Using remote substituents to control solution structure and anion binding in lanthanide complexes.

A study of the anion-binding properties of three structurally related lanthanide complexes, which all contain chemically identical anion-binding motifs, has revealed dramatic differences in their anion affinity. These arise as a consequence of changes in the substitution pattern on the periphery of the molecule, at a substantial distance from the binding pocket. Herein, we explore these remote substituent effects and explain the observed behaviour through discussion of the way in which remote substituents can influence and control the global structure of a molecule through their demands upon conformational space. Peripheral modifications to a binuclear lanthanide motif derived from α,α′-bis(DO3 Ayl)-m-xylene are shown to result in dramatic changes to the binding constant for isophthalate. In this system, the parent compound displays considerable conformational flexibility, yet can be assumed to bind to isophthalate through a well-defined conformer. Addition of steric bulk remote from the binding site restricts conformational mobility, giving rise to an increase in binding constant on entropic grounds as long as the ideal binding conformation is not excluded from the available range of conformers

Using Remote Substituents to Control Solution Structure and Anion Binding in Lanthanide Complexes

A study of the anion-binding properties of three structurally related lanthanide complexes, which all contain chemically identical anion-binding motifs, has revealed dramatic differences in their anion affinity. These arise as a consequence of changes in the substitution pattern on the periphery of the molecule, at a substantial distance from the binding pocket. Herein, we explore these remote substituent effects and explain the observed behaviour through discussion of the way in which remote substituents can influence and control the global structure of a molecule through their demands upon conformational space. Peripheral modifications to a binuclear lanthanide motif derived from α,α′-bis(DO3 Ayl)-m-xylene are shown to result in dramatic changes to the binding constant for isophthalate. In this system, the parent compound displays considerable conformational flexibility, yet can be assumed to bind to isophthalate through a well-defined conformer. Addition of steric bulk remote from the binding site restricts conformational mobility, giving rise to an increase in binding constant on entropic grounds as long as the ideal binding conformation is not excluded from the available range of conformers

The effectiveness and cost-effectiveness of a participative community singing programme as a health promotion initiative for older people: protocol for a randomised controlled trial

Background The growth in numbers of older people represents a considerable cost to health and social care services in the United Kingdom. There is an acknowledged need to address issues of social exclusion and both the physicial and mental health of this age group. In recent years there has been much interest in the potential contribution of the arts to the health of communities and individuals. There is some evidence that participative singing may be of benefit to older people, however studies to date are limited in number and have lacked rigour. There is therefore a need to build on this knowledge base to provide more quantifiable evidence of both effectiveness and cost efffectness of singing as a health intervention of this population group. Methods The proposed study is a pragmatic randomised controlled trial with two parallel arms. The primary hypothesis is that singing groups for older people improve both physical and mental aspects of qualaity of life when compared to usual activities. Potential participants will be volunteers over 60 years living in the community and recruited through publicity. Eligible and consenting participants will be randomized to either a singing group or a control group. Singing groups will take part in a twelve week planned programme of singing and control groups will continue with usual activities. The primary outcome measure will be the York SF-12, a health related quality of life measure which will be administered at baseline, three and six months after baseline. The study will evaluate both effectiveness and cost-effectiveness. Discussion This study proposes to add to the exisiting body of evidence on the value of singing for older people by using a rigorous methodological design, which includes a power calucation, a standardised intervention and assessment of cost-effectiveness. It should be regarded as a stage in a progressive programme of studies in this area. If group singing is found to be effective and cost-effective it may offer an alternative means to maintaining the health of people in later life

Variability in the Effect of 5-HTTLPR on Depression in a Large European Population: The Role of Age, Symptom Profile, Type and Intensity of Life Stressors.

