Molecular-Modified Photocathodes for Applications in Artificial Photosynthesis and Solar-to-Fuel Technologies.

Nature offers inspiration for developing technologies that integrate the capture, conversion, and storage of solar energy. In this review article, we highlight principles of natural photosynthesis and artificial photosynthesis, drawing comparisons between solar energy transduction in biology and emerging solar-to-fuel technologies. Key features of the biological approach include use of earth-abundant elements and molecular interfaces for driving photoinduced charge separation reactions that power chemical transformations at global scales. For the artificial systems described in this review, emphasis is placed on advancements involving hybrid photocathodes that power fuel-forming reactions using molecular catalysts interfaced with visible-light-absorbing semiconductors.

Perceptions of friendship, peers and influence on adolescent smoking according to tobacco control context: a systematic review and meta-ethnography of qualitative research.

BACKGROUND: A relationship between smoking and interpersonal influences has been well established within the literature. There have been cultural shifts in denormalisation and a reduction in tobacco smoking in many countries. Hence there is a need to understand social influences on adolescents' smoking across smoking normalisation contexts. METHODS: The search was conducted in July 2019 and updated in March 2022 within 11 databases and secondary sources. Search terms included schools, adolescents, smoking, peers, social norms and qualitative research. Screening was conducted by two researchers independently and in duplicate. Study quality was assessed using the eight-item Evidence for Policy and Practice Information and Co-ordinating Centre (EPPI-centre) tool for the appraisal of qualitative studies. Results were synthesised using a meta-narrative lens for meta-ethnography and compared across smoking normalisation contexts. RESULTS: Forty one studies were included and five themes were developed, mapping onto the socio ecological model. The social processes by which adolescents take up smoking differed according to a mixture of school type, peer group structure and the smoking culture within the school, as well as the wider cultural context. Data available from smoking denormalised contexts, described changes in social interactions around smoking to cope with its stigmatisation. This was manifested through i) direct peer influence, whereby subtle techniques were employed, ii) group belonging whereby smoking was less likely to be seen as a key determinant of group membership and smoking was less commonly reported to be used as a social tool, and iii) popularity and identity construction, whereby smoking was perceived more negatively in a denormalised context, compared with a normalised context. CONCLUSIONS: This meta-ethnography is the first study to demonstrate, drawing on international data, that peer processes in adolescent smoking may undergo changes as smoking norms within society change. Future research should focus on understanding differences across socioeconomic contexts, to inform the adaptation of interventions.

Exploring the association between school-based peer networks and smoking according to socioeconomic status and tobacco control context: a systematic review.

BACKGROUND: Whilst prevalence of youth smoking in middle and high income countries has decreased, inequality has prevailed. The introduction of legislation regulating tobacco use in public spaces varies across countries, impacting the tobacco control context. Thus reviewing our knowledge of how social networks may influence smoking differently within different contexts is required to facilitate the development of context-specific interventions. METHODS: The search, conducted on 31st May 2019, included the following smoking-related terms; schools, adolescents, peers and social networks. Inclusion and exclusion criteria were applied throughout the title and abstract screening and full text screening. Quality assessment and synthesis followed. Studies were narratively synthesised to identify changes according to legislative context. This synthesis was conducted separately for findings relating to three categories: socioeconomic status; social selection and influence; and network position. RESULTS: Thirty studies were included. Differences in the relationship between network characteristics and smoking according to socioeconomic status were measured in five out of fifteen studies in Europe. Results varied across studies, with differences in network characteristics and their association with smoking varying both between schools of a differing and those of a similar socioeconomic composition. For studies conducted both before and after the introduction of comprehensive smoking legislation, the evidence for selection processes was more consistent than influence, which varied according to reciprocity. Findings showed that isolates were more likely to smoke and in-degree and out-degree centrality were related to smoking both before and after the introduction of legislation. The relationship between popularity and smoking was contingent on school level smoking prevalence in studies conducted before the introduction of legislation, but not after. CONCLUSIONS: Overall, effects according to socioeconomic status were underreported in the included studies and no consistent evidence of change after the introduction of a comprehensive smoking ban was observed. Further network analyses are required using more recent data to obtain a comprehensive understanding of how network processes may influence smoking differently according to socioeconomic status, and how adaptation could be used to enhance intervention effectiveness. SYSTEMATIC REVIEW REGISTRATION: International Prospective Register of Systematic Reviews (PROSPERO) registration number: CRD42019137358 .

