Enhanced Nanostructure Dynamics on Au(111) with Adsorbed Sulfur due to Au-S Complex Formation.

Chemisorbed species can enhance the fluxional dynamics of nanostructured metal surfaces which has implications for applications such as catalysis. Scanning tunneling microscopy studies at room temperature reveal that the presence of adsorbed sulfur (S) greatly enhances the decay rate of 2D Au islands in the vicinity of extended step edges on Au(111). This enhancement is already significant at S coverages, θS , of a few hundredths of a monolayer (ML), and is most pronounced for 0.1-0.3 ML where the decay rate is increased by a factor of around 30. For θS close to saturation at about 0.6 ML, sulfur induces pitting and reconstruction of the entire surface, and Au islands are stabilized. Enhanced coarsening at lower θS is attributed to the formation and diffusion across terraces of Au-S complexes, particularly AuS2 and Au4 S4 , with some lesser contribution from Au3 S4 . This picture is supported by density functional theory analysis of complex formation energies and diffusion barriers.

Reshaping, Intermixing, and Coarsening for Metallic Nanocrystals: Nonequilibrium Statistical Mechanical and Coarse-Grained Modeling.

Self-assembly of supported 2D or 3D nanocrystals (NCs) by vacuum deposition and of 3D NCs by solution-phase synthesis (with possible subsequent transfer to a support) produces intrinsically nonequilibrium systems. Individual NCs can have far-from-equilibrium shapes and composition profiles. The free energy of NC ensembles is lowered by coarsening which can involve Ostwald ripening or Smoluchowski ripening (NC diffusion and coalescence). Preservation of individual NC structure and inhibition of coarsening are key, e.g., for avoiding catalyst degradation. This review focuses on postsynthesis evolution of metallic NCs. Atomistic-level modeling typically utilizes stochastic lattice-gas models to access appropriate time and length scales. However, predictive modeling requires incorporation of realistic rates for relaxation mechanisms, e.g., periphery diffusion and intermixing, in numerous local environments (rather than the use of generic prescriptions). Alternative coarse-grained modeling must also incorporate appropriate mechanisms and kinetics. At the level of individual NCs, we present analyses of reshaping, including sintering and pinch-off, and of compositional evolution in a vacuum environment. We also discuss modeling of coarsening including diffusion and decay of individual NCs and unconventional coarsening processes. We describe high-level modeling integrated with scanning tunneling microscopy (STM) studies for supported 2D epitaxial nanoclusters and developments in modeling for 3D NCs motivated by in situ transmission electron microscopy (TEM) studies.

Structure of chalcogen overlayers on Au(111): Density functional theory and lattice-gas modeling.

Ordering of different chalcogens, S, Se, and Te, on Au(111) exhibit broad similarities but also some distinct features, which must reflect subtle differences in relative values of the long-range pair and many-body lateral interactions between adatoms. We develop lattice-gas (LG) models within a cluster expansion framework, which includes about 50 interaction parameters. These LG models are developed based on density functional theory (DFT) analysis of the energetics of key adlayer configurations in combination with the Monte Carlo (MC) simulation of the LG models to identify statistically relