Lattice dynamics and vibrational spectra of the orthorhombic, tetragonal and cubic phases of methylammonium lead iodide

The hybrid halide perovskite CH3NH3PbI3 exhibits a complex structural behaviour, with successive transitions between orthorhombic, tetragonal and cubic polymorphs at ca. 165 K and 327 K. Herein we report first-principles lattice dynamics (phonon spectrum) for each phase of CH3NH3PbI3. The equilibrium structures compare well to solutions of temperature-dependent powder neutron diffraction. By following the normal modes we calculate infrared and Raman intensities of the vibrations, and compare them to the measurement of a single crystal where the Raman laser is controlled to avoid degradation of the sample. Despite a clear separation in energy between low frequency modes associated with the inorganic PbI3 network and high-frequency modes of the organic CH3NH3+ cation, significant coupling between them is found, which emphasises the interplay between molecular orientation and the corner-sharing octahedral networks in the structural transformations. Soft modes are found at the boundary of the Brillouin zone of the cubic phase, consistent with displacive instabilities and anharmonicity involving tilting of the PbI6 octahedra around room temperature.Comment: 9 pages, 4 figure

UK monitoring and deposition of tephra from the May 2011 eruption of Grímsvötn, Iceland

Mapping the transport and deposition of tephra is important for the assessment of an eruption’s impact on health, transport, vegetation and infrastructure, but it is challenging at large distances from a volcano (> 1000 km), where it may not be visible to the naked eye. Here we describe a range of methods used to quantify tephra deposition and impact on air quality during the 21–28 May 2011 explosive basaltic eruption of Grímsvötn volcano, Iceland. Tephra was detected in the UK with tape-on-paper samples, rainwater samples, rainwater chemistry analysis, pollen slides and air quality measurements. Combined results show that deposition was mainly in Scotland, on 23–25 May. Deposition was patchy, with adjacent locations recording different results. Tape-on-paper samples, collected by volunteer citizen scientists, and giving excellent coverage across the UK, showed deposition at latitudes >55°N, mainly on 24 May. Rainwater samples contained ash grains mostly 20–30 μm long (maximum recorded grainsize 80 μm) with loadings of up to 116 grainscm-2. Analysis of rainwater chemistry showed high concentrations of dissolved Fe and Al in samples from N Scotland on 24–27 May. Pollen slides recorded small glass shards (3–4 μm long) deposited during rainfall on 24–25 May and again on 27 May. Air quality monitoring detected increased particulate matter concentrations in many parts of the country. An hourly concentration of particles  53°N) on 24 May but no negative effects on health were reported. Although the eruption column reached altitudes of 20 km above sea level, air mass trajectories suggest that only tephra from the lowest 4 km above sea level of the eruption plume was transported to the UK. This demonstrates that even low plumes could deliver tephra to the UK and suggests that the relative lack of basaltic tephra in the tephrochronological record is not due to transport processes

A tri-dimensional approach for auditing brand loyalty

Over the past twenty years brand loyalty has been an important topic for both marketing practitioners and academics. While practitioners have produced proprietary brand loyalty audit models, there has been little academic research to make transparent the methodology that underpins these audits and to enable practitioners to understand, develop and conduct their own audits. In this paper, we propose a framework for a brand loyalty audit that uses a tri-dimensional approach to brand loyalty, which includes behavioural loyalty and the two components of attitudinal loyalty: emotional and cognitive loyalty. In allowing for different levels and intensity of brand loyalty, this tri-dimensional approach is important from a managerial perspective. It means that loyalty strategies that arise from a brand audit can be made more effective by targeting the market segments that demonstrate the most appropriate combination of brand loyalty components. We propose a matrix with three dimensions (emotional, cognitive and behavioural loyalty) and two levels (high and low loyalty) to facilitate a brand loyalty audit. To demonstrate this matrix, we use the example of financial services, in particular a rewards-based credit card

Methods to estimate the between-study variance and its uncertainty in meta-analysis

Meta‐analyses are typically used to estimate the overall/mean of an outcome of interest. However, inference about between‐study variability, which is typically modelled using a between‐study variance parameter, is usually an additional aim. The DerSimonian and Laird method, currently widely used by default to estimate the between‐study variance, has been long challenged. Our aim is to identify known methods for estimation of the between‐study variance and its corresponding uncertainty, and to summarise the simulation and empirical evidence that compares them. We identified 16 estimators for the between‐study variance, seven methods to calculate confidence intervals, and several comparative studies. Simulation studies suggest that for both dichotomous and continuous data the estimator proposed by Paule and Mandel and for continuous data the restricted maximum likelihood estimator are better alternatives to estimate the between‐study variance. Based on the scenarios and results presented in the published studies, we recommend the Q‐profile method and the alternative approach based on a ‘generalised Cochran between‐study variance statistic’ to compute corresponding confidence intervals around the resulting estimates. Our recommendations are based on a qualitative evaluation of the existing literature and expert consensus. Evidence‐based recommendations require an extensive simulation study where all methods would be compared under the same scenarios. © 2015 The Authors. Research Synthesis Methods published by John Wiley & Sons Ltd

Vitamin D metabolites are associated with musculoskeletal injury in young adults: a prospective cohort study.

