Molecular and Electronic Structures and Single-Molecule Magnet Behavior of Tris(thioether)-Iron Complexes Containing Redox-Active α-Diimine Ligands

Incorporating radical ligands into metal complexes is one of the emerging trends in the design of single-molecule magnets (SMMs). While significant effort has been expended to generate multinuclear transition metal-based SMMs with bridging radical ligands, less attention has been paid to mononuclear transition metal–radical SMMs. Herein, we describe the first α-diiminato radical-containing mononuclear transition metal SMM, namely, [κ2-PhTt tBu]­Fe­(AdNCHCHNAd) (1), and its analogue [κ2-PhTt tBu]­Fe­(CyNCHCHNCy) (2) (PhTt tBu = phenyltris­(tert-butylthiomethyl)­borate, Ad = adamantyl, and Cy = cyclohexyl). 1 and 2 feature nearly identical geometric and electronic structures, as shown by X-ray crystallography and electronic absorption spectroscopy. A more detailed description of the electronic structure of 1 was obtained through EPR and Mössbauer spectroscopies, SQUID magnetometry, and DFT, TD-DFT, and CAS calculations. 1 and 2 are best described as high-spin iron­(II) complexes with antiferromagnetically coupled α-diiminato radical ligands. A strong magnetic exchange coupling between the iron­(II) ion and the ligand radical was confirmed in 1, with an estimated coupling constant J \u3c −250 cm–1 (J = −657 cm–1, DFT). Calibrated CAS calculations revealed that the ground-state Fe­(II)−α-diiminato radical configuration has significant ionic contributions, which are weighted specifically toward the Fe­(I)-neutral α-diimine species. Experimental data and theoretical calculations also suggest that 1 possesses an easy-axis anisotropy, with an axial zero-field splitting parameter D in the range from −4 to–1 cm–1. Finally, dynamic magnetic studies show that 1 exhibits slow magnetic relaxation behavior with an energy barrier close to the theoretical maximum, 2|D|. These results demonstrate that incorporating strongly coupled α-diiminato radicals into mononuclear transition metal complexes can be an effective strategy to prepare SMMs

Systematic review and meta-analysis of reduction in all-cause mortality from walking and cycling and shape of dose response relationship

BACKGROUND AND OBJECTIVE: Walking and cycling have shown beneficial effects on population risk of all-cause mortality (ACM). This paper aims to review the evidence and quantify these effects, adjusted for other physical activity (PA). DATA SOURCES: We conducted a systematic review to identify relevant studies. Searches were conducted in November 2013 using the following health databases of publications: Embase (OvidSP); Medline (OvidSP); Web of Knowledge; CINAHL; SCOPUS; SPORTDiscus. We also searched reference lists of relevant texts and reviews. STUDY ELIGIBILITY CRITERIA AND PARTICIPANTS: Eligible studies were prospective cohort design and reporting walking or cycling exposure and mortality as an outcome. Only cohorts of individuals healthy at baseline were considered eligible. STUDY APPRAISAL AND SYNTHESIS METHODS: Extracted data included study population and location, sample size, population characteristics (age and sex), follow-up in years, walking or cycling exposure, mortality outcome, and adjustment for other co-variables. We used random-effects meta-analyses to investigate the beneficial effects of regular walking and cycling. RESULTS: Walking (18 results from 14 studies) and cycling (8 results from 7 studies) were shown to reduce the risk of all-cause mortality, adjusted for other PA. For a standardised dose of 11.25 MET.hours per week (or 675 MET.minutes per week), the reduction in risk for ACM was 11% (95% CI = 4 to 17%) for walking and 10% (95% CI = 6 to 13%) for cycling. The estimates for walking are based on 280,000 participants and 2.6 million person-years and for cycling they are based on 187,000 individuals and 2.1 million person-years. The shape of the dose-response relationship was modelled through meta-analysis of pooled relative risks within three exposure intervals. The dose-response analysis showed that walking or cycling had the greatest effect on risk for ACM in the first (lowest) exposure interval. CONCLUSIONS AND IMPLICATIONS: The analysis shows that walking and cycling have population-level health benefits even after adjustment for other PA. Public health approaches would have the biggest impact if they are able to increase walking and cycling levels in the groups that have the lowest levels of these activities. REVIEW REGISTRATION: The review protocol was registered with PROSPERO (International database of prospectively registered systematic reviews in health and social care) PROSPERO 2013: CRD42013004266

Modelling Future Coronary Heart Disease Mortality to 2030 in the British Isles.

