Synthesis, X-ray Structures, Electronic Properties, and O\u3csub\u3e2\u3c/sub\u3e/NO Reactivities of Thiol Dioxygenase Active-Site Models

Mononuclear non-heme iron complexes that serve as structural and functional mimics of the thiol dioxygenases (TDOs), cysteine dioxygenase (CDO) and cysteamine dioxygenase (ADO), have been prepared and characterized with crystallographic, spectroscopic, kinetic, and computational methods. The high-spin Fe(II) complexes feature the facially coordinating tris(4,5-diphenyl-1-methylimidazol-2-yl)phosphine (Ph2TIP) ligand that replicates the three histidine (3His) triad of the TDO active sites. Further coordination with bidentate l-cysteine ethyl ester (CysOEt) or cysteamine (CysAm) anions yielded five-coordinate (5C) complexes that resemble the substrate-bound forms of CDO and ADO, respectively. Detailed electronic-structure descriptions of the [Fe(Ph2TIP)(LS,N)]BPh4 complexes, where LS,N = CysOEt (1) or CysAm (2), were generated through a combination of spectroscopic techniques [electronic absorption, magnetic circular dichroism (MCD)] and density functional theory (DFT). Complexes 1 and 2 decompose in the presence of O2 to yield the corresponding sulfinic acid (RSO2H) products, thereby emulating the reactivity of the TDO enzymes and related complexes. Rate constants and activation parameters for the dioxygenation reactions were measured and interpreted with the aid of DFT calculations for O2-bound intermediates. Treatment of the TDO models with nitric oxide (NO)—a well-established surrogate of O2—led to a mixture of high-spin and low-spin {FeNO}7 species at low temperature (−70 °C), as indicated by electron paramagnetic resonance (EPR) spectroscopy. At room temperature, these Fe/NO adducts convert to a common species with EPR and infrared (IR) features typical of cationic dinitrosyl iron complexes (DNICs). To complement these results, parallel spectroscopic, computational, and O2/NO reactivity studies were carried out using previously reported TDO models that feature an anionic hydrotris(3-phenyl-5-methyl-pyrazolyl)borate (Ph,MeTp–) ligand. Though the O2 reactivities of the Ph2TIP- and Ph,MeTp-based complexes are quite similar, the supporting ligand perturbs the energies of Fe 3d-based molecular orbitals and modulates Fe–S bond covalency, suggesting possible rationales for the presence of neutral 3His coordination in CDO and ADO

‘Enfer des femmes’: Britain and the Ravensbrück-Hamburg Trials

Between December 1946 and June 1948 a series of seven Trials were conducted by a British Military Court. Known as the Ravensbrück-Hamburg Trials (RHTs), the defendants were former guards, doctors, nurses and prisoner functionaries (Kapos) from Ravensbrück Concentration Camp. These Trials are part of a number of forgotten trials concerning Nazi war crimes. Ravenbrück’s status as the largest women’s Camp during the Second World War means that evidence from the Trials sheds an important light on the experiences of women in concentration camps, as prisoners and perpetrators. This thesis has two aims; firstly to produce a history of the RHTs, unveiling political decisions made by Britain and the Allied powers leading up to and during the Trials. These include decisions that were influenced by the growing Cold War, such as Britain’s refusal to hand Ravesbrück defendant’s to Warsaw in 1946, and the reasons behind the Trials fading from public memory. The second aim is to utilize evidence from the Trials to evaluate the role of Ravensbrück within the wider history of concentration camps, exposing the atrocities that took place therein and sharing the experiences of female prisoners

Continuum Damage Mechanics (CDM) modelling of dislocation creep in 9-12% Cr creep resistant steels

