IONIZATION MEASUREMENT AND SPECTROSCOPY OF ThS AND ThS+^+

Author Institution: Department of Chemistry, Emory University, Atlanta; Ga 30322Gas-phase thorium sulfide has been produced via laser ablation of thorium in a jet-cooled expansion of 0.1\% H$_2$S/He carrier gas. Electronic spectra have been recorded for the first time by laser-induced fluorescence (LIF) over the region 17500-23650 cm$^{-1}$. Resonance-enhanced multiphoton ionization (REMPI) was used in conjunction with a Wiley-McLaren time-of-flight mass spectrometer to confirm LIF assigments of seven rotationally-resolved bands belonging to ThS. Dispersing fluorescence from the \italic{[22.13]}$^1$$\Pi$-\italic{X}$^1$$\Sigma$$_g$ transition revealed a vibrational progression of the ground electronic state of ThS, for which the vibrational constants were $\omega$$_e$ = 520.0(7) cm$^{-1}$ and $\omega$$_e$$\chi$$_e$ = 11.0(9) cm$^{-1}$. An accurate value for the ionization potential of ThS as well as term energies of ThS$^+$ up to v$^+$ = 7 in the $^2$$\Sigma$$^+$ ground state and v$^+$ = 3 in the $^2$$\Delta$$_{3/2}$ first excited state have been obtained using two-photon pulsed-field ionization zero kinetic energy photoelectron spectroscopy (PFI-ZEKE). Vibrational constants for these states have also been detemined. High-level electronic structure calculations performed for ThS and ThS$^+$ gave term energies and molecular parameters that are in excellent agreement with the experimental results. The change in bond characteristics upon ionization of ThS is found to be consistent with that observed for HfO, HfS, and ThO

Estimating the incidence, prevalence and true cost of asthma in the UK: secondary analysis of national stand-alone and linked databases in England, Northern Ireland, Scotland and Wales-a study protocol.

INTRODUCTION: Asthma is now one of the most common long-term conditions in the UK. It is therefore important to develop a comprehensive appreciation of the healthcare and societal costs in order to inform decisions on care provision and planning. We plan to build on our earlier estimates of national prevalence and costs from asthma by filling the data gaps previously identified in relation to healthcare and broadening the field of enquiry to include societal costs. This work will provide the first UK-wide estimates of the costs of asthma. In the context of asthma for the UK and its member countries (ie, England, Northern Ireland, Scotland and Wales), we seek to: (1) produce a detailed overview of estimates of incidence, prevalence and healthcare utilisation; (2) estimate health and societal costs; (3) identify any remaining information gaps and explore the feasibility of filling these and (4) provide insights into future research that has the potential to inform changes in policy leading to the provision of more cost-effective care. METHODS AND ANALYSIS: Secondary analyses of data from national health surveys, primary care, prescribing, emergency care, hospital, mortality and administrative data sources will be undertaken to estimate prevalence, healthcare utilisation and outcomes from asthma. Data linkages and economic modelling will be undertaken in an attempt to populate data gaps and estimate costs. Separate prevalence and cost estimates will be calculated for each of the UK-member countries and these will then be aggregated to generate UK-wide estimates. ETHICS AND DISSEMINATION: Approvals have been obtained from the NHS Scotland Information Services Division's Privacy Advisory Committee, the Secure Anonymised Information Linkage Collaboration Review System, the NHS South-East Scotland Research Ethics Service and The University of Edinburgh's Centre for Population Health Sciences Research Ethics Committee. We will produce a report for Asthma-UK, submit papers to peer-reviewed journals and construct an interactive map

Operation and recovery of a seasonally-loaded UK waste stabilisation pond system

An intermittent discharge waste stabilisation pond system was trialled for treatment of a seasonal wastewater load from a campsite. The system showed rapid acclimatisation to incoming load, with chlorophyll-a exceeding 700 mg l?1 within 2 weeks and filtered and unfiltered effluent biochemical oxygen demand below 20 and 30 mg l?1 respectively. Good performance continued for some weeks, after which photosynthetic oxygenation capacity in the first pond was seriously impaired by a shock loading believed to include fatty material. Inflow to the system was suspended and a surface film was broken up, after which the pond recovered within an 8-day period. Laboratory experiments indicated that interventions such as artificial aeration and dilution with effluent had no beneficial effect although mixing may have increased the rate of recovery

Anaerobic digestion of whole-crop winter wheat silage for renewable energy production

With biogas production expanding across Europe in response to renewable energy incentives, a wider variety of crops need to be considered as feedstock. Maize, the most commonly used crop at present, is not ideal in cooler, wetter regions, where higher energy yields per hectare might be achieved with other cereals. Winter wheat is a possible candidate because, under these conditions, it has a good biomass yield, can be ensiled, and can be used as a whole crop material. The results showed that, when harvested at the medium milk stage, the specific methane yield was 0.32 m3 CH4 kg–1 volatile solids added, equal to 73% of the measured calorific value. Using crop yield values for the north of England, a net energy yield of 146–155 GJ ha–1 year–1 could be achieved after taking into account both direct and indirect energy consumption in cultivation, processing through anaerobic digestion, and spreading digestate back to the land. The process showed some limitations, however: the relatively low density of the substrate made it difficult to mix the digester, and there was a buildup of soluble chemical oxygen demand, which represented a loss in methane potential and may also have led to biofoaming. The high nitrogen content of the wheat initially caused problems, but these could be overcome by acclimatization. A combination of these factors is likely to limit the loading that can be applied to the digester when using winter wheat as a substrat

