Understanding Color Tuning and Reversible Oxidation of Conjugated Azomethines.

With the aim of achieving reversible oxidation and color tuning, the effect of the central aromatic on the spectroscopic, electrochemical, and spectrochemical properties of a series of electrochromic azomethine triads was investigated. The absorption of the alkylated thiophene derivatives was blue-shifted relative to their unalkylated counterparts when the central aromatic was either a bi- or terthiophene. It was further found that the alkylated thiophene derivatives had larger Stokes shifts than their unsubstituted counterparts. Theoretical calculations demonstrated that the torsion angles of these alkylated cores with respect to the flanking azomethines were responsible for the spectroscopic effects. While the electrochemical oxidation potential of the triads varied by only 100 mV, the reversibility of their anodic process was contingent on the central aromatic. The absorption of the electrochemically produced state red-shifted between 165 and 280 nm from its corresponding neutral state, leading to perceived color changes between orange and blue. Reversible color changes were chemically mediated with ferric chloride/hydrazine. The absorption of the chemically oxidized state shifted between 155 and 220 nm from the corresponding neutral state, contingent on the central aromatic. The palette of perceived colors that was possible with oxidation included orange, yellow, blue, and gray.

Unusually high fluorescence quantum yield of a homopolyfluorenylazomethine--towards a universal fluorophore.

The absolute fluorescence quantum yield (Φfl) of a polyfluorenyl azomethine homopolymer was measured as a function of solvent polarity. The solvent induced and temperature dependent fluorescence of the homopolymer were also investigated and they were compared to the corresponding monomer and copolymer. The Φfl of the homopolymer was consistent (45-70%), regardless of solvent polarity with Stokes shifts up to 7460 cm(-1) in ethanol. In contrast, the Φfl of its corresponding monomer decreased from 60% in ethanol to 1% in toluene, whereas a Φfl < 5% for its analogous copolymer was measured. Moderate fluorescence yields (Φfl ≈ 25%) were also possible in thin film when co-depositing the homopolymer with PMMA. Cryofluorescence was used to probe the excited state deactivation modes. Deactivation by internal conversion was found to compete with fluorescence. The fluorescence deactivation pathways of the homopolymer and its corresponding monomer could be suppressed at 77 K, resulting in fluorescence turn-on. Both fluorophores were found to detect nitroaromatics.

Educator appraisal--occurrence and experience of hospital consultants in north-west England.

BACKGROUND: It is recommended all hospital consultants with educational responsibilities undergo appraisal of their educational role by their employer: a key component of revalidation. To support this process locally, the North Western Deanery developed guidance on educational appraisal. We wished to establish the frequency and perceived value of educator appraisal. METHODS: A web-based questionnaire of 605 hospital consultants with educational responsibilities in north-western England was conducted to collect data. RESULTS: Only 17.7% had been appraised for their educational responsibilities in the previous 36 months despite 92.7% undergoing appraisal of clinical work. Educational leads were statistically more likely to have had educational appraisal than educational supervisors (ES), similarly ES were more likely to have had appraisal than clinical supervisors (CS). Clinical specialty does not appear to be a major determining factor. The majority found the supporting documentation helpful in guiding data collection and subsequent recording of evidence. All respondents felt appraisals were conducted in a supportive manner with 76.6% stating appraisal had reassured them they were fulfilling their educational roles and helped 78.5% to identify an education personal development plan. CONCLUSIONS: The incidence of educator appraisal remains low but the experience is considered valuable and contributes effectively to educators' professional development.

Twelve tips for junior doctors interested in a career in medical education.

BACKGROUND: As with the many specialities within medicine, the expanding field of medical education is becoming a more formal and professionalised arena. AIM: This article aims to assist junior doctors wishing to pursue formal educational roles in their future careers. METHODS: We offer twelve tips for junior doctors with these aspirations in mind, exploring a range of potential roles, resources and opportunities available. RESULTS: Twelve practical suggestions on how junior doctors can nurture their portfolios of evidence and subsequent future careers in medical education. CONCLUSIONS: The developing world of medical education is becoming evermore structured and professionalised. Educators of the future will need to demonstrate evidence of their knowledge, skills and experience in the field in order to effectively assume and perform educational roles.

Conjugated 4-methoxybipyrrole thiophene azomethines: synthesis, opto-electronic properties, and crystallographic characterization.

In the search of functional materials with improved electrochromic properties, thiophenes and asymmetric bipyrroles have been conjugated with azomethine units. 4-Methoxy-2,2'-bipyrroles 3-6 were first synthesized by a general route from 4-hydroxyproline and converted subsequently to dialdehydes 8-15, which underwent condensations with different aminothiophenes to provide azomethine conjugates 14-18 and 20-22. The crystallization and X-ray analysis of 20 showed the heterocycles and azomethine bonds were all co-planar with the heterocycles adopting an anti-parallel arrangement. These configurations result in extended conjugation and enhanced opto-electronic properties of the azomethines. Oxidation potential (E(pa)) was tailored by modification of the substitution pattern of the terminal thiophenes and central pyrroles of the azomethines. The combined low E(pa) and extended azomethine degree of conjugation resulted in stark color transitions occurring between their neutral and oxidized states. Reversible color formation was induced both electrochemically and by doping/de-doping with trifluoroacetic acid/triethylamine.