The generation of electricity to meet an ever-growing demand has become a defining characteristic of the modern world for both developed and developing nations alike. This, coupled with the intensifying concern with pollution and its effects on the environment has put immense pressure on how quickly and efficiently power is produced. Being the most prevalent source of electricity generation, coal fired power plants have been subject to increasing scrutiny and study in an effort to improve the efficiency at which they operate. Hence, coal fired power plants are being run at increased temperatures and pressures such as those observed in Super-critical and Ultra-super-critical plants. This has by extension put excessive demand on materials used in these plants specifically within the boiler and superheater pipe sections where the most extreme thermodynamic conditions are experienced. The most commonly used materials for these applications are in the family of ferritic/martensitic 9-12% Cr steels chosen for their superior material properties especially during long-term exposure as coal fired power plants typically operate for over 20 years before being decommissioned. One of the lesser understood aspects of 9-12%Cr steels is with regard to their long-term material properties specifically that of creep degradation and deformation. This has been partially due to the reliance of creep life predictions in the past being based on accelerated creep testing and empirically based modelling. With the relatively recent revelations of empirically based modelling shown to be inaccurate when extrapolated to the long-term, a need has been identified amongst researchers to develop more accurate models based on physical relationships and material microstructure. Moreover, the insight obtained from modern experimental techniques and technologies as well as ever-expanding computing capabilities provide an opportunity to produce microstructurally based models with a high degree of complexity. Thus motivated, the focus of this dissertation was to develop a physically based dislocation creep model using the Continuum Damage Mechanics (CDM) approach. A dislocation CDM model was developed and implemented in the current work for uniaxial creep loading using the numerical modelling software Matlabᵀᴹ. The CDM approach was built upon fundamental dislocation theory as well as other microstructural considerations pertaining to dislocation creep including subgrain coarsening, M₂₃C₆ precipitate coarsening and stress redistribution. The CDM model was found to require calibration in order to be applied to specific 9- 12% Cr steels which was implemented using a parameter optimisation routine. The results obtained were compared with experimentally obtained, long-term creep-time and microstructural data for the 11% Cr steel CB8 and the 9% Cr steel P92. The CDM creep-time predictions were found to vary in accuracy depending upon the experimental data against which the model was calibrated. Upon further investigation, it was hypothesised that the discrepancy observed was due to the formation of the Modified Z-phase in some of the long term creep data but not in others which was based primarily on the differing creep exposure times of the various samples. The CDM creep-time predictions for P92 were found to be accurate when compared with experimental results regardless of creep exposure times. The apparent difference in the approximation of the creep deformation for the two steels was concluded as being due to the formation of the Modified Z-phase in CB8 but not in P92 as Modified Zphase formation is intrinsically linked with the Cr content of the steel

The curious case of Skokholm: equilibrium, non-equilibrium and a phase shift in an island landbird assemblage

Previous work has indicated that the landbirds of Skokholm island (Wales) are not in equilibrium as defined in MacArthur–Wilson's classic theory of island biogeography. This study takes a new dataset with over six decades of data and investigates equilibrium on Skokholm using cluster analysis to identify periods of turnover stability. The attributes of the identified periods were investigated in relation to the MacArthur–Wilson model using analyses of change in numbers of species, S, from one year to the next and measures of variability in S quantified for each of the periods identified together with a consideration of the dynamics in the numbers of species by habitat groupings. Cluster analysis identified four main periods of which two middle periods appeared to be in equilibrium but with a phase shift in-between. The first and last periods showed non-equilibrium dynamics but plots of species by habitat groupings suggested that this was due to habitat changes going on at those times. This decadal long dataset indicates that the landbirds of Skokholm exhibit periods of both equilibrium and non-equilibrium with the latter attributable to habitat change. The apparent phase shift in the equilibrium number of species was unexpected within the framework of island biogeographic theory and not easily explained using the current MacArthur–Wilson framework. There is a need to integrate the theory of island biogeography with more recent work on alternative stable states, tipping points, and phase (or regime) shifts, together with equilibrium and non-equilibrium dynamics, into a single framework

School-based well-being programs for children living in regional and rural Australia:stakeholder views

Children living in regional and rural areas report poorer mental health than metropolitan children, however, there are few, if any, evidence-based school well-being programs tailored for this group. This study aimed to elicit the views of stakeholders about what should be included in well-being programs for these young people and how they should be delivered. Nine online focus groups were conducted with 29 participants including children, teachers, parents/caregivers, school leaders, and school well-being staff. Thematic analysis was conducted, and findings revealed several unique aspects of rural life that should be included in school well-being programs for these communities. These included the losses and isolation experienced in these communities, the cumulative risk and impact of disasters in rural areas, and inadequate access to mental health and support services. The results can be used to justify further investment and delivery of targeted well-being programs for students living in regional and rural locations.</p

Elephants as actors in the political ecology of human–elephant conflict

This paper examines the agency of African elephants as important actors in the political ecology of human-elephant conflict, and in shaping the politics of land in post-colonial Kenya. The paper is based on field research in Laikipia, northern Kenya. It considers the role of elephants, with their size, sagacity, hunger, mobility and complex interactions with people, as powerful actors in shared landscapes, and therefore in the politics surrounding their own conservation. The paper uses spatial data and interviews to explore elephant behaviour and movements through the landscape and their interactions with people, and explore the way in which those interactions affect the separation of ‘animal spaces’ set aside for conservation and the ‘beastly places’ of smallholder farming and crop-raiding, and the conflict and transgressions involved when elephants cross from one to the other. The elephant is a lively actor in the inter-species power play of Laikipia, and the politics of conservation and of land. A mutually respectful multispecies politics in northern Kenya demands a clear understanding and acceptance of the needs of elephants

Bio-Geo-Graphy: Landscape, Dwelling, and the Political Ecology of Human-Elephant Relations

The relation between the bio and the geo has been amongst geography's most enduring concerns. This paper contributes to ongoing attempts in human geography to politicise the dynamics and distribution of life. Drawing upon postcolonial environmental history, animal ecology, and more-than-human geography, the paper examines how humans and elephants cohabit with and against the grain of cartographic design. Through fieldwork in northeast India, it develops a ‘dwelt political ecology’ that reanimates landscape as a dwelt achievement whilst remaining sensitive to postcolonial histories and subaltern concerns. The paper conceptualises and deploys a methodology of ‘tracking’ through which archival material, elephant ecology, and voices of the marginalised can be integrated and mapped. It concludes by discussing the implications of this work for fostering new conversations between more-than-human geography and subaltern political ecology

Sub-lethal exposure to lead is associated with heightened aggression in an urban songbird

Many urban areas have elevated soil lead concentrations due to prior large-scale use of lead in products such as paint and automobile gasoline. This presents a potential problem for the growing numbers of wildlife living in urbanized areas as lead exposure is known to affect multiple physiological systems, including the nervous system, in vertebrate species. In humans and laboratory animals, low-level lead exposure is associated with neurological impairment, but less is known about how lead may affect the behavior of urban wildlife. We focused on the Northern Mockingbird Mimus polyglottos, a common, omnivorous North American songbird, to gain insights into how lead may affect the physiology and behavior of urban wildlife. We predicted that birds living in neighborhoods with high soil lead concentrations would (a) exhibit elevated lead concentrations in their blood and feathers, (b) exhibit lower body condition, (c) exhibit less diverse and consistent vocal repertoires, and (d) behave more aggressively during simulated conspecific territorial intrusions compared to birds living in neighborhoods with lower soil lead concentrations. Controlling for other habitat differences, we found that birds from areas of high soil lead had elevated lead concentrations in blood and feathers, but found no differences in body condition or vocal repertoires. However, birds from high lead areas responded more aggressively during simulated intrusions. These findings indicate that sub-lethal lead exposure may be common among wildlife living in urban areas, and that this exposure is associated with increased aggression. Better understanding of the extent of the relationship between lead exposure and aggression and the consequences this could have for survival and reproduction of wild animals are clear priorities for future work in this and other urban ecosystems

Projecting Land-Use Change and Its Consequences for Biodiversity in Northern Thailand

Rapid deforestation has occurred in northern Thailand over the last few decades and it is expected to continue. The government has implemented conservation policies aimed at maintaining forest cover of 50% or more and promoting agribusiness, forestry, and tourism development in the region. The goal of this paper was to analyze the likely effects of various directions of development on the region. Specific objectives were (1) to forecast land-use change and land-use patterns across the region based on three scenarios, (2) to analyze the consequences for biodiversity, and (3) to identify areas most susceptible to future deforestation and high biodiversity loss. The study combined a dynamic land-use change model (Dyna-CLUE) with a model for biodiversity assessment (GLOBIO3). The Dyna-CLUE model was used to determine the spatial patterns of land-use change for the three scenarios. The methodology developed for the Global Biodiversity Assessment Model framework (GLOBIO 3) was used to estimate biodiversity intactness expressed as the remaining relative mean species abundance (MSA) of the original species relative to their abundance in the primary vegetation. The results revealed that forest cover in 2050 would mainly persist in the west and upper north of the region, which is rugged and not easily accessible. In contrast, the highest deforestation was expected to occur in the lower north. MSA values decreased from 0.52 in 2002 to 0.45, 0.46, and 0.48, respectively, for the three scenarios in 2050. In addition, the estimated area with a high threat to biodiversity (an MSA decrease >0.5) derived from the simulated land-use maps in 2050 was approximately 2.8% of the region for the trend scenario. In contrast, the high-threat areas covered 1.6 and 0.3% of the region for the integrated-management and conservation-oriented scenarios, respectively. Based on the model outcomes, conservation measures were recommended to minimize the impacts of deforestation on biodiversity. The model results indicated that only establishing a fixed percentage of forest was not efficient in conserving biodiversity. Measures aimed at the conservation of locations with high biodiversity values, limited fragmentation, and careful consideration of road expansion in pristine forest areas may be more efficient to achieve biodiversity conservation. © 2010 Springer Science+Business Media, LLC