Universal tight binding model for chemical reactions in solution and at surfaces. III. Stoichiometric and reduced surfaces of titania and the adsorption of water

We demonstrate a model for stoichiometric and reduced titanium dioxide intended for use in molecular dynamics and other atomistic simulations and based in the polarizable ion tight binding theory. This extends the model introduced in two previous papers from molecular and liquid applications into the solid state, thus completing the task of providing a comprehensive and unified scheme for studying chemical reactions, particularly aimed at problems in catalysis and electrochemistry. As before, experimental results are given priority over theoretical ones in selecting targets for model fitting, for which we used crystal parameters and band gaps of titania bulk polymorphs, rutile and anatase. The model is applied to six low index titania surfaces, with and without oxygen vacancies and adsorbed water molecules, both in dissociated and non-dissociated states. Finally, we present the results of molecular dynamics simulation of an anatase cluster with a number of adsorbed water molecules and discuss the role of edge and corner atoms of the cluster. (C) 2014 AIP Publishing LLC.

Universal tight binding model for chemical reactions in solution and at surfaces. I. Organic molecules

As is now well established, a first order expansion of the Hohenberg-Kohn total energy density functional about a trial input density, namely, the Harris-Foulkes functional, can be used to rationalize a non self consistent tight binding model. If the expansion is taken to second order then the energy and electron density matrix need to be calculated self consistently and from this functional one can derive a charge self consistent tight binding theory. In this paper we have used this to describe a polarizable ion tight binding model which has the benefit of treating charge transfer in point multipoles. This admits a ready description of ionic polarizability and crystal field splitting. It is necessary in constructing such a model to find a number of parameters that mimic their more exact counterparts in the density functional theory. We describe in detail how this is done using a combination of intuition, exact analytical fitting, and a genetic optimization algorithm. Having obtained model parameters we show that this constitutes a transferable scheme that can be applied rather universally to small and medium sized organic molecules. We have shown that the model gives a good account of static structural and dynamic vibrational properties of a library of molecules, and finally we demonstrate the model's capability by showing a real time simulation of an enolization reaction in aqueous solution. In two subsequent papers, we show that the model is a great deal more general in that it will describe solvents and solid substrates and that therefore we have created a self consistent quantum mechanical scheme that may be applied to simulations in heterogeneous catalysis.

Interspecific competition in honeybee intracellular gut parasites is asymmetric and favours the spread of an emerging infectious disease

There is increasing appreciation that hosts in natural populations are subject to infection by multiple parasite species. Yet the epidemiological and ecological processes determining the outcome of mixed infections are poorly understood. Here, we use two intracellular gut parasites (Microsporidia), one exotic and one co-evolved in the western honeybee (Apis mellifera), in an experiment in which either one or both parasites were administered either simultaneously or sequentially. We provide clear evidence of within-host competition; order of infection was an important determinant of the competitive outcome between parasites, with the first parasite significantly inhibiting the growth of the second, regardless of species. However, the strength of this ‘priority effect’ was highly asymmetric, with the exotic Nosema ceranae exhibiting stronger inhibition of Nosema apis than vice versa. Our results reveal an unusual asymmetry in parasite competition that is dependent on order of infection. When incorporated into a mathematical model of disease prevalence, we find asymmetric competition to be an important predictor of the patterns of parasite prevalence found in nature. Our findings demonstrate the wider significance of complex multi-host–multi-parasite interactions as drivers of host–pathogen community structure

Stress in parents of children born very preterm is predicted by child externalising behaviour and parent coping at age 7 years

Objective: To examine factors which predict parenting stress in a longitudinal cohort of children born very preterm seen at age seven years.
Methods: We recruited 100 very preterm (< 32 weeks GA) child-parent dyads and a control group of 50 term-born dyads born between 2001 and 2004 with follow-up at seven years. Parents completed the Parenting Stress Index, Ways of Coping Questionnaire, Child Behavior Check List, Beck Depression Inventory and the State Trait Anxiety Inventory questionnaires. Child IQ was assessed using the Wechsler Intelligence Scale-IV.
Results: After controlling for maternal education, parents of preterm children (95% CI, 111.1 to 121.4) scored higher (p = .027) on the Parenting Stress Index than term born controls (95% CI, 97.8 to 113.2). Regression analyses showed that child externalising behaviour, sex and parent escape/avoidance coping style, predicted higher parenting stress in the preterm group. Parents of preterm girls expressed higher levels of stress than those of boys. 
Conclusions: Maladaptive coping strategies contribute to greater stress in parents of very preterm children. Our findings suggest that these parents need support for many years after birth of a very preterm infant.