The relationship between vitamin D metabolites and lower body (pelvis and lower limb) overuse injury is unclear. In a prospective cohort study, we investigated the association between vitamin D metabolites and incidence of lower body overuse musculoskeletal and bone stress injury in young adults undergoing initial military training during all seasons. In 1637 men and 530 women (age, 22.6 ± 7.5 years; BMI, 24.0 ± 2.6 kg∙m−2; 94.3% white ethnicity), we measured serum 25-hydroxyvitamin D (25(OH)D) and 24,25-dihydroxyvitamin D (24,25(OH)2D) by high-performance liquid chromatography tandem mass spectrometry, and 1,25-dihydroxyvitamin D (1,25(OH)2D) by immunoassay during week 1 of training. We examined whether the relationship between 25(OH)D and 1,25(OH)2D:24,25(OH)2D ratio was associated with overuse injury. During 12 weeks training, 21.0% sustained ≥1 overuse musculoskeletal injury, and 5.6% sustained ≥1 bone stress injury. After controlling for sex, BMI, 2.4 km run time, smoking, bone injury history, and Army training course (Officer, standard, or Infantry), lower body overuse musculoskeletal injury incidence was higher for participants within the second lowest versus highest quartile of 24,25(OH)2D (OR: 1.62 [95%CI 1.13–2.32; P = 0.009]) and lowest versus highest cluster of 25(OH)D and 1,25(OH)2D:24,25(OH)2D (OR: 6.30 [95%CI 1.89–21.2; P = 0.003]). Lower body bone stress injury incidence was higher for participants within the lowest versus highest quartile of 24,25(OH)2D (OR: 4.02 [95%CI 1.82–8.87; P < 0.001]) and lowest versus highest cluster of 25(OH)D and 1,25(OH)2D:24,25(OH)2D (OR: 22.08 [95%CI 3.26–149.4; P = 0.001]), after controlling for the same covariates. Greater conversion of 25(OH)D to 24,25(OH)2D, relative to 1,25(OH)2D (i.e., low 1,25(OH)2D:24,25(OH)2D), and higher serum 24,25(OH)2D were associated with a lower incidence of lower body overuse musculoskeletal and bone stress injury. Serum 24,25(OH)2D may have a role in preventing overuse injury in young adults undertaking arduous physical training

Making a home, finding a job: investigating early housing and employment outcomes for young people leaving care

This paper presents findings from a new study of outcomes for young people leaving care funded by the Department for Education and Skills. It reports findings for a sample of 106 young people in relation to progress made in housing and employment some 12-15 months after leaving care. The generally poor employment outcomes of care leavers are acknowledged, but ingredients that make for success are also highlighted, including the value of settled care and post-care careers, sound career planning and, significantly, the value of delaying young people's transitions from care. Early career paths also interconnect with how young people fare in housing, in developing life skills and with other problems in their lives after leaving care. Housing outcomes were more encouraging and predominantly shaped by events after leaving care, and faring well in housing was the factor most closely associated with positive mental well-being in young people. Some groups that are at risk of faring badly are identified, including young people with mental-health problems, young people with persistent offending or substance misuse problems and, in some respects, young disabled people. The implications of these findings for leaving care services are considered

The current and potential health benefits of the National Health Service Health Check cardiovascular disease prevention programme in England: A microsimulation study.

