Electrochemical, spectrophotometric, electroanalytical and electrochemical quartz crystal microbalance studies of some redox-active films

Redox films are a broad class of electrochemically active films with many potential uses. In the present work, Prussian Blue and carbon coated electrodes have been investigated as possible electrochemical sensors for ascorbic acid and pH, respectively. The potential of Prussian Blue as an optical sensor has also been investigated. In the case of Prussian Blue, it has been discovered that up to 100 monolayers can be systematically deposited on gold electrodes by a new technique that we have called "directed assembly". This provides control of layer thickness with nanometer precision. In the case of carbon coated electrodes, we have developed a mechanical coating technique for quartz crystals, which allows them to be used in electrochemical cells, simultaneously as working electrodes and as mass sensors in a quartz crystal microbalance. This opens up the possibility of developing a variety of new sensor technologies, including pH-sensitive microelectrodes

Critical behavior of gravitating sphalerons

We examine the gravitational collapse of sphaleron type configurations in Einstein--Yang--Mills--Higgs theory. Working in spherical symmetry, we investigate the critical behavior in this model. We provide evidence that for various initial configurations, there can be three different critical transitions between possible endstates with different critical solutions sitting on the threshold between these outcomes. In addition, we show that within the dispersive and black hole regimes, there are new possible endstates, namely a stable, regular sphaleron and a stable, hairy black hole.Comment: Latex, 14 pages, 8 figure

The Millstone Grit Group (Pennsylvanian) of the Northumberland-Solway Basin and Alston Block of northern England

In the Northumberland–Solway Basin and Alston Block of northern England, some aspects of the stratigraphical and sedimentological relationships between the Millstone Grit Group, the Stainmore Formation (Namurian part of the Yoredale Group) and the Westphalian Pennine Coal Measures Group are uncertain. Also, confusion has resulted from discontinuation of Millstone Grit as a formal lithostratigraphical term north of the Stainmore Basin. This paper presents the evidence for, and describes the nature of, a Kinderscoutian (early Pennsylvanian) abrupt transition from typical ‘Yoredale cyclicity’, characterized by marine limestones in a dominantly siliciclastic succession but including marked fluvial channels, to a sandstone-dominated fluvial succession recognizable as the Millstone Grit Group. Sandbodies present in this region are probably the fluvial feeder systems to many of the fluvio-deltaic successions recorded farther south in the Central Pennine Basin. However, onset of the Millstone Grit Group occurs much earlier to the south, during the Pendleian (late Mississippian), despite the entry of fluvial systems into the Central Pennines Basin from the north. In addition to explaining this counter-intuitive relationship, the paper also recognizes continuation of the fluvial regime into the lowermost part of the Pennine Coal Measures Group

The direct electrochemistry of ferritin compared with the direct electrochemistry of nanoparticulate hydrous ferric oxide

Horse spleen ferritin is a naturally occurring iron storage protein, consisting of a protein shell encapsulating a hydrous ferric oxide core about 8 nm in diameter. It is known from prior work that the protein can be adsorbed onto the surface of tin-doped indium oxide (ITO) electrodes, where it undergoes voltammetric reduction at about –0.6 V vs Ag/AgCl. This is accompanied by dissolution of Fe(II) through channels in the protein shell. In the present work, it is demonstrated that a pre-wave at about –0.4 V vs Ag/AgCl is due to the reduction of FePO4 also present inside the protein shell. In order to prove that the pre-wave was due to the reduction of FePO4, it was first necessary to prepare 8 nm diameter hydrous ferric oxide nanoparticles without protein shells, adsorb them onto ITO electrodes, and then study their electrochemistry. Having achieved that, it was then necessary to establish that their behaviour was analogous to that of ferritin. This was achieved in several ways, but principally by noting that the same electrochemical reduction reactions occurred at negative potentials, accompanied by the dissolution of Fe(II). Finally, by switching to aqueous phosphate buffer, the pre-wave could be unambiguously identified as the reduction of FePO4 present as a thin layer on the hydrous ferric oxide nanoparticle surfaces. Although the bare and protein-coated hydrous ferric oxide nanoparticles were found to behave identically toward electrochemical reduction, they nevertheless reacted very differently towards H2O2. The bare nanoparticles acted as potent electrocatalysts for both the oxidation and the reduction of H2O2, whereas the horse spleen ferritin had a much lesser effect. It seems likely therefore that the protein shell in ferritin blocks the formation of key intermediates in hydrogen peroxide decomposition

The legacy of social anxiety-linked negative expectancy: A pathway from pre-event negative expectancies to post-event negative thinking

This is the final version. Available from Elsevier via the DOI in this record. Repository: Materials, data, and analysis outputs described in this manuscript are available at https://osf.io/sghuj/Background and objectives: Following engagement in a social event people with heightened vulnerability to social anxiety report elevated levels of negative thinking about the event, and this post-event negative thinking is implicated in the maintenance of social anxiety vulnerability. It has also been established that heightened social anxiety vulnerability is associated with disproportionately negative expectations of upcoming social events. However, contribution of social anxiety-linked pre-event negative expectancy to post-event negative thinking has not been directly investigated. The objective of the present study was to test the hypothesis that the relationship between social anxiety vulnerability and post-event negative thinking is mediated by pre-event negative expectancies that drive increased state anxiety at the time of encountering the event. Methods: One-hundred and ten participants who varied in social anxiety vulnerability completed a simulated job interview. Participants reported negativity of expectancies before the event, state anxiety experienced at the time of encountering the event, and post-event negative thinking across the seven days following the event. Results: Analyses revealed elevated social anxiety predicted increased negative post-event thinking. The association between social anxiety and post-event negative thinking was fully mediated by a mediation pathway involving pre-event negative expectancies and state anxiety at the time of encountering the interview event. Limitations: The study used a laboratory-based social experience, and conclusions could usefully be tested in the context of natural social events. Conclusions: The findings suggest that social anxiety-linked variation in pre-event negative expectancy may contribute to post-event negative thinking following a social event via its impact on state anxiety.Australian Research Counci

Role of serum vascular endothelial growth factor (VEGF) as a potential biomarker of response to immune checkpoint inhibitor therapy in advanced melanoma: results of a pilot study

Background: The development of biomarkers predictive of response to immune checkpoint inhibitor (ICI) therapies in advanced melanoma is an area of great interest in oncology. Our study evaluated the potential role of serum vascular endothelial growth factor (VEGF) as a predictive biomarker of clinical benefit and response to treatment with ICIs. Methods: Pre-treatment peripheral blood samples were obtained from advanced melanoma patients undergoing ICI therapy as monotherapy or in combination at two tertiary care hospitals in Western Australia. Serum VEGF levels were correlated with response to therapy and survival outcomes. Results: Serum VEGF samples were collected from a total of 130 patients treated with ICI therapy (pembrolizumab 73, ipilimumab 15, and ipilimumab/nivolumab combination 42). Median serum VEGF level was significantly higher in the non-responders (82.15 pg/mL) vs. responders (60.40 pg/mL) in the ipilimumab monotherapy cohort (P \u3c 0.0352). However, no difference was seen in VEGF levels between non-responders and responders in pembrolizumab and ipilimumab/nivolumab treated patients. Conclusions: The results of our study confirm previous observations that that high pre-treatment serum VEGF levels in advanced melanoma patients may predict poor response to ipilimumab. However, serum VEGF is not predictive of outcome in patients treated with anti-PD-1 agents alone or in combination with ipilimumab

On the shopfloor: exploring the impact of teacher trade unions on school-based industrial relations

Teachers are highly unionised workers and their trade unions exert an important influence on the shaping and implementation of educational policy. Despite this importance there is relatively little analysis of the impact of teacher trade unions in educational management literature. Very little empirical research has sought to establish the impact of teacher unions at school level. In an era of devolved management and quasi-markets this omission is significant. New personnel issues continue to emerge at school level and this may well generate increased trade union activity at the workplace. This article explores the extent to which devolved management is drawing school-based union representation into a more prominent role. It argues that whilst there can be significant differences between individual schools, increased school autonomy is raising the profile of trade union activity in the workplace, and this needs to be better reflected in educational management research

Magnetic resonance elastography reveals altered brain viscoelasticity in experimental autoimmune encephalomyelitis

Cerebral magnetic resonance elastography (MRE) measures the viscoelastic properties of brain tissues in vivo. It was recently shown that brain viscoelasticity is reduced in patients with multiple sclerosis (MS), highlighting the potential of cerebral MRE to detect tissue pathology during neuroinflammation. To further investigate the relationship between inflammation and brain viscoelasticity, we applied MRE to a mouse model of MS, experimental autoimmune encephalomyelitis (EAE). EAE was induced and monitored by MRE in a 7-tesla animal MRI scanner over 4 weeks. At the peak of the disease (day 14 after immunization), we detected a significant decrease in both the storage modulus (G') and the loss modulus (G″), indicating that both the elasticity and the viscosity of the brain are reduced during acute inflammation. Interestingly, these parameters normalized at a later time point (day 28) corresponding to the clinical recovery phase. Consistent with this, we observed a clear correlation between viscoelastic tissue alteration and the magnitude of perivascular T cell infiltration at both day 14 and day 28. Hence, acute neuroinflammation is associated with reduced mechanical cohesion of brain tissues. Moreover, the reduction of brain viscoelasticity appears to be a reversible process, which is restored when inflammation resolves. For the first time, our study has demonstrated the applicability of cerebral MRE in EAE, and showed that this novel imaging technology is highly sensitive to early tissue alterations resulting from the inflammatory processes. Thus, MRE may serve to monitor early stages of perivascular immune infiltration during neuroinflammation

The beta Pictoris association: Catalog of photometric rotational periods of low-mass members and candidate members

We intended to compile the most complete catalog of bona fide members and candidate members of the beta Pictoris association, and to measure their rotation periods and basic properties from our own observations, public archives, and exploring the literature. We carried out a multi-observatories campaign to get our own photometric time series and collected all archived public photometric data time series for the stars in our catalog. Each time series was analyzed with the Lomb-Scargle and CLEAN periodograms to search for the stellar rotation periods. We complemented the measured rotational properties with detailed information on multiplicity, membership, and projected rotational velocity available in the literature and discussed star by star. We measured the rotation periods of 112 out of 117 among bona fide members and candidate members of the beta Pictoris association and, whenever possible, we also measured the luminosity, radius, and inclination of the stellar rotation axis. This represents to date the largest catalog of rotation periods of any young loose stellar association. We provided an extensive catalog of rotation periods together with other relevant basic properties useful to explore a number of open issues, such as the causes of spread of rotation periods among coeval stars, evolution of angular momentum, and lithium-rotation connection.Comment: Forthcoming article, Received: 20 June 2016 / Accepted: 09 September 2016; 40 pages, 2 figures. The online figures A1-A73 are available at CD