Comments on the phase diagrams and crystallisation paths of Y-Ba-Cu-O materials

Our micro structural characterisation of Y-Ba-Cu-O quenched partial melts shows that the BaCuO2 (BC1) phase is crystalline at temperatures as high as 1100°C, and that the partial melt self-establishes a micro structural gradient from the surface towards the interior of the samples, which can be associated with a gradient in an equivalent partial pressure of O2 (pO2). The extension of the Y2BaCuO5-YBa2Cu3O7-x (Y211-Y123) tie-line intersects the primary crystallisation field of BC1 first. The actual peritectic reaction that takes place is Y2BaCuO5(s) + BaCuO2(s) + 2BaCu2O2(L) + 1/2O2 → 2YBa2Cu3O6(s). Two schematic representations which allow an analysis of the pO2 dependence are given. The gradient in micro structure self-established by the sample acts as a driving force for texturing. With this new perspective gained about the actual peritectic reaction and mechanisms of melt-texturing of Y123, it is possible to explain most of the aspects about partial melt-texturing. In addition, it seems possible to devise heat treatments that may allow for the production of well-oriented single domains with very large diameters. © 1999 Elsevier Science B.V.

Acute hamstring strain injury in track and field athletes : a 3-year observational study at the Penn Relay Carnival

Purpose To observe the incidence rates of hamstring strain injuries (HSIs) across different competition levels and ages during the Penn Relays Carnival. Methods Over a 3-year period all injuries treated by the medical staff were recorded. The type of injury, anatomic location, event in which the injury occurred, competition level and demographic data were documented. Absolute and relative HSI (per 1000 participants) were determined and odds ratios (OR) were calculated between genders, competition levels and events. Results Throughout the study period 48,473 athletes registered to participate in the Penn Relays Carnival, with 118 HSIs treated by the medical team. High school females displayed lesser risk of HSI than high school males (OR = 0.55, p = 0.021), and masters athletes were more likely than high school (OR = 4.26, p < 0.001) and college (OR = 3.55, p = 0.001) level athletes to suffer a HSI. The 4x400m relay displayed a greater likelihood of HSI compared to the 4x100m relay (OR = 1.77, p = 0.008). Conclusions High school males and masters levels athletes are most likely to suffer HSI, and there is higher risk in 400m events compared to 100m events.

Peripheral refraction patterns out to large field angles

Purpose To investigate hyperopic shifts and the oblique (or 45-degree/135-degree) component of astigmatism at large angles in the horizontal visual field using the Hartmann-Shack technique. Methods The adult participants consisted of 6 hypermetropes, 13 emmetropes and 11 myopes. Measurements were made with a modified COAS-HD Hartmann-Shack aberrometer across T60 degrees along the horizontal visual field in 5-degree steps. Eyes were dilated with 1% cyclopentolate. Peripheral refraction was estimated as mean spherical (or spherical equivalent) refraction, with/against the rule of astigmatism and oblique astigmatism components, and as horizontal and vertical refraction components based on 3-mm major diameter elliptical pupils. Results Thirty percent of eyes showed a pattern that was a combination of type IV and type I patterns of Rempt et al. (Rempt F, Hoogerheide J, Hoogenboom WP. Peripheral retinoscopy and the skiagram. Ophthalmologica 1971;162:1Y10), which shows the characteristics of type IV (relative hypermetropia along the vertical meridian and relative myopia along the horizontal meridian) out to an angle of between 40 and 50 degrees before behaving like type I (both meridians show relative hypermetropia). We classified this pattern as type IV/I. Seven of 13 emmetropes had this pattern. As a group, there was no significant variation of the oblique component of astigmatism with angle, but about one-half of the eyes showed significant positive slopes (more positive or less negative values in the nasal field than in the temporal field) and one-fourth showed significant negative slopes. Conclusions It is often considered that a pattern of relative peripheral hypermetropia predisposes to the development of myopia. In this context, the finding of a considerable portion of emmetropes with the IV/I pattern suggests that it is unlikely that refraction at visual field angles beyond 40 degrees from fixation contributes to myopia development.

Galvanic replacement mediated synthesis of hollow Pt nanocatalysts : significance of residual Ag for the H2 evolution reaction

With the increasing popularity of the galvanic replacement approach towards the development of bimetallic nanocatalysts, special emphasis has been focused on minimizing the use of expensive metal (e.g. Pt), in the finally formed nanomaterials (e.g. Ag/Pt system as a possible catalyst for fuel cells). However, the complete removal of the less active sacrificial template is generally not achieved during galvanic replacement, and its residual presence may significantly impact on the electrocatalytic properties of the final material. Here, we investigate the hydrogen evolution reaction (HER) activity of Ag nanocubes replaced with different amounts of Pt, and demonstrate how the bimetallic composition significantly affects the activity of the alloyed nanomaterial.