Study protocol for a cluster randomised controlled feasibility trial evaluating personalised care planning for older people with frailty: PROSPER V2 27/11/18

Background Frailty is characterised by increased vulnerability to falls, disability, hospitalisation and care home admission. However, it is relatively reversible in the early stages. Older people living with frailty often have multiple health and social issues which are difficult to address but could benefit from proactive, person-centred care. Personalised care planning aims to improve outcomes through better self-management, care coordination and access to community resources. Methods This feasibility cluster randomised controlled trial aims to recruit 400 participants from 11 general practice clusters across Bradford and Leeds in the north of England. Eligible patients will be aged over 65 with an electronic frailty index score of 0.21 (identified via their electronic health record), living in their own homes, without severe cognitive impairment and not in receipt of end of life care. After screening for eligible patients, a restricted 1:1 cluster-level randomisation will be used to allocate practices to the PROSPER intervention, which will be delivered over 12 weeks by a personal independence co-ordinator worker, or usual care. Following initial consent, participants will complete a baseline questionnaire in their own home including measures of health-related quality of life, activities of daily living, depression and health and social care resource use. Follow-up will be at six and 12 months. Feasibility outcomes relate to progression criteria based around recruitment, intervention delivery, retention and follow-up. An embedded process evaluation will contribute to iterative intervention optimisation and logic model development by examining staff training, intervention implementation and contextual factors influencing delivery and uptake of the intervention. Discussion Whilst personalised care planning can improve outcomes in long-term conditions, implementation in routine settings is poor. We will evaluate the feasibility of conducting a cluster randomised controlled trial of personalised care planning in a community population based on frailty status. Key objectives will be to test fidelity of trial design, gather data to refine sample size calculation for the planned definitive trial, optimise data collection processes and optimise the intervention including training and delivery. Trial registration ISRCTN12363970 – 08/11/18

The politics of health services research: health professionals as hired hands in a commissioned research project in England

Previous health services research has failed to account for the role played by clinical staff in the collection of data. In this paper we use the work of Roth on hired hand research to examine the politics of evidence production within health services research. Sociologies of work predict lack of engagement in the research tasks by subordinated groups of workers. We examine the role of midwives in researching ante-natal screening for sickle cell and thalassaemia in England, and construct three ideal types: repairers, refractors, and resisters to account for the variable engagement of health staff with research. We find some features of the hired hand phenomenon predicted by Roth to be in evidence, and suggest that the context of our project is similar to much health services research. We conclude that without concerted attempts (1) to change the social relations of research production; (2) to mitigate hired hand effects; (3) to assess the impact of the hired hand effect on the validity and reliability of findings, and (4) to report on these limitations, that health services research involving large teams of subordinated clinical staff as data collectors will be prone to produce evidence that is of limited trustworthiness. Keywords: evidence-based research; health services research; hired hands; politics of evidence; screening; midwives; research methodology; work and employment

Electronic Structure and Bonding of Icosahedral Core-Shell Gold-Silver Nanoalloy Clusters Au_(144-x)Ag_x(SR)_60

Atomically precise thiolate-stabilized gold nanoclusters are currently of interest for many cross-disciplinary applications in chemistry, physics and molecular biology. Very recently, synthesis and electronic properties of "nanoalloy" clusters Au_(144-x)Ag_x(SR)_60 were reported. Here, density functional theory is used for electronic structure and bonding in Au_(144-x)Ag_x(SR)_60 based on a structural model of the icosahedral Au_144(SR)_60 that features a 114-atom metal core with 60 symmetry-equivalent surface sites, and a protecting layer of 30 RSAuSR units. In the optimal configuration the 60 surface sites of the core are occupied by silver in Au_84Ag_60(SR)_60. Silver enhances the electron shell structure around the Fermi level in the metal core, which predicts a structured absorption spectrum around the onset (about 0.8 eV) of electronic metal-to-metal transitions. The calculations also imply element-dependent absorption edges for Au(5d) \rightarrow Au(6sp) and Ag(4d) \rightarrow Ag(5sp) interband transitions in the "plasmonic" region, with their relative intensities controlled by the Ag/Au mixing ratio.Comment: 4 figure

Medical communication and technology: a video-based process study of the use of decision aids in primary care