Process evaluation of the healthy primary School of the Future: the key learning points.

BACKGROUND: While schools have potential to contribute to children's health and healthy behaviour, embedding health promotion within complex school systems is challenging. The 'Healthy Primary School of the Future' (HPSF) is an initiative that aims to integrate health and well-being into school systems. Central to HPSF are two top-down changes that are hypothesized as being positively disruptive to the Dutch school system: daily free healthy lunches and structured physical activity sessions. These changes are expected to create momentum for bottom-up processes leading to additional health-promoting changes. Using a programme theory, this paper explores the processes through which HPSF and the school context adapt to one another. The aim is to generate and share knowledge and experiences on how to implement changes in the complex school system to integrate school health promotion. METHODS: The current study involved a mixed methods process evaluation with a contextual action-oriented research approach. The processes of change were investigated in four Dutch primary schools during the development year (2014-2015) and the first two years of implementation (2015-2017) of HPSF. The schools (each with 15-26 teachers and 233-389 children) were in low socio-economic status areas. Measurements included interviews, questionnaires, observations, and analysis of minutes of meetings. RESULTS: Top-down advice, combined with bottom-up involvement and external practical support were key facilitators in embedding HPSF within the schools' contexts. Sufficient coordination and communication at the school level, team cohesion, and feedback loops enhanced implementation of the changes. Implementation of the healthy lunch appeared to be disruptive and create momentum for additional health-promoting changes. CONCLUSIONS: Initiating highly visible positive disruptions to improve school health can act as a catalyst for wider school health promotion efforts. Conditions to create a positive disruption are enough time, and sufficient bottom-up involvement, external support, team cohesion and coordination. The focus should be on each specific school, as each school has their own starting point and process of change. TRIAL REGISTRATION: The study was retrospectively registered in the ClinicalTrials.gov database on 14 June 2016 (NCT02800616).

Cobalt Porphyrin-Polypyridyl Surface Coatings for Photoelectrosynthetic Hydrogen Production.

Hybrid materials that link light capture and conversion technologies with the ability to drive reductive chemical transformations are attractive as components in photoelectrosynthetic cells. We show that thin-film polypyridine surface coatings provide a molecular interface to assemble cobalt porphyrin catalysts for hydrogen evolution onto a visible-light-absorbing p-type gallium phosphide semiconductor. Spectroscopic techniques, including grazing angle attenuated total reflection Fourier transform infrared spectroscopy, confirm that the cobalt centers of the porphyrin macrocycles coordinate to pyridyl nitrogen sites of the organic surface coating. The cobalt porphyrin surface concentration and fraction of pyridyl sites coordinated to a cobalt center are quantified using complementary methods of ellipsometry, inductively coupled plasma mass spectrometry, and X-ray photoelectron spectroscopy. In aqueous solutions under simulated solar illumination the modified cathode is photochemically active for hydrogen production, generating the product gas with near-unity Faradaic efficiency at a rate of ≈10 µL min-1 cm-2 when studied in a three-electrode configuration and polarized at the equilibrium potential of the H+/H2 couple. This equates to a photoelectrochemical hydrogen evolution reaction activity of 17.6 H2 molecules s-1 Co-1, the highest value reported to date for a molecular-modified semiconductor. Key features of the functionalized photocathode include (1) the relative ease of synthetic preparation made possible by application of an organic surface coating that provides molecular recognition sites for immobilizing the cobalt porphyrin complexes at the semiconductor surface and (2) the use of visible light to drive cathodic fuel-forming reactions in aqueous solutions with no added organic acids or sacrificial chemical reductants.

Do stronger school smoking policies make a difference? Analysis of the health behaviour in school-aged children survey.

BACKGROUND: Associations of the strength of school smoking policies with cigarette, e-cigarette and cannabis use in Wales were examined. METHODS: Nationally representative cross-sectional survey of pupils aged 11-16 years (N=7376) in Wales. Senior management team members from 67 schools completed questionnaires about school smoking policies, substance use education and tobacco cessation initiatives. Multi-level, logistic regression analyses investigated self-reported cigarette, e-cigarette and cannabis use, for all students and those aged 15-16 years. RESULTS: Prevalence of current smoking, e-cigarette use and cannabis use in the past month were 5.3%, 11.5% and 2.9%, respectively. Of schools that provided details about smoking policies (66/67), 39.4% were strong (written policy applied to everyone in all locations), 43.9% were moderate (written policy not applied to everyone in all locations) and 16.7% had no written policy. There was no evidence of an association of school smoking policies with pupils' tobacco or e-cigarette use. However, students from schools with a moderate policy [OR = 0.47; 95% (confidence interval) CI: 0.26-0.84] were less likely to have used cannabis in the past month compared to schools with no written policy. This trend was stronger for students aged 15-16 years (moderate policy: OR = 0.42; 95% CI: 0.22-0.80; strong policy: OR = 0.45; 95% CI: 0.23-0.87). CONCLUSIONS: School smoking policies may exert less influence on young people's smoking behaviours than they did during times of higher adolescent smoking prevalence. Longitudinal studies are needed to examine the potential influence of school smoking policies on cannabis use and mechanisms explaining this association.

Free healthy breakfasts in primary schools: a cluster randomised controlled trial of a policy intervention in Wales, UK.

OBJECTIVE: The present study evaluated the impact of a national school programme of universal free healthy breakfast provision in Wales, UK. DESIGN: A cluster randomised controlled trial with repeated cross-sectional design and a 12-month follow-up. Primary outcomes were breakfast skipping, breakfast diet and episodic memory. Secondary outcomes were frequency of eating breakfast at home and at school, breakfast attitudes, rest-of-day diet and class behaviour. SETTING: Primary schools in nine local education authority areas. SUBJECTS: A total of 4350 students (aged 9-11 years) at baseline and 4472 at follow-up in 111 schools. RESULTS: Students in intervention schools reported significantly higher numbers of healthy food items consumed at breakfast and more positive attitudes towards breakfast eating at 12 months. Parents in intervention schools reported significantly higher rates of consumption of breakfast at school and correspondingly lower rates of breakfast consumption at home. No other significant differences were found. CONCLUSIONS: The intervention did not reduce breakfast skipping; rather, pupils substituted breakfast at home for breakfast at school. However, there were improvements in children's nutritional intake at breakfast time, if not the rest of the day, and more positive attitudes to breakfast, which may have implications for life-course dietary behaviours. There was no impact on episodic memory or classroom behaviour, which may require targeting breakfast skippers.

Development of a scale to measure 9-11-year-olds' attitudes towards breakfast.

OBJECTIVE: Development and validation of a questionnaire to measure children's attitudes towards breakfast. DESIGN: A pilot study was used to select questionnaire items and assess test-retest reliability. The questionnaire was then administered to a larger sample of children together with a dietary recall questionnaire. Randomly selected subsets of these children also completed a dietary recall interview or their parents were asked to complete a questionnaire relating to their child's breakfast eating habits. SETTING: Primary schools in south, west and north Wales, UK. SUBJECTS: A total of 2495 children (199 in pilot testing, 2382 in the main study) in years 5 and 6 (aged 9-11 years). RESULTS: The 13-item scale showed good construct validity, high internal reliability and acceptable test-retest reliability. Boys displayed more positive attitudes towards breakfast than girls but differences between the two age groups did not reach statistical significance. Children who did not skip breakfast displayed more positive attitudes than children who skipped breakfast. In addition, more positive attitudes towards breakfast were significantly correlated with consumption of a greater number of 'healthy' foods for breakfast (i.e., fruit, bread, cereal, milk products), consumption of fewer 'unhealthy' foods for breakfast (i.e., sweet items, crisps) and parental perceptions that their child usually ate a healthy breakfast. CONCLUSIONS: The breakfast attitudes questionnaire is a robust measure that is relatively quick to administer and simple to score. These qualities make it ideal for use where validity at the individual level is important or where more time-consuming dietary measures are not feasible.