A study of the galvanic replacement reaction at surfaces and the role of lateral charge propagation

The galvanic replacement of isolated nanostructures of copper and silver on conducting supports as well as continuous films of copper with gold is reported. The surface morphology was characterized by scanning electron microscopy and the replacement with gold was confirmed by EDX analysis. It was found that lateral charge propagation during the replacement reaction had a significant effect in all cases. For the isolated nanostructures the deposition of gold was observed not only at the sacrificial template but also at the surrounding unmodified areas of the conducting substrate. In the case of copper films the role of lateral charge propagation was also confirmed by connecting it to an ITO electrode through an external circuit upon which gold deposition was also observed to occur. Interestingly, by inhibiting the rate of charge propagation, through the introduction of a series resistor, the morphology of gold on the copper substrate could be changed from discrete surface decoration with cube like nanoparticles to a more porous rough surface.

Study of the initial stage of solid electrolyte interphase formation upon chemical reaction of lithium metal and N-Methyl-N-Propyl-Pyrrolidinium-Bis (Fluorosulfonyl) Imide

Chemical reaction studies of N-methyl-N-propyl-pyrrolidinium-bis(fluorosulfonyl)imide-based ionic liquid with the lithium metal surface were performed using ab initio molecular dynamics (aMD) simulations and X-ray Photoelectron Spectroscopy (XPS). The molecular dynamics simulations showed rapid and spontaneous decomposition of the ionic liquid anion, with subsequent formation of long-lived species such as lithium fluoride. The simulations also revealed the cation to retain its structure by generally moving away from the lithium surface. The XPS experiments showed evidence of decomposition of the anion, consistent with the aMD simulations and also of cation decomposition and it is envisaged that this is due to the longer time scale for the XPS experiment compared to the time scale of the aMD simulation. Overall experimental results confirm the majority of species suggested by the simulation. The rapid chemical decomposition of the ionic liquid was shown to form a solid electrolyte interphase composed of the breakdown products of the ionic liquid components in the absence of an applied voltage.

Electrochemical formation of porous copper 7, 7, 8, 8-tetracyanoquinodimethane and copper 2, 3, 5, 6-tetrafluoro-7, 7, 8, 8-tetracyanoquinodimethane honeycomb surfaces with superhydrophobic properties

The electrochemical formation of highly porous CuTCNQ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) and CuTCNQF4 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) materials was undertaken via the spontaneous redox reaction between a porous copper template, created using a hydrogen bubbling template technique, and an acetonitrile solution containing TCNQ or TCNQF4. It was found that activation of the surface via vigorous hydrogen evolution that occurs during porous copper deposition and TCNQ mass transport being hindered through the porous network of the copper template influenced the growth of CuTCNQ and CuTCNQF4. This approach resulted in the fabrication of a honeycomb layered type structure where the internal walls consist of very fine crystalline needles or spikes. This combination of microscopic and nanoscopic roughness was found to be extremely beneficial for anti-wetting properties where superhydrophobic materials with contact angles as high as 177° were created. Given that CuTCNQ and CuTCNQF4 have shown potential as molecular based electronic materials in the area of switching and field emission, the creation of a surface that is moisture resistant may be of applied interest.

Students' cultural capital : a study of assessment for learning as a field of exchange

This study was conducted within the context of a flexible education institution where conventional educational assessment practices and tests fail to recognise and assess the creativity and cultural capital of a cohort of marginalised young people. A new assessment model which included an electronic-portfolio-social-networking system (EPS) was developed and trialled to identify and exhibit evidence of students' learning. The study aimed to discern unique forms of cultural capital (Bourdieu, 1986) possessed by students who attend the Edmund Rice Education Australia Flexible Learning Centre Network (EREAFLCN). The EPS was trialled at the case study schools in an intervention and developed a space where students could make evident culturally specific forms of capital and funds of knowledge (Gonzalez, Moll, & Amanti, 2005). These resources were evaluated, modified and developed through dialogic processes utilising assessment for learning approaches (Qualifications and Curriculum Development Agency, 2009) in online and classroom settings. Students, peers and staff engaged in the recognition, judgement, revision and evaluation of students' cultural capital in a subfield of exchange (Bourdieu, 1990). The study developed the theory of assessment for learning as a field of exchange incorporating an online system as a teaching and assessment model. The term efield has been coined to describe this particular capital exchange model. A quasi-ethnographic approach was used to develop a collective case study (Stake, 1995). This case study involved an in-depth exploration of five students' forms of cultural capital and the ways in which this capital could be assessed and exchanged using the efield model. A comparative analysis of the five cases was conducted to identify the emergent issues of students' recognisable cultural capital resources and the processes of exchange that can be facilitated to acquire legitimate credentials for these students in the Australian field of education. The participants in the study were young people at two EREAFLC schools aged between 12 and 18 years. Data was collected through interviews, observations and examination of documents made available by the EREAFLCN. The data was coded and analysed using a theoretical framework based on Bourdieu's analytical tools and a sociocultural psychology theoretical perspective. Findings suggest that processes based on dialogic relationships can identify and recognise students' forms of cultural capital that are frequently misrecognised in mainstream school environments. The theory of assessment for learning as a field of exchange was developed into praxis and integrated in an intervention. The efield model was found to be an effective sociocultural tool in converting and exchanging students' capital resources for legitimated cultural and symbolic capital in the field of education.

