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A new family of cyclometallated gold(III) thiolato complexes based on pyrazine-centred pincer ligands has been prepared, (C^Npz ^C)AuSR, where C^Npz ^C=2,6-bis(4-But C6 H4 )pyrazine dianion and R=Ph (1), C6 H4 tBu-4 (2), 2-pyridyl (3), 1-naphthyl (1-Np, 4), 2-Np (5), quinolinyl (Quin, 6), 4-methylcoumarinyl (Coum, 7) and 1-adamantyl (8). The complexes were isolated as yellow to red solids in high yields using mild synthetic conditions. The single-crystal X-ray structures revealed that the colour of the deep-red solids is associated with the formation of a particular type of short (3.2-3.3â Å) intermolecular pyrazineâ â â pyrazine π-interactions. In some cases, yellow and red crystal polymorphs were formed; only the latter were emissive at room temperature. Combined NMR and UV/Vis techniques showed that the supramolecular π-stacking interactions persist in solution and give rise to intense deep-red photoluminescence. Monomeric molecules show vibronically structured green emissions at low temperature, assigned to ligand-based 3 IL(C^N^C) triplet emissions. By contrast, the unstructured red emissions correlate mainly with a 3 LLCT(SRâ{(C^Npz ^C)2 }) charge transfer transition from the thiolate ligand to the πâ â â π dimerized pyrazine. Unusually, the π-interactions can be influenced by sample treatment in solution, such that the emissions can switch reversibly from red to green. To our knowledge this is the first report of aggregation-enhanced emission in gold(III) chemistry.
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Introduction: Policies aiming to prevent ill health and reduce health inequalities need to consider the full complexity of health systems, including environmental determinants. A learning health system that incorporates environmental factors needs healthcare, social care and non-health data linkage at individual and small-area levels. Our objective was to establish privacy-preserving household record linkage for England to ensure person-level data remain secure and private when linked with data from households or the wider environment. Methods: A stakeholder workshop with participants from our regional health board, together with the regional data processor, and the national data provider. The workshop discussed the risks and benefits of household linkages. This group then co-designed actionable dataflows between national and local data controllers and processors. Results: A process was defined whereby the Personal Demographics Service, which includes the addresses of all patients of the National Health Service (NHS) in England, was used to match patients to a home identifier, for the time they are recorded as living at that address. Discussions with NHS England resulted in secure and quality-assured data linkages and a plan to flow these pseudonymised data onwards into regional health boards. Methods were established, including the generation of matching algorithms, transfer processes and information governance approvals. Our collaboration accelerated the development of a new data governance application, facilitating future public health intervention evaluations. Conclusion: These activities have established a secure method for protecting the privacy of NHS patients in England, while allowing linkage of wider environmental data. This enables local health systems to learn from their data and improve health by optimizing non-health factors. Proportionate governance of health and linked non-health data is practical in England for incorporating key environmental factors into a learning health system.
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BACKGROUND: Many health systems are experimenting with integrated care models to improve outcomes and reduce healthcare demand. Evidence for effects on health service utilisation is variable, with few studies investigating impacts on mortality or differences by socioeconomic group. OBJECTIVE: To examine the impact of a multidisciplinary, integrated care team intervention on emergency admissions and mortality, and whether effects differed by deprivation group. DESIGN: A longitudinal matched controlled study using difference-in-differences analysis comparing the change in unplanned emergency admissions twelve months before and after the intervention, and inverse probability of treatment-weighted survival analysis comparing mortality, between intervention and matched control groups. SETTING: A relatively deprived city in England, U.K. INTERVENTION: A case-management integrated care programme delivered through multidisciplinary teams and aimed at complex needs and/or high hospitalisation risk patients. RESULTS: The intervention was associated with a small increase in emergency admissions of 15 per 1,000 patients per month (95% CI 5 to 24, p = 0.003) after the intervention relative to the control group and no significant change in survival between intervention and control groups (HR 0.9, 95% CI 0.84 to 1.13, p = 0.7). Effects were similar across age and deprivation groups. CONCLUSIONS: It is unlikely that similar interventions lead to reduced emergency admissions or increased survival. Further studies should use experimental methods and assess impacts on quality of life.
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Prestação Integrada de Cuidados de Saúde , Qualidade de Vida , Serviço Hospitalar de Emergência , Hospitalização , Hospitais , Humanos , Estudos LongitudinaisRESUMO
OBJECTIVE: To assess the effect of a real world, ongoing telehealth service on the use of secondary healthcare. DESIGN: A retrospective observational study with anonymous matched controls. SETTING: Primary and community healthcare. Patients were recruited over 4 years in 89 general practices in Liverpool, UK and remotely managed by a dedicated clinical team in Liverpool Community Health. PARTICIPANTS: 5154 patients with chronic obstructive pulmonary disease, heart failure or diabetes were enrolled in the programme, of whom 3562 satisfied the inclusion criteria of this study. INTERVENTION: At least 9 weeks of telehealth including vital sign collection, questionnaires, education, support and informal coaching by clinical staff. PRIMARY OUTCOME: Reduction in the number of emergency admissions in the 12 months after start, compared with the year before start. Secondary subgroup analysis to improve future targeting and personalisation of the service. RESULT: The average number of emergency admissions for the intervention group at baseline is 0.35, 95% CI 0.32 to 0.38. The differential decrease in emergency admissions in the intervention group in comparison with the control group, the average treatment effect, is 0.08, 95 CI 0.05 to 0.11, corresponding to an average percentage decrease of 22.7%. In subgroup analysis, a score is calculated that can be used prospectively to predict individual benefit from the intervention. Patients with an above median score (37%) are predicted average reduction in emergency admissions of 0.15, 95% CI 0.09 to 0.2, corresponding to a percentage decrease in admissions of 25.3%. CONCLUSION: The telehealth intervention has a positive impact across a wide cohort of patients with different diseases. Prospective scoring of patients and allocation to targeted telehealth interventions is likely to improve the effectiveness and efficiency of the service.