Emotional development among early school-age children: Gender differences in the role of problem behaviours

There has been an increasing focus on social and emotional development in educational programmes in early childhood as both variables are believed to influence behavioural outcomes in the classroom. However, relationships between social and emotional development and behaviour in early childhood have rarely been explored. This article sets out to investigate the conceptualisation of these variables and their inter-relationships. Structural equation models were used to assess if differences exist between boys and girls in relation to social and emotional competences, which could affect the relative success of such programmes. This article is based on cross-sectional data collected from 749 four- to six-year-olds and their teachers. The findings generally supported the hypothesised relationships between social and emotional development variables and prosocial behaviour (including internalising behaviour) for boys and girls. However, some gender differences were noted in externalising behaviour, which teachers often consider to be most significant due to its potentially disruptive nature in the classroom.

Seasonal variation in month of diagnosis in children with type 1 diabetes registered in 23 European centers during 1989-2008: little short-term influence of sunshine hours or average temperature

BACKGROUND: The month of diagnosis in childhood type 1 diabetes shows seasonal variation.

OBJECTIVE: We describe the pattern and investigate if year-to-year irregularities are associated with meteorological factors using data from 50 000 children diagnosed under the age of 15 yr in 23 population-based European registries during 1989-2008.

METHODS: Tests for seasonal variation in monthly counts aggregated over the 20 yr period were performed. Time series regression was used to investigate if sunshine hour and average temperature data were predictive of the 240 monthly diagnosis counts after taking account of seasonality and long term trends.

RESULTS: Significant sinusoidal pattern was evident in all but two small centers with peaks in November to February and relative amplitudes ranging from ±11 to ±38% (median ±17%). However, most centers showed significant departures from a sinusoidal pattern. Pooling results over centers, there was significant seasonal variation in each age-group at diagnosis, with least seasonal variation in those under 5 yr. Boys showed greater seasonal variation than girls, particularly those aged 10-14 yr. There were no differences in seasonal pattern between four 5-yr sub-periods. Departures from the sinusoidal trend in monthly diagnoses in the period were significantly associated with deviations from the norm in average temperature (0.8% reduction in diagnoses per 1 °C excess) but not with sunshine hours.

CONCLUSIONS: Seasonality was consistently apparent throughout the period in all age-groups and both sexes, but girls and the under 5 s showed less marked variation. Neither sunshine hour nor average temperature data contributed in any substantial way to explaining departures from the sinusoidal pattern.

Emotional insecurity in the family and community and youth delinquency in Northern Ireland: A person-oriented analysis across five-waves

Background: Over one billion children are exposed worldwide to political violence and armed conflict. Currently, conclusions about bases for adjustment problems are qualified by limited longitudinal research from a process-oriented, social-ecological perspective. In this study, we examined a theoretically-based model for the impact of multiple levels of the social ecology (family, community) on adolescent delinquency. Specifically, this study explored the impact of children’s emotional insecurity about both the family and community on youth delinquency in Northern Ireland. Methods: In the context of a five-wave longitudinal research design, participants included 999 mother-child dyads in Belfast (482 boys, 517 girls), drawn from socially-deprived, ethnically-homogenous areas that had experienced political violence. Youth ranged in age from 10 to 20 and were 12.18 (SD = 1.82) years old on average at Time 1. Findings: The longitudinal analyses were conducted in hierarchical linear modeling (HLM), allowing for the modeling of inter-individual differences in intra-individual change. Intra-individual trajectories of emotional insecurity about the family related to children’s delinquency. Greater insecurity about the community worsened the impact of family conflict on youth’s insecurity about the family, consistent with the notion that youth’s insecurity about the community sensitizes them to exposure to family conflict in the home. Conclusions: The results suggest that ameliorating children’s insecurity about family and community in contexts of political violence is an important goal toward improving adolescents’ well-being, including reduced risk for delinquency.