Student health and well-being in secondary schools: the role of school support staff alongside teaching staff.

A growing evidence base indicates that health and educational attainment are synergistic goals. Students' relationships with teachers and other students in the school environment are consistently predictive of a broad range of health and well-being outcomes. Despite the potential importance of relationships between students and a broad range of actors within a school, research tends to reduce 'school staff' to 'teachers'. Previous research has highlighted incongruence between the power imbalance within a teacher-student relationship and the dynamics required to address health and well-being-related issues. To date, there has been no investigation into how the nature of the relationships between students and support staff may differ from those with teaching staff. This article aims to conceptualise the role of support versus teaching staff in promoting health and well-being to understand how school system functioning may affect relationships between school staff and students. Semi-structured interviews were conducted to obtain the perceptions of staff, students and parents within four exploratory case study schools of differing socio-economic status, geographical location and size. In line with the Theory of Health Promoting Schools and Human Functioning, findings demonstrated that the prominence of well-being relies on provision of staffing structures which include a team of support staff to work alongside teaching staff to provide the time and space to deal with issues immediately and build trust and rapport in a one-to-one setting. Further mixed-methods research is required to investigate how staffing structures can facilitate the development of mutually trusting relationships between staff and students.

Validation of a self-completion measure of breakfast foods, snacks and fruits and vegetables consumed by 9- to 11-year-old schoolchildren.

OBJECTIVE: To evaluate the validity and reliability of a dietary recall questionnaire, designed for group-level comparisons of foods eaten at breakfast and intake of fruits, vegetables, sweet items and crisps. DESIGN: Validity was assessed relative to 24-h dietary recall interviews, and reliability by comparing the baseline data with 4-month follow-up data. SUBJECTS AND SETTING: Fifty-eight schools took part in the validity assessments, with 374 children completing both measures. Reliability was assessed using 29 schools, with 1233 children at baseline and 1033 at follow-up. Children were aged 9-11 years and schools were located in socio-economically deprived areas of Wales. RESULTS: Results indicated moderate to substantial agreements for most foods eaten at breakfast on the day of reporting and fair to moderate agreements for breakfast foods the previous day. For items throughout the rest of the previous day, agreement was fair to substantial during school hours, but slight after school. Correlations were moderate in terms of 'healthy' items and 'unhealthy' items consumed at breakfast on the day of reporting, but weaker for the previous breakfast. Correlations between measures in terms of fruits, vegetables, sweet items and crisps throughout the rest of the previous day were fair to moderate. The measure demonstrated fair to substantial group-level reliability. CONCLUSIONS: The questionnaire, while subject to a number of limitations, gives an adequately valid and reliable overview of selected aspects of children's diet. It is likely to be of value at group-level in randomized controlled trials of school-based interventions.

Metalloporphyrin-modified semiconductors for solar fuel production.

We report a direct one-step method to chemically graft metalloporphyrins to a visible-light-absorbing gallium phosphide semiconductor with the aim of constructing an integrated photocathode for light activating chemical transformations that include capturing, converting, and storing solar energy as fuels. Structural characterization of the hybrid assemblies is achieved using surface-sensitive spectroscopic methods, and functional performance for photoinduced hydrogen production is demonstrated via three-electrode electrochemical testing combined with photoproduct analysis using gas chromatography. Measurements of the total per geometric area porphyrin surface loadings using a cobalt-porphyrin based assembly indicate a turnover frequency ≥3.9 H2 molecules per site per second, representing the highest reported to date for a molecular-catalyst-modified semiconductor photoelectrode operating at the H+/H2 equilibrium potential under 1-sun illumination.

Colonic telangiectasias in scleroderma.