Challenges to the provision of emergency obstetric care in Iraq.

To assess the availability of, and challenges to the provision of emergency obstetric care in order to raise awareness and assist policy-makers and development partners in making appropriate decisions to help pregnant women in Iraq. Descriptive and exploratory study based on self-administered questionnaires, an in-depth interview and a Focus Group Discussion. The setting was 19 major hospitals in 8 out of the 18 Governorates and the participants were 31 Iraqi doctors and 1 midwife. The outcome measures were availability of emergency obstetric care (EOC) in hospitals and challenges to the provision of EOC. Only 26.3% (5/19) of hospitals had been able to provide all the 8 signal functions of comprehensive emergency obstetric care in the previous 3 months. All the 19 hospitals provided parenteral antibiotics and uterine evacuation, 94.7% (18/19) were able to provide parenteral oxytocics and perform manual removal of retained placenta, magnesium sulphate for eclampsia was available in 47.4% (9/19) of hospitals, 42.1% (8/19) provided assisted vaginal delivery, 26.5% (5/19) provided blood transfusion and 89.5% (17/19) offered Caesarean section. The identified challenges for health care providers include difficulties travelling to work due to frequent checkpoints and insecurity, high level of insecurity for patients referred or admitted to hospitals, inadequate staffing due mainly to external migration and premature deaths as a result of the war, lack of drugs, supplies and equipment (including blood for transfusion), and falling standards of training and regulation. Most women and their families do not currently have access to comprehensive emergency obstetric care. Health care providers recommend reconstruction and strengthening of all components of the Iraqi health system which may only be achieved if security returns to the country.

Publisher Correction: Common schizophrenia alleles are enriched in mutation-intolerant genes and in regions under strong background selection.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Common schizophrenia alleles are enriched in mutation-intolerant genes and in regions under strong background selection.

Schizophrenia is a debilitating psychiatric condition often associated with poor quality of life and decreased life expectancy. Lack of progress in improving treatment outcomes has been attributed to limited knowledge of the underlying biology, although large-scale genomic studies have begun to provide insights. We report a new genome-wide association study of schizophrenia (11,260 cases and 24,542 controls), and through meta-analysis with existing data we identify 50 novel associated loci and 145 loci in total. Through integrating genomic fine-mapping with brain expression and chromosome conformation data, we identify candidate causal genes within 33 loci. We also show for the first time that the common variant association signal is highly enriched among genes that are under strong selective pressures. These findings provide new insights into the biology and genetic architecture of schizophrenia, highlight the importance of mutation-intolerant genes and suggest a mechanism by which common risk variants persist in the population.

Mothers' narratives about having a child with cancer: A view through the attachment lens.

This study explored mothers' narratives about having a child with cancer through the novel addition of an attachment lens. Six mothers were interviewed about their experiences. Their pattern of attachment was assessed through a separate interview using the Dynamic-Maturational Model of adult attachment. The results showed marked differences in themes and performative aspects between the narratives of mothers classified as Type B pattern of attachment, balanced integration of affect and cognition, and those classified as Type A, focus on cognition and dismissal of affect. For mothers classified as Type B, narrative themes of 'protecting my child' and 'questioning and evaluating the experience' were identified. Mothers classified as Type A discussed narrative themes of 'being strong and positive' and 'playing down feelings'. The presence of unresolved childhood loss or trauma appeared to inhibit ability to construct a coherent and temporally ordered narrative. It was also possible to observe attachment-based strategies operating within these narratives. Clinical implications of the work are discussed.

High-efficiency particulate arrest-filter vacuum cleaners increase personal cat allergen exposure in homes with cats.

BACKGROUND: On the basis of experimental chamber studies, vacuum cleaners with double-thickness bags and integral high-efficiency particulate arrest (HEPA) air filters are claimed to reduce airborne allergen levels and are currently recommended to allergic patients. OBJECTIVES: The objective of this study was to investigate the effect of vacuum cleaning on personal inhaled cat allergen exposure in homes with cats. METHODS: Five unused new vacuum cleaners were compared with an old non-HEPA filter vacuum cleaner. Each vacuum cleaner was tested in an experimental chamber and in 5 homes with cats. Inhaled cat allergen was measured by nasal air sampling. RESULTS: New vacuum cleaners failed to leak any allergen in the experimental chamber. There was a significant increase in inhaled cat allergen during vacuum cleaning in homes (F = 48.39, df = 1.4, P =.002) with no difference between the old vacuum cleaner and the unused new vacuum cleaners (5-fold and 3-fold increase compared to baseline, respectively; F = 0.005, df = 1.4, P =.95). CONCLUSIONS: The use of new HEPA-filter vacuum cleaners increases inhaled cat allergen in homes with cats. The use of HEPA-filter modern vacuum cleaners to reduce pet allergen exposure in the homes of pet owners should not be justified merely on the basis of experimental chamber data.