Background: much of the research on decision-making in health care has focused on consultation outcomes. Less is known about the process by which clinicians and patients come to a treatment decision. This study aimed to quantitatively describe the behaviour shown by doctors and patients during primary care consultations when three types of decision aids were used to promote treatment decision-making in a randomised controlled trial.Methods: a video-based study set in an efficacy trial which compared the use of paper-based guidelines (control) with two forms of computer-based decision aids (implicit and explicit versions of DARTS II). Treatment decision concerned warfarin anti-coagulation to reduce the risk of stroke in older patients with atrial fibrillation. Twenty nine consultations were video-recorded. A ten-minute 'slice' of the consultation was sampled for detailed content analysis using existing interaction analysis protocols for verbal behaviour and ethological techniques for non-verbal behaviour.Results: median consultation times (quartiles) differed significantly depending on the technology used. Paper-based guidelines took 21 (19–26) minutes to work through compared to 31 (16–41) minutes for the implicit tool; and 44 (39–55) minutes for the explicit tool. In the ten minutes immediately preceding the decision point, GPs dominated the conversation, accounting for 64% (58–66%) of all utterances and this trend was similar across all three arms of the trial. Information-giving was the most frequent activity for both GPs and patients, although GPs did this at twice the rate compared to patients and at higher rates in consultations involving computerised decision aids. GPs' language was highly technically focused and just 7% of their conversation was socio-emotional in content; this was half the socio-emotional content shown by patients (15%). However, frequent head nodding and a close mirroring in the direction of eye-gaze suggested that both parties were active participants in the conversationConclusion: irrespective of the arm of the trial, both patients' and GPs' behaviour showed that they were reciprocally engaged in these consultations. However, even in consultations aimed at promoting shared decision-making, GPs' were verbally dominant, and they worked primarily as information providers for patients. In addition, computer-based decision aids significantly prolonged the consultations, particularly the later phases. These data suggest that decision aids may not lead to more 'sharing' in treatment decision-making and that, in their current form, they may take too long to negotiate for use in routine primary car

First enantioseparation and circular dichroism spectra of Au38 clusters protected by achiral ligands

Bestowing chirality to metals is central in fields such as heterogeneous catalysis and modern optics. Although the bulk phase of metals is symmetric, their surfaces can become chiral through adsorption of molecules. Interestingly, even achiral molecules can lead to locally chiral, though globally racemic, surfaces. A similar situation can be obtained for metal particles or clusters. Here we report the first separation of the enantiomers of a gold cluster protected by achiral thiolates, Au38(SCH2CH2Ph)24, achieved by chiral high-performance liquid chromatography. The chirality of the nanocluster arises from the chiral arrangement of the thiolates on its surface, forming 'staple motifs'. The enantiomers show mirror-image circular dichroism responses and large anisotropy factors of up to 4×10−3. Comparison with reported circular dichroism spectra of other Au38 clusters reveals that the influence of the ligand on the chiroptical properties is minor

PeRsOnaliSed care Planning for oldER people with frailty (PROSPER): protocol for a randomised controlled trial

This is the final version. Available on open access from BMC via the DOI in this recordAvailability of data and materials: Bradford Teaching Hospitals Foundation Trust (BTHFT) is the Data Controller. BTHFT will store non-trial data and the University of Leeds CTRU store trial data. Data will not be released prior to the end of the study, either for study publication or oral presentation purposes, without the permission of the TSC and subject to a data sharing agreement. During the archiving period, any requests for access to or copies of data will be considered by all collaborators in consultation. BTHFT will be the final arbiter of whether any disclosure/sharing should be agreed.BACKGROUND: Frailty is common in older age and is characterised by loss of biological reserves across multiple organ systems. These changes associated with frailty mean older people can be vulnerable to sudden, dramatic changes in health because of relatively small problems. Older people with frailty are at increased risk of adverse outcomes including disability, hospitalisation, and care home admission, with associated reduction in quality of life and increased NHS and social care costs. Personalised Care Planning offers an anticipatory, preventative approach to supporting older adults to live independently for longer, but it has not been robustly evaluated in a population of older adults with frailty. METHODS: Following an initial feasibility study, this multi-centre, individually randomised controlled trial aims to establish whether personalised care planning for older people improves health-related quality of life. It will recruit 1337 participants from general practices across Yorkshire and Humber and Mid-Mersey in the North of England. Eligible patients will be aged 65 and over with an electronic frailty index score of 0.21 or above, living in their own homes, without severe cognitive impairment and not in receipt of end-of-life care. Following confirmation of eligibility, informed consent and baseline data collection, participants will be individually randomised to the PeRsOnaliSed care Planning for oldER people with frailty (PROSPER) intervention or usual care in a 2.6:1 allocation ratio. Participants will not be blinded to allocation, but data collection and analysis will be blinded. The intervention will be delivered over 12 weeks by a Personal Independence Co-ordinator worker based within a voluntary sector organisation, Age UK. The primary outcomes are health-related quality of life, measured using both the physical and mental components of the Short-Form 12 Item Health Questionnaire at 12 months after randomisation. Secondary outcomes comprise activities of daily living, self-management capabilities and loneliness, admission to care homes, hospitalisations, and health and social care resource use at 12 months post randomisation. Parallel cost-effectiveness and process evaluations will be conducted alongside the trial. DISCUSSION: The PROSPER study will evaluate the effectiveness and cost-effectiveness of a personalised care planning approach for older people with frailty and inform the process of its implementation. TRIAL REGISTRATION: ISRCTN16123291 .  Registered on  28 August 2020.National Institute for Health and Care Research (NIHR