OBJECTIVE: Despite rapid declines over the last two decades, coronary heart disease (CHD) mortality rates in the British Isles are still amongst the highest in Europe. This study uses a modelling approach to compare the potential impact of future risk factor scenarios relating to smoking and physical activity levels, dietary salt and saturated fat intakes on future CHD mortality in three countries: Northern Ireland (NI), Republic of Ireland (RoI) and Scotland. METHODS: CHD mortality models previously developed and validated in each country were extended to predict potential reductions in CHD mortality from 2010 (baseline year) to 2030. Risk factor trends data from recent surveys at baseline were used to model alternative future risk factor scenarios: Absolute decreases in (i) smoking prevalence and (ii) physical inactivity rates of up to 15% by 2030; relative decreases in (iii) dietary salt intake of up to 30% by 2030 and (iv) dietary saturated fat of up to 6% by 2030. Probabilistic sensitivity analyses were then conducted. RESULTS: Projected populations in 2030 were 1.3, 3.4 and 3.9 million in NI, RoI and Scotland respectively (adults aged 25-84). In 2030: assuming recent declining mortality trends continue: 15% absolute reductions in smoking could decrease CHD deaths by 5.8-7.2%. 15% absolute reductions in physical inactivity levels could decrease CHD deaths by 3.1-3.6%. Relative reductions in salt intake of 30% could decrease CHD deaths by 5.2-5.6% and a 6% reduction in saturated fat intake might decrease CHD deaths by some 7.8-9.0%. These projections remained stable under a wide range of sensitivity analyses. CONCLUSIONS: Feasible reductions in four cardiovascular risk factors (already achieved elsewhere) could substantially reduce future coronary deaths. More aggressive polices are therefore needed in the British Isles to control tobacco, promote healthy food and increase physical activity

Development of a Thin-Film Solar Cell Interconnect for the Powersphere Concept

Dual junction amorphous silicon (a-Si) solar cells produced on polyimide substrate have been selected as the best candidate to produce a lightweight solar array for the PowerSphere program. The PowerSphere concept features a space-inflatable, geodetic solar array approximately 0.6 meters in diameter and capable of generating about 20W of electrical power. Trade studies of various wiring concepts and connection methods led to an interconnect design with a copper contact that wraps around the edge, to the back of the solar cell. Applying Plasma Vapor Deposited (PVD) copper film to both sides and the edge of the solar cell produces the wrap around contact. This procedure results in a contact pad on the back of the solar cell, which is then laser welded to a flex circuit material. The flex circuit is constructed of copper in a custom designed routing pattern, and then sandwiched in a Kapton insulation layer. The flex circuit then serves as the primary power distribution system between the solar cells and the spacecraft. Flex circuit material is the best candidate for the wiring harness because it allows for low force deployment of the solar cells by the inflatable hinges on the PowerSphere. An additional frame structure, fabricated and assembled by ILC Dover, will reinforce the wrap around contact-flex blanket connection, thus providing a mechanically robust solar cell interconnect for the PowerSphere multifunctional program. The PowerSphere team will use the wraparound contact design approach as the primary solution for solar cell integration and the flex blanket for power distribution

Associated reading skills in children with a history of Specific Language Impairment (SLI)