BACKGROUND: Although 5-HTTLPR has been shown to influence the risk of life stress-induced depression in the majority of studies, others have produced contradictory results, possibly due to weak effects and/or sample heterogeneity. METHODS: In the present study we investigated how age, type and intensity of life-stressors modulate the effect of 5-HTTLPR on depression and anxiety in a European population cohort of over 2300 subjects. Recent negative life events (RLE), childhood adversity (CHA), lifetime depression, Brief Symptoms Inventory (BSI) depression and anxiety scores were determined in each subject. Besides traditional statistical analysis we calculated Bayesian effect strength and relevance of 5-HTTLPR genotypes in specified models. RESULTS: The short (s) low expressing allele showed association with increased risk of depression related phenotypes, but all nominally significant effects would turn to non-significant after correction for multiple testing in the traditional analysis. Bayesian effect strength and relevance analysis, however, confirmed the role of 5-HTTLPR. Regarding current (BSI) and lifetime depression 5-HTTLPR-by-RLE interactions were confirmed. Main effect, with other words direct association, was supported with BSI anxiety. With more frequent RLE the prevalence or symptoms of depression increased in ss carriers. Although CHA failed to show an interaction with 5-HTTLPR, in young subjects CHA sensitized towards the depression promoting effect of even mild RLE. Furthermore, the direct association of anxiety with the s allele was driven by young (</=30) individuals. LIMITATIONS: Our study is cross-sectional and applies self-report questionnaires. CONCLUSIONS: Albeit 5-HTTLPR has only weak/moderate effects, the s allele is directly associated with anxiety and modulates development of depression in homogeneous subgroups

New Insights into the Mechanism of Visible Light Photocatalysis

ABSTRACT: In recent years, the area of developing visible-lightactive photocatalysts based on titanium dioxide has been enormously investigated due to its wide range of applications in energy and environment related fields. Various strategies have been designed to efficiently utilize the solar radiation and to enhance the efficiency of photocatalytic processes. Building on the fundamental strategies to improve the visible light activity of TiO2-based photocatalysts, this Perspective aims to give an insight into many contemporary developments in the field of visible-light-active photocatalysis. Various examples of advanced TiO2 composites have been discussed in relation to their visible light induced photoconversion efficiency, dynamics of electron− hole separation, and decomposition of organic and inorganic pollutants, which suggest the critical need for further development of these types of materials for energy conversion and environmental remediation purposes

CHEMICAL CARTOGRAPHY with APOGEE: METALLICITY DISTRIBUTION FUNCTIONS and the CHEMICAL STRUCTURE of the MILKY WAY DISK

Using a sample of 69,919 red giants from the SDSS-III/APOGEE Data Release 12, we measure the distribution of stars in the [/Fe] versus [Fe/H] plane and the metallicity distribution functions (MDFs) across an unprecedented volume of the Milky Way disk, with radius 3 < R < 15 kpc and height kpc. Stars in the inner disk (R < 5 kpc) lie along a single track in [/Fe] versus [Fe/H], starting with -enhanced, metal-poor stars and ending at [/Fe] ∼ 0 and [Fe/H] ∼ +0.4. At larger radii we find two distinct sequences in [/Fe] versus [Fe/H] space, with a roughly solar- sequence that spans a decade in metallicity and a high- sequence that merges with the low- sequence at super-solar [Fe/H]. The location of the high- sequence is nearly constant across the disk

Depression care management for late-life depression in China primary care: Protocol for a randomized controlled trial

<p>Abstract</p> <p>Background</p> <p>As a major public health issue in China and worldwide, late-life depression is associated with physical limitations, greater functional impairment, increased utilization and cost of health care, and suicide. Like other chronic diseases in elders such as hypertension and diabetes, depression is a chronic disease that the new National Health Policy of China indicates should be managed in primary care settings. Collaborative care, linking primary and mental health specialty care, has been shown to be effective for the treatment of late-life depression in primary care settings in Western countries. The primary aim of this project is to implement a depression care management (DCM) intervention, and examine its effectiveness on the depressive symptoms of older patients in Chinese primary care settings.</p> <p>Methods/Design</p> <p>The trial is a multi-site, primary clinic based randomized controlled trial design in Hangzhou, China. Sixteen primary care clinics will be enrolled in and randomly assigned to deliver either DCM or care as usual (CAU) (8 clinics each) to 320 patients (aged ≥ 60 years) with major depression (20/clinic; n = 160 in each treatment condition). In the DCM arm, primary care physicians (PCPs) will prescribe 16 weeks of antidepressant medication according to the treatment guideline protocol. Care managers monitor the progress of treatment and side effects, educate patients/family, and facilitate communication between providers; psychiatrists will provide weekly group psychiatric consultation and CM supervision. Patients in both DCM and CAU arms will be assessed by clinical research coordinators at baseline, 4, 8, 12, 18, and 24 months. Depressive symptoms, functional status, treatment stigma and clients' satisfaction will be used to assess patients' outcomes; and clinic practices, attitudes/knowledge, and satisfaction will be providers' outcomes.</p> <p>Discussion</p> <p>This will be the first trial of the effectiveness of a collaborative care intervention aiming to the management of late-life depression in China primary care. If effective, its finding will have relevance to policy makers who wish to scale up DCM treatments for late-life depression in national wide primary care across China.</p> <p>Study Registration</p> <p>The DCM project is registered through the National Institutes of Health sponsored by clinical trials registry and has been assigned the identifier: <a href="http://www.clinicaltrials.gov/ct2/show/NCT01287494">NCT01287494</a></p