Gender and the Curriculum

Curriculum resides in relationship with the concept of gender in complex and multifaceted ways. Such a relationship acknowledges also the interconnectedness of curriculum, with assessment and pedagogy as well as with gender and demands that we look beyond gender as ‘sex-group differences’ to a deeper understanding of this notion as a cultural artifact, with more nuanced and complex understandings of boys and of girls and how gender affects young people’s identities as learners, as consumers of knowledge and skills, as well as differentially mediating their learning and ultimately their attainment. The chapter explores how we have moved from considerations of gender as a dichotomous variable (male/female) against which curriculum and assessment outcomes can be measured or evaluated, into considerations of gender as a culturally, fluid understanding of how boys and girls identify as individuals and as learners and how they differentially interact with subjects, subject knowledge and skills, as well as how these are taught and assessed.

Mojo Mickybo by Owen McCafferty

Mojo Mickybo is a vibrant and fast-paced tale of two boys’
friendship when they meet during the scorching summer of 1970.
One may be from ‘up the road’ and the other from ‘over the bridge’
but they are brought together by setting world records in headers,
fighting off bullies in the park and sneaking into the cinema to see
Butch Cassidy and The Sundance Kid. The two Cowboys friendship
takes them on a whirlwind adventure, from Belfast to Newcastle
Co. Down and back, blissfully unaware of the violence around them.

A sting in the spit: widespread cross-infection of multiple RNA viruses across wild and managed bees

Declining populations of bee pollinators are a cause of concern, with major repercussions for biodiversity loss and food security. RNA viruses associated with honeybees represent a potential threat to other insect pollinators, but the extent of this threat is poorly understood. This study aims to attain a detailed understanding of the current and ongoing risk of emerging infectious disease (EID) transmission between managed and wild pollinator species across a wide range of RNA viruses. Within a structured large-scale national survey across 26 independent sites, we quantify the prevalence and pathogen loads of multiple RNA viruses in co-occurring managed honeybee (Apis mellifera) and wild bumblebee (Bombus spp.) populations. We then construct models that compare virus prevalence between wild and managed pollinators. Multiple RNA viruses associated with honeybees are widespread in sympatric wild bumblebee populations. Virus prevalence in honeybees is a significant predictor of virus prevalence in bumblebees, but we remain cautious in speculating over the principle direction of pathogen transmission. We demonstrate species-specific differences in prevalence, indicating significant variation in disease susceptibility or tolerance. Pathogen loads within individual bumblebees may be high and in the case of at least one RNA virus, prevalence is higher in wild bumblebees than in managed honeybee populations. Our findings indicate widespread transmission of RNA viruses between managed and wild bee pollinators, pointing to an interconnected network of potential disease pressures within and among pollinator species. In the context of the biodiversity crisis, our study emphasizes the importance of targeting a wide range of pathogens and defining host associations when considering potential drivers of population decline.

Evaluating the effectiveness of domestic abuse prevention education: Are certain children more or less receptive to the messages conveyed?

Purpose
A number of school-based domestic abuse prevention programmes have been developed in the United Kingdom, but evidence as to the effectiveness of such programmes is limited. The aim of the research was to evaluate the effectiveness of one such programme and to see whether the outcomes differ by gender and experiences of domestic abuse.

Method
Pupils aged 13–14 years, across seven schools, receiving a 6-week education programme completed a questionnaire to measure their attitudes towards domestic violence at pre-, post-test, and 3-month follow-up, and also responded to questions about experiences of abuse (as victims, perpetrators, and witnesses) and help seeking. Children in another six schools not yet receiving the intervention responded to the same questions at pre- and post-test. In total, 1,203 children took part in the research.

Results
Boys and girls who had received the intervention became less accepting of domestic violence and more likely to seek help from pre- to post-test compared with those in the control group; outcomes did not vary by experiences of abuse. There was evidence that the change in attitudes for those in the intervention group was maintained at 3-month follow-up.