Hemi-field and full-field form-deprivation induce timing changes in multifocal ERG responses in chick

Purpose: In animal models hemi-field deprivation results in localised, graded vitreous chamber elongation and presumably deprivation induced localised changes in retinal processing. The aim of this research was to determine if there are variations in ERG responses across the retina in normal chick eyes and to examine the effect of hemi-field and full-field deprivation on ERG responses across the retina and at earlier times than have previously been examined electrophysiologically. Methods: Chicks were either untreated, wore monocular full-diffusers or half-diffusers (depriving nasal retina) (n = 6-8 each group) from day 8. mfERG responses were measured using the VERIS mfERG system across the central 18.2º× 16.7º (H × V) field. The stimulus consisted of 61 unscaled hexagons with each hexagon modulated between black and white according to a pseudorandom binary m-sequence. The mfERG was measured on day 12 in untreated chicks, following 4 days of hemi-field diffuser wear, and 2, 48 and 96 h after application of full-field diffusers. Results: The ERG response of untreated chick eyes did not vary across the measured field; there was no effect of retinal location on the N1-P1 amplitude (p = 0.108) or on P1 implicit time (p > 0.05). This finding is consistent with retinal ganglion cell density of the chick varying by only a factor of two across the entire retina. Half-diffusers produced a ramped retina and a graded effect of negative lens correction (p < 0.0001); changes in retinal processing were localized. The untreated retina showed increasing complexity of the ERG waveform with development; form-deprivation prevented the increasing complexity of the response at the 2, 48 and 96 h measurement times and produced alterations in response timing. Conclusions: Form-deprivation and its concomitant loss of image contrast and high spatial frequency images prevented development of the ERG responses, consistent with a disruption of development of retinal feedback systems. The characterisation of ERG responses in normal and deprived chick eyes across the retina allows the assessment of concurrent visual and retinal manipulations in this model. (Ophthalmic & Physiological Optics © 2013 The College of Optometrists.)

Design, implementation and multisite evaluation of a system suitability protocol for the quantitative assessment of instrument performance in liquid chromatography-multiple reaction monitoring-MS (LC-MRM-MS)

Multiple reaction monitoring (MRM) mass spectrometry coupled with stable isotope dilution (SID) and liquid chromatography (LC) is increasingly used in biological and clinical studies for precise and reproducible quantification of peptides and proteins in complex sample matrices. Robust LC-SID-MRM-MS-based assays that can be replicated across laboratories and ultimately in clinical laboratory settings require standardized protocols to demonstrate that the analysis platforms are performing adequately. We developed a system suitability protocol (SSP), which employs a predigested mixture of six proteins, to facilitate performance evaluation of LC-SID-MRM-MS instrument platforms, configured with nanoflow-LC systems interfaced to triple quadrupole mass spectrometers. The SSP was designed for use with low multiplex analyses as well as high multiplex approaches when software-driven scheduling of data acquisition is required. Performance was assessed by monitoring of a range of chromatographic and mass spectrometric metrics including peak width, chromatographic resolution, peak capacity, and the variability in peak area and analyte retention time (RT) stability. The SSP, which was evaluated in 11 laboratories on a total of 15 different instruments, enabled early diagnoses of LC and MS anomalies that indicated suboptimal LC-MRM-MS performance. The observed range in variation of each of the metrics scrutinized serves to define the criteria for optimized LC-SID-MRM-MS platforms for routine use, with pass/fail criteria for system suitability performance measures defined as peak area coefficient of variation <0.15, peak width coefficient of variation <0.15, standard deviation of RT <0.15 min (9 s), and the RT drift <0.5min (30 s). The deleterious effect of a marginally performing LC-SID-MRM-MS system on the limit of quantification (LOQ) in targeted quantitative assays illustrates the use and need for a SSP to establish robust and reliable system performance. Use of a SSP helps to ensure that analyte quantification measurements can be replicated with good precision within and across multiple laboratories and should facilitate more widespread use of MRM-MS technology by the basic biomedical and clinical laboratory research communities.

