotinoid exposure was significantly associated with a reduced propensity to swarm during the next spring. Both short-term and long-term effects of neonicotinoids on colony performance were significantly influenced by the honeybees' genetic background. CONCLUSIONS/SIGNIFICANCE: Sublethal neonicotinoid exposure did not provoke increased winter losses. Yet, significant detrimental short and long-term impacts on colony performance and queen fate suggest that neonicotinoids may contribute to colony weakening in a complex manner. Further, we highlight the importance of the genetic basis of neonicotinoid susceptibility in honeybees which can vary substantially.

The Vida of Queen Fredegund in Tote Listoire de France: vernacular translation and genre in thirteenth-century French and Occitan literature

This article examines the role that translation may have played in the development of medieval vernacular literature. It analyses an extract of an early 13th-c. translation into a hybrid French-Occitan vernacular of an 8th-c. historical text, the 'Liber Historiae Francorum'. The translation coincides with the adoption of narrative prose both in Old French and in Occitan literature, which reflects a growing interest in historical writings. The second half of the article compares the anecdote with the narrative structures and content of one of the troubadour 'vidas' and 'razos' - biographical texts in prose that emerged in the same period and regions as this translation. The article concludes by suggesting that the new vernacular genre shares narrative features with the early medieval Latin text that are preserved in its translation.

The multidimensional character of accounting numbers

This paper takes as its motivation debates surrounding the multiplicity of functions of accounting information. We are in particular interested in the existential function of accounting numbers and argue that numerical signs having discursive possibilities may acquire new meanings through reframing. Drawing on Goffman’s (1974) frame analysis and Vollmer’s (2007) work on three-dimensional character of numerical signs, we explore the ways in which numbers can go through instantaneous transformations and tell a new kind of story. In our analysis, we look at the main historical developments and current controversies surrounding accounting practice with a specific focus on scandals involving numerical signs as moments where our understandings and the discursive function of previously inoffensive signs shifts through a collective involvement. We map the purpose and usefulness of Vollmer’s three-dimensional framework in the analysis of selected financial accounting practices and scandals as examples of instances where numbers are reframed to suddenly perform a different existential function in context of their calculative and symptomatic dimensions.

The “Great Queen of Lightninge Flashes”: the transmission of female-voiced burlesque poetry in the early seventeenth century

The essay uncovers evidence for the construction of the ‘woman author’ in the largely male vogue for bawdy burlesque poetry by tracing the circulation of a pair of verses through seventeenth-century manuscript and print miscellanies. It argues that just as these verses are reworked and recontextualised through the process of transmission, so to their ‘authors’ are re-embodied and ascribed different identities in different publication contexts. Female-voiced bawdy poetry raises particular problems for authorial attribution, rather than searching for the real woman behind the text, the essay examines how the ‘authors’ of female-voiced bawdy poetry were produced and reproduced through shifting formal frameworks and socioliterary networks.