Conclusions
These findings suggest that such a programme shows great promise, with both boys and girls benefiting from the intervention, and those who have experienced abuse and those who have not (yet) experienced abuse showing a similar degree of attitude change.

Young teenagers' experiences of domestic abuse

This article reports on the first findings from the Boys to Men Research Project. In total, 1143 pupils aged 13–14 years completed a questionnaire to assess their experiences of domestic abuse as victims, witnesses and perpetrators. Overall, 45% of pupils who had been in a dating relationship reported having been victimised, 25% having perpetrated it, with the only difference in rates of victimisation and perpetration between boys and girls being in relation to sexual victimisation. Of the whole sample, 34% reported having witnessed it in their own family. There was a relationship between victimisation and perpetration with the vast majority of perpetrators (92%) also reporting experiencing abuse from a boyfriend/girlfriend. There was also a relationship between experiencing abuse and help seeking from adults, with those who have been victimised less likely to say they would seek help if they were hit by a partner than those who had yet to experience any abuse. The relationship between help seeking and experiences of abuse is further complicated by gender, with girls twice as likely to seek help than boys, but with girls who have previously hit a partner among the most reticent group. The paper concludes with highlighting the implications of these findings for those undertaking preventative work in schools.

Impact of Free Glasses and a Teacher Incentive on Children's Use of Eyeglasses: A Cluster-Randomized Controlled Trial.

Purpose: To study the effect of free glasses combined with teacher incentives on in-school glasses wear among Chinese urban migrant children. Design: Cluster-randomized controlled trial. Methods: Children with VA <= 6/12 in either eye due to refractive error in 94 randomly-chosen primary schools underwent randomization by school to receive free glasses, education on their use and a teacher incentive (Intervention), or glasses prescriptions only (Control). Intervention group teachers received a tablet computer if >= 80% of children given glasses wore them during un-announced visits 6 weeks and 6 months (main outcome) after intervention. Results: Among 4376 children, 728 (16.7%, mean age 10.9 years, 51.0% boys) met enrollment criteria and were randomly allocated, 358 (49.2%, 47 schools) to Intervention and 370 (50.8%, 47 schools) to Control. Among these, 693 children (95.2%) completed the study and underwent analysis. Spectacle wear was significantly higher at 6 months among Intervention children (Observed [main outcome]: 68.3% versus 23.9%, Adjusted Odds Ratio [OR]=11.5, 95% Confidence Interval [CI] 5.91-22.5, P<0.001; Self-reported: 90.6% versus 32.1%, OR = 43.7, 95% CI = 21.7-88.5, P < 0.001). Other predictors of observed wear at 6 months included baseline spectacle wear (P<0.001), uncorrected VA<6/18 (P=0.01) and parental spectacle wear (P=0.02). The 6-month observed wear rate was only 41% among similar-aged children provided free glasses in our previous trial without teacher incentives. Conclusions: Free spectacles and teacher incentives maintain classroom wear in the large majority of children needing glasses over a school year. Low wear among Control children demonstrates the need for interventions.

Still Unequal at Birth: Birth Weight, Socioeconomic Status and Outcomes at Age 9

The prevalence of low birth weight is an important aspect of public health which has been linked to increased risk of infant death, increased cost of care, and a range of later life outcomes. Using data from a new Irish cohort study, I document the relationship between birth weight and socio-economic status. The association of maternal education with birth weight does not appear to be due to the timing of birth or complications during pregnancy, even controlling for a wide range of background characteristics. However, results do suggest intergenerational persistence in the transmission of poor early life conditions. Birth weight predicts a number of outcomes at age 9, including test scores, hospital stays and health. An advantage of the data is that I am able to control for a number of typically unmeasured variables. I determine whether parental investments (as measured by the quality of interaction with the child, parenting style, or school quality) mediate the association between birth weight and later indicators. For test scores, there is evidence of non-linearity, and boys are more adversely affected than girls. I also consider whether there are heterogeneous effects by ability using quantile regression. These results are consistent with a literature which finds that there is a causal relationship between early life conditions and later outcomes.