Prognostic value of hTERT mRNA expression in surgical samples of lung cancer patients : the European Early Lung Cancer Project

Lung cancer is the most important cause of cancer-related mortality. Resectability and eligibility for treatment with adjuvant chemotherapy is determined by staging according to the TNM classification. Other determinants of tumour behaviour that predict disease outcome, such as molecular markers, may improve decision-making. Activation of the gene encoding human telomerase reverse transcriptase (hTERT) is implicated in the pathogenesis of lung cancer, and consequently detection of hTERT mRNA might have prognostic value for patients with early stage lung cancer. A cohort of patients who underwent a complete resection for early stage lung cancer was recruited as part of the European Early Lung Cancer (EUELC) project. In 166 patients expression of hTERT mRNA was determined in tumour tissue by quantitative real-time RT-PCR and related to that of a house-keeping gene (PBGD). Of a subgroup of 130 patients tumour-distant normal tissue was additionally available for hTERT mRNA analysis. The correlation between hTERT levels of surgical samples and disease-free survival was determined using a Fine and Gray hazard model. Although hTERT mRNA positivity in tumour tissue was significantly associated with clinical stage (Fisher's exact test p=0.016), neither hTERT mRNA detectability nor hTERT mRNA levels in tumour tissue were associated with clinical outcome. Conversely, hTERT positivity in adjacent normal samples was associated with progressive disease, 28% of patients with progressive disease versus 7.5% of disease-free patients had detectable hTERT mRNA in normal tissue [adjusted HR: 3.60 (1.64-7.94), p=0.0015]. hTERT mRNA level in tumour tissue has no prognostic value for patients with early stage lung cancer. However, detection of hTERT mRNA expression in tumour-distant normal lung tissue may indicate an increased risk of progressive disease.

The impact of spatial scales and spatial smoothing on the outcome of Bayesian spatial model

Discretization of a geographical region is quite common in spatial analysis. There have been few studies into the impact of different geographical scales on the outcome of spatial models for different spatial patterns. This study aims to investigate the impact of spatial scales and spatial smoothing on the outcomes of modelling spatial point-based data. Given a spatial point-based dataset (such as occurrence of a disease), we study the geographical variation of residual disease risk using regular grid cells. The individual disease risk is modelled using a logistic model with the inclusion of spatially unstructured and/or spatially structured random effects. Three spatial smoothness priors for the spatially structured component are employed in modelling, namely an intrinsic Gaussian Markov random field, a second-order random walk on a lattice, and a Gaussian field with Matern correlation function. We investigate how changes in grid cell size affect model outcomes under different spatial structures and different smoothness priors for the spatial component. A realistic example (the Humberside data) is analyzed and a simulation study is described. Bayesian computation is carried out using an integrated nested Laplace approximation. The results suggest that the performance and predictive capacity of the spatial models improve as the grid cell size decreases for certain spatial structures. It also appears that different spatial smoothness priors should be applied for different patterns of point data.

Perdido : the first Smart Field in the western hemisphere

Located in the Gulf of Mexico in nearly 8,000 feet of water, the Perdido development is the world’s deepest spar and Shell’s first Smart Field in the Western hemisphere. Jointly developed by Shell, BP, and Chevron, the spar and the subsea equipment connected to it will eventually capture approximately an order of magnitude more data than is collected from any other Shell-designed and managed development currently operating in the Gulf of Mexico. This paper will describe Shell’s Smart Fields design philosophy, briefly explain the five design elements that underpin “smartness” in Shell’s North and South American operations—specifically, remote assisted operations, exception-based surveillance, collaborative work environments, hydrocarbon development tools and workflows, and Smart Fields Foundation IT infrastructure—and shed light on the process by which a highly customized Smart Fields development and management plan was put together for Perdido.

A field experiment in moral suasion and tax compliance focusing on underdeclaration and overdeduction

One of very few field experiments in tax compliance, this study generates a unique data set on Swiss taxpayers’ underdeclaration of income and wealth and overdeduction of tax credits by obtaining exclusive access to tax-return corrections made by the tax administration. Using this commune-level data from Switzerland, it explores the influence on tax compliance of moral suasion, introduced through a treatment in which taxpayers receive a letter containing normative appeals signed by the commune’s fiscal commissioner. This letter also serves to operationalize elements of social identity and (mutual) trust. Interestingly, the results not only echo the earlier finding that moral suasion has barely any effect on taxpayer compliance, but show clear differences between underdeclaration and overdeduction.