A large cohort of 200 eleven-year-old children with Specific Language Impairment (SLI) were assessed on basic reading accuracy and on reading comprehension as well as language tasks. Reading skills were examined descriptively and in relation to early language and literacy factors. Using stepwise regression analyses in which age and nonverbal IQ were controlled for, it was found that a single word reading measure taken at 7 years was unsurprisingly a strong predictor of the two different types of reading ability. However, even with this measure included, a receptive syntax task (TROG) entered when reading accuracy score was the DV. Furthermore, a test of expressive syntax/narrative and a receptive syntax task completed at 7 years entered into the model for word reading accuracy. When early reading accuracy was excluded from the analyses, early phonological skills also entered as a predictor of both reading accuracy and comprehension at 11 years. The group of children with a history of SLI were then divided into those with no literacy difficulties at 11 and those with some persisting literacy impairment. Using stepwise logistic regression, and again controlling for IQ and age, 7 years receptive syntax score (but not tests of phonology, expressive vocabulary or expressive syntax/narrative) entered as a positive predictor of membership of the ‘no literacy problems’ group regardless of whether early reading accuracy was controlled for in step one. The findings are discussed in relation to the overlap of SLI and dyslexia and the long term sequelae of language impairment

A pilot randomised controlled trial of personalised care for depressed patients with symptomatic coronary heart disease in South London general practices: the UPBEAT-UK RCT protocol and recruitment.

ABSTRACT: Background: Community studies reveal people with coronary heart disease (CHD) are twice as likely to be depressed as the general population and that this co-morbidity negatively affects the course and outcome of both conditions. There is evidence for the efficacy of collaborative care and case management for depression treatment, and whilst NICE guidelines recommend these approaches only where depression has not responded to psychological, pharmacological, or combined treatments, these care approaches may be particularly relevant to the needs of people with CHD and depression in the earlier stages of stepped care in primary care settings. Methods: This pilot randomised controlled trial will evaluate whether a simple intervention involving a personalised care plan, elements of case management and regular telephone review is a feasible and acceptable intervention that leads to better mental and physical health outcomes for these patients. The comparator group will be usual general practitioner (GP) care. 81 participants have been recruited from CHD registers of 15 South London general practices. Eligible participants have probable major depression identified by a score of ≥8 on the Hospital Anxiety and Depression Scale depression subscale (HADS-D) together with symptomatic CHD identified using the Modified Rose Angina Questionnaire. Consenting participants are randomly allocated to usual care or the personalised care intervention which involves a comprehensive assessment of each participant’s physical and mental health needs which are documented in a care plan, followed by regular telephone reviews by the case manager over a 6-month period. At each review, the intervention participant’s mood, function and identified problems are reviewed and the case manager uses evidence based behaviour change techniques to facilitate achievement of goals specified by the patient with the aim of increasing the patient’s self efficacy to solve their problems. Depressive symptoms measured by HADS score will be collected at baseline and 1, 6- and 12 months post randomisation. Other outcomes include CHD symptoms, quality of life, wellbeing and health service utilisation. Discussion: This practical and patient-focused intervention is potentially an effective and accessible approach to the health and social care needs of people with depression and CHD in primary care. Trial registration: ISRCTN21615909

A 19-SNP coronary heart disease gene score profile in subjects with type 2 diabetes: the coronary heart disease risk in type 2 diabetes (CoRDia study) study baseline characteristics

Background The coronary risk in diabetes (CoRDia) trial (n = 211) compares the effectiveness of usual diabetes care with a self-management intervention (SMI), with and without personalised risk information (including genetics), on clinical and behavioural outcomes. Here we present an assessment of randomisation, the cardiac risk genotyping assay, and the genetic characteristics of the recruits. Methods Ten-year coronary heart disease (CHD) risk was calculated using the UKPDS score. Genetic CHD risk was determined by genotyping 19 single nucleotide polymorphisms (SNPs) using Randox’s Cardiac Risk Prediction Array and calculating a gene score (GS). Accuracy of the array was assessed by genotyping a subset of pre-genotyped samples (n = 185). Results Overall, 10-year CHD risk ranged from 2–72 % but did not differ between the randomisation groups (p = 0.13). The array results were 99.8 % concordant with the pre-determined genotypes. The GS did not differ between the Caucasian participants in the CoRDia SMI plus risk group (n = 66) (p = 0.80) and a sample of UK healthy men (n = 1360). The GS was also associated with LDL-cholesterol (p = 0.05) and family history (p = 0.03) in a sample of UK healthy men (n = 1360). Conclusions CHD risk is high in this group of T2D subjects. The risk array is an accurate genotyping assay, and is suitable for estimating an individual’s genetic CHD risk. Trial registration This study has been registered at ClinicalTrials.gov; registration identifier NCT0189178