Gastrointestinal tract involvement in progressive systemic sclerosis (PSS) is common. A 46-year-old woman with PSS and calcinosis, Raynaud's phenomenon, esophageal hypomotility, sclerodactyly, and telangiectasias with evidence of widespread intestinal tract involvement is described in whom multiple colonic telangiectasias (angiodysplasias) were found on colonoscopy, a finding not previously reported to our knowledge. The telangiectasias represent a potential cause of gastrointestinal tract bleeding.

Dissociation between emotional and endocrine responses preceding an academic examination in male medical students.

A study was made in 2 consecutive years of the emotional states and morning and afternoon serum levels of prolactin, cortisol and testosterone of male medical students during a 4- to 5-week period preceding a major university examination. 'Distress', 'anxiety' and, to a lesser degree, 'depression' increased during the 2 weeks immediately preceding the examination and were positively correlated with personality anxiety or neuroticism traits. Group means for hormones showed no consistent change over the same period. Neither was there evidence for a correlation between endocrine and emotional changes within individual students during the pre-examination period. A restricted study showed that there were significant increments in cortisol in samples taken during the examination itself. Changes in emotional state before an examination occurred in the absence of equally dramatic changes in levels of the three hormones studied, though this relationship may have altered during the examination itself. This suggests that the factors controlling the two categories of response may relate differently, in some way, to the imminence of this stressful event.

Circadian rhythms in serum and CSF cortisol of rhesus monkeys, and their modulation by timed injections of L-5-hydroxytryptophan.

Levels of in serum and cerebrospinal fluid have been studied in male and female rhesus monkeys. Untreated animals showed circadian rhythms of cortisol in both compartments, highest values occurring at 08.00 h and lowest at 20.00 h, but the decline following the morning peak was slower in cerebrospinal fluid (CSF) than in serum. Both levels and CSF/serum ratios (c. 0.017-0.027) were similar in males and females. The ratio between highest and lowest points on the circadian rhythm was greater for CSF (males: 2.50; females: 2.63) than for serum (1.69 and 1.78). There were significant correlations between CSF and serum levels in individual monkeys at each of the four time points studied. No circadian rhythm in CSF homovanillic acid (HVA) or 5-hydroxyindoleacetic acid (5-HIAA) was found, nor any correlation between these monoamine metabolites and cortisol levels. Injecting cortisol once daily in the evening (18.00h) resulted in greater proportional elevation in the CSF than in serum cortisol in samples taken two hours later, and the values in the two compartments were no longer correlated at this time. There was no effect on CSF 5-HIAA levels, Injecting L-5-hydroxytryptophan (L-5-HTP) (2.5 mg/kg) at four different time points produced abnormal daily patterns of cortisol secretion, the peak following the injection of L-5-HTP. The distortion of the normal circadian rhythm thus induced was greater in the CSF than in he serum, and CSF/serum ratios were increased one hour following L-5-HTP administration. The data suggested, but did not prove, that L-5-HTP injection may have produced the least Proportional elevation of cortisol at 08.00 h (at the time of normal daily maxima). 5-HIAA, but not HVA, was elevated one hour after L-5-HTP to 2-3 ties normal . A dose of 0.2 mg dexamethasone at 23.00 h suppressed cortisol levels in serum examined at 08.00 h the next day. This suppression was partially reversed by giving L-5-HTP one hour before taking the next morning's sample. Rhythmic and episodic changes in serum cortisol thus have a proportionally greater effect on the daily pattern of cortisol level in the CSF (and hence the cerebral compartment) than that in the vascular compartment, and thus the exposure of cortisol-sensitive tissues in the two compartments to cortisol may differ.

Endocrine responses and examination anxiety.