BACKGROUND: The National Health Service (NHS) Health Check programme was introduced in 2009 in England to systematically assess all adults in midlife for cardiovascular disease risk factors. However, its current benefit and impact on health inequalities are unknown. It is also unclear whether feasible changes in how it is delivered could result in increased benefits. It is one of the first such programmes in the world. We sought to estimate the health benefits and effect on inequalities of the current NHS Health Check programme and the impact of making feasible changes to its implementation. METHODS AND FINDINGS: We developed a microsimulation model to estimate the health benefits (incident ischaemic heart disease, stroke, dementia, and lung cancer) of the NHS Health Check programme in England. We simulated a population of adults in England aged 40-45 years and followed until age 100 years, using data from the Health Survey of England (2009-2012) and the English Longitudinal Study of Aging (1998-2012), to simulate changes in risk factors for simulated individuals over time. We used recent programme data to describe uptake of NHS Health Checks and of 4 associated interventions (statin medication, antihypertensive medication, smoking cessation, and weight management). Estimates of treatment efficacy and adherence were based on trial data. We estimated the benefits of the current NHS Health Check programme compared to a healthcare system without systematic health checks. This counterfactual scenario models the detection and treatment of risk factors that occur within 'routine' primary care. We also explored the impact of making feasible changes to implementation of the programme concerning eligibility, uptake of NHS Health Checks, and uptake of treatments offered through the programme. We estimate that the NHS Health Check programme prevents 390 (95% credible interval 290 to 500) premature deaths before 80 years of age and results in an additional 1,370 (95% credible interval 1,100 to 1,690) people being free of disease (ischaemic heart disease, stroke, dementia, and lung cancer) at age 80 years per million people aged 40-45 years at baseline. Over the life of the cohort (i.e., followed from 40-45 years to 100 years), the changes result in an additional 10,000 (95% credible interval 8,200 to 13,000) quality-adjusted life years (QALYs) and an additional 9,000 (6,900 to 11,300) years of life. This equates to approximately 300 fewer premature deaths and 1,000 more people living free of these diseases each year in England. We estimate that the current programme is increasing QALYs by 3.8 days (95% credible interval 3.0-4.7) per head of population and increasing survival by 3.3 days (2.5-4.1) per head of population over the 60 years of follow-up. The current programme has a greater absolute impact on health for those living in the most deprived areas compared to those living in the least deprived areas (4.4 [2.7-6.5] days of additional quality-adjusted life per head of population versus 2.8 [1.7-4.0] days; 5.1 [3.4-7.1] additional days lived per head of population versus 3.3 [2.1-4.5] days). Making feasible changes to the delivery of the existing programme could result in a sizable increase in the benefit. For example, a strategy that combines extending eligibility to those with preexisting hypertension, extending the upper age of eligibility to 79 years, increasing uptake of health checks by 30%, and increasing treatment rates 2.5-fold amongst eligible patients (i.e., 'maximum potential' scenario) results in at least a 3-fold increase in benefits compared to the current programme (1,360 premature deaths versus 390; 5,100 people free of 1 of the 4 diseases versus 1,370; 37,000 additional QALYs versus 10,000; 33,000 additional years of life versus 9,000). Ensuring those who are assessed and eligible for statins receive statins is a particularly important strategy to increase benefits. Estimates of overall benefit are based on current incidence and management, and future declines in disease incidence or improvements in treatment could alter the actual benefits observed in the long run. We have focused on the cardiovascular element of the NHS Health Check programme. Some important noncardiovascular health outcomes (e.g., chronic obstructive pulmonary disease [COPD] prevention from smoking cessation and cancer prevention from weight loss) and other parts of the programme (e.g., brief interventions to reduce harmful alcohol consumption) have not been modelled. CONCLUSIONS: Our model indicates that the current NHS Health Check programme is contributing to improvements in health and reducing health inequalities. Feasible changes in the organisation of the programme could result in more than a 3-fold increase in health benefits

'Sexercise': Working out heterosexuality in Jane Fonda’s fitness books

This is an Author's Accepted Manuscript of an article published in Leisure Studies, 30(2), 237 - 255, 2011, copyright Taylor & Francis, available online at: http://www.tandfonline.com/10.1080/02614367.2010.523837.This paper explores the connection between the promotion of heterosexual norms in women’s fitness books written by or in the name of Jane Fonda during the 1980s and the commodification of women’s fitness space in both the public and private spheres. The paper is set in the absence of overt discussions of normative heterosexuality in leisure studies and draws on critical heterosexual scholarship as well as the growing body of work theorising geographies of corporeality and heterosexuality. Using the principles of media discourse analysis, the paper identifies three overlapping characteristics of heterosexuality represented in Jane Fonda’s fitness books, and embodied through the exercise regimes: respectable heterosexual desire, monogamous procreation and domesticity. The paper concludes that the promotion and prescription of exercise for women in the Jane Fonda workout books centred on the reproduction and embodiment of heterosexual corporeality. Set within an emerging commercial landscape of women’s fitness in the 1980s, such exercise practices were significant in the legitimation and institutionalisation of heteronormativity