Coding, Recording and Incidence of Different Forms of Coronary Heart Disease in Primary Care

To evaluate the coding, recording and incidence of coronary heart disease (CHD) in primary care electronic medical records.Data were drawn from the UK General Practice Research Database. Analyses evaluated the occurrence of 271 READ medical diagnostic codes, including categories for 'Angina', 'Myocardial Infarction', 'Coronary Artery Bypass Grafting' (CABG), 'percutaneous transluminal coronary angioplasty' (PCTA) and 'Other Coronary Heart Disease'. Time-to-event analyses were implemented to evaluate occurrences of different groups of codes after the index date.Among 300,020 participants aged greater than 30 years there were 75,197 unique occurrences of coronary heart disease codes in 24,244 participants, with 12,495 codes for incident events and 62,702 for prevalent events. Among incident event codes, 3,607 (28.87%) were for angina, 3,262 (26.11%) were for MI, 514 (4.11%) for PCTA, 161 (1.29%) for CABG and 4,951 (39.62%) were for 'Other CHD'. Among prevalent codes, 20,254 (32.30%) were for angina, 3,644 (5.81%) for MI, 34,542 (55.09%) for 'Other CHD' and 4,262 (6.80%) for CABG or PCTA. Among 3,685 participants initially diagnosed exclusively with 'Other CHD' codes, 17.1% were recorded with angina within 5 years, 5.6% with myocardial infarction, 6.3% with CABG and 8.6% with PCTA. From 2000 to 2010, the overall incidence of CHD declined, as did the incidence of angina, but the incidence of MI did not change. The frequency of CABG declined, while PCTA increased.In primary care electronic records, a substantial proportion of coronary heart disease events are recorded with codes that do not distinguish between different clinical presentations of CHD. The results draw attention to the need to improve coding practice in primary care. The results also draw attention to the importance of code selection in research studies and the need for sensitivity analyses using different sets of codes

Carbon stable isotope analysis of cereal remains as a way to reconstruct water availability: preliminary results

Reconstructing past water availability, both as rainfall and irrigation, is important to answer questions about the way society reacts to climate and its changes and the role of irrigation in the development of social complexity. Carbon stable isotope analysis of archaeobotanical remains is a potentially valuable method for reconstructing water availability. To further define the relationship between water availability and plant carbon isotope composition and to set up baseline values for the Southern Levant, grains of experimentally grown barley and sorghum were studied. The cereal crops were grown at three stations under five different irrigation regimes in Jordan. Results indicate that a positive but weak relationship exists between irrigation regime and total water input of barley grains, but no relationship was found for sorghum. The relationship for barley is site-specific and inter-annual variation was present at Deir ‘Alla, but not at Ramtha and Khirbet as-Samra

A statistical model to describe longitudinal and correlated metabolic risk factors: the Whitehall II prospective study.

Background Novel epidemiology models are required to link correlated variables over time, especially haemoglobin A1c (HbA1c) and body mass index (BMI) for diabetes prevention policy analysis. This article develops an epidemiology model to correlate metabolic risk factor trajectories. Method BMI, fasting plasma glucose, 2-h glucose, HbA1c, systolic blood pressure, total cholesterol and high density lipoprotein (HDL) cholesterol were analysed over 16 years from 8150 participants of the Whitehall II prospective cohort study. Latent growth curve modelling was employed to simultaneously estimate trajectories for multiple metabolic risk factors allowing for variation between individuals. A simulation model compared simulated outcomes with the observed data. Results The model identified that the change in BMI was associated with changes in glycaemia, total cholesterol and systolic blood pressure. The statistical analysis quantified associations among the longitudinal risk factor trajectories. Growth in latent glycaemia was positively correlated with systolic blood pressure and negatively correlated with HDL cholesterol. The goodness-of-fit analysis indicates reasonable fit to the data. Conclusions This is the first statistical model that estimates trajectories of metabolic risk factors simultaneously for diabetes to predict joint correlated risk factor trajectories. This can inform comparisons of the effectiveness and cost-effectiveness of preventive interventions, which aim to modify metabolic risk factors