Roadmap on Photovoltaic Absorber Materials for Sustainable Energy Conversion

Photovoltaics (PVs) are a critical technology for curbing growing levels of anthropogenic greenhouse gas emissions, and meeting increases in future demand for low-carbon electricity. In order to fulfil ambitions for net-zero carbon dioxide equivalent (CO2eq) emissions worldwide, the global cumulative capacity of solar PVs must increase by an order of magnitude from 0.9 TWp in 2021 to 8.5 TWp by 2050 according to the International Renewable Energy Agency, which is considered to be a highly conservative estimate. In 2020, the Henry Royce Institute brought together the UK PV community to discuss the critical technological and infrastructure challenges that need to be overcome to address the vast challenges in accelerating PV deployment. Herein, we examine the key developments in the global community, especially the progress made in the field since this earlier roadmap, bringing together experts primarily from the UK across the breadth of the photovoltaics community. The focus is both on the challenges in improving the efficiency, stability and levelized cost of electricity of current technologies for utility-scale PVs, as well as the fundamental questions in novel technologies that can have a significant impact on emerging markets, such as indoor PVs, space PVs, and agrivoltaics. We discuss challenges in advanced metrology and computational tools, as well as the growing synergies between PVs and solar fuels, and offer a perspective on the environmental sustainability of the PV industry. Through this roadmap, we emphasize promising pathways forward in both the short- and long-term, and for communities working on technologies across a range of maturity levels to learn from each other.Comment: 160 pages, 21 figure

Robust estimation of bacterial cell count from optical density

Optical density (OD) is widely used to estimate the density of cells in liquid culture, but cannot be compared between instruments without a standardized calibration protocol and is challenging to relate to actual cell count. We address this with an interlaboratory study comparing three simple, low-cost, and highly accessible OD calibration protocols across 244 laboratories, applied to eight strains of constitutive GFP-expressing E. coli. Based on our results, we recommend calibrating OD to estimated cell count using serial dilution of silica microspheres, which produces highly precise calibration (95.5% of residuals &lt;1.2-fold), is easily assessed for quality control, also assesses instrument effective linear range, and can be combined with fluorescence calibration to obtain units of Molecules of Equivalent Fluorescein (MEFL) per cell, allowing direct comparison and data fusion with flow cytometry measurements: in our study, fluorescence per cell measurements showed only a 1.07-fold mean difference between plate reader and flow cytometry data

Associations between hippocampal morphology, diffusion characteristics, and salivary cortisol in older men

High, unabated glucocorticoid (GC) levels are thought to selectively damage certain tissue types. The hippocampus is thought to be particularly susceptible to such effects, and though findings from animal models and human patients provide some support for this hypothesis, evidence for associations between elevated GCs and lower hippocampal volumes in older age (when GC levels are at greater risk of dysregulation) is inconclusive. To address the possibility that the effects of GCs in non-pathological ageing may be too subtle for gross volumetry to reliably detect, we analyse associations between salivary cortisol (diurnal and reactive measures), hippocampal morphology and diffusion characteristics in 88 males, aged ∼73 years. However, our results provide only weak support for this hypothesis. Though nominally significant peaks in morphology were found in both hippocampi across all salivary cortisol measures (standardised β magnitudes < 0.518, p(uncorrected) > 0.0000003), associations were both positive and negative, and none survived false discovery rate correction. We found one single significant association (out of 12 comparisons) between a general measure of hippocampal diffusion and reactive cortisol slope (β = 0.290, p = 0.008) which appeared to be driven predominantly by mean diffusivity but did not survive correction for multiple testing. The current data therefore do not clearly support the hypothesis that elevated cortisol levels are associated with subtle variations in hippocampal shape or microstructure in non-pathological older age