Endocrine and psychological function (measuring both affect and attitudes to study) were studied in 38 male medical students 4 weeks and 1-2 h before a major examination. Anxiety (or tension) and emotionality increased just before the examination, as did the 'denial' subscale of a 'coping' questionnaire. Serum cortisol and prolactin increased; serum testosterone and LH were unchanged. Both urinary noradrenaline and adrenaline were elevated. Increased cortisol correlated with increased prolactin across subjects; so, too, did levels of urinary noradrenaline and adrenaline, but the two sets of endocrine responses were not correlated with each other. Several of the trait scales predicted the endocrine response to the examination. The 'lie' scale of the Eysenck Personality Questionnaire correlated negatively with changes in both cortisol and prolactin, as did 'debilitating' anxiety, as defined by the Alpert-Haber scale. However, although there were no significant correlations between changes in hormone levels and those in any of the state scales, there was some relation between absolute hormone levels on the day of the examination. Measures of academic strategies or psychological responses to examinations do not predict the nature of the considerable hormonal response which occurs in this homogeneous set of high-achieving students.

Jugular foramen peripheral nerve sheath tumors.

Though jugular foramen nerve sheath tumors are uncommon, they involve a critical area of the skull base. Therefore, a precise classification system is needed to accurately define the extent of these tumors and reflect their surgical management. A series of seven cases is reviewed incorporating such a classification system to illustrate the management of these lesions using the infratemporal fossa type A approach.

Extended follow-up of total inferior turbinate resection for relief of chronic nasal obstruction.

Total inferior turbinectomy has been proposed as a treatment for chronic nasal airway obstruction refractory to other, more conservative, methods of treatment. Traditionally, it has been criticized because of its adverse effects on nasophysiology. In this study, patients who had previously undergone total inferior turbinectomy were evaluated with the use of an extensive questionnaire. It confirms that total inferior turbinectomy carries significant morbidity and should be condemned.

Transient salivary gland hypertrophy in bulimics.

Transient salivary gland hypertrophy is a reported clinical finding in patients with bulimia. A retrospective chart review of 49 patients enrolled in the University of Nebraska Medical Center Eating Disorders Program with a diagnosis of bulimia showed 29% (14/49) had at some time either parotid and/or submandibular gland hypertrophy noted on physical exam. Resolution of the salivary gland enlargement occurred in all of our patients after treatment of their bulimia. Bulimia must, therefore, be considered in the differential diagnosis of salivary gland hypertrophy, and treatment should be directed at the underlying behavioral disorder.

Early versus late gold weight implantation for rehabilitation of the paralyzed eyelid.

OBJECTIVES/HYPOTHESIS: The purpose of this study is to evaluate the outcomes and complications associated with early gold weight implantation for management of the paralyzed eyelid. STUDY DESIGN: A retrospective review of clinical charts was conducted to analyze results and complications in patients who underwent gold weight implantation within 30 days of onset of facial nerve paralysis and to compare these outcomes with those of patients who received gold weights after a traditional waiting period. METHODS: The charts of 67 patients who underwent gold weight implantation during the time period of this study were reviewed. Patients were categorized into "early" or "late" groups based on whether gold weights were implanted before or after 30 days following onset of facial nerve paralysis. Etiology of facial nerve paralysis, degree of paralysis, timing of surgery, and outcomes of the procedure, including degree of lid closure and complication rates, were compared between the two groups. RESULTS: Of the 67 patients, 49.3% underwent gold weight implantation within 30 days of onset of paralysis and 50.7% received gold weights after 30 days. A total of 89.2% of all patients who underwent implantation in this study achieved satisfactory lid closure after the initial procedure. Both early and late implantation groups had statistically similar lid closure and complication rates. CONCLUSIONS: Implantation of gold weights within 30 days of paralysis is as effective for the management of paralytic lagophthalmos as delayed implantation and is not associated with higher complication rates. Early implantation of gold weights should be considered in all patients with paralytic lagophthalmos.

Lightning and its effects on the auditory system.

Patients struck by lightning can present with a wide variety of unusual otologic problems including burns to the external auditory canal, tympanic membrane rupture, middle ear injury, and sensorineural hearing loss. Four patients who incurred various otologic problems, including one patient with previously unreported bilateral oval window fistulas following lightning injury, are presented. Audiologic, otologic, and surgical findings are reviewed as well as patient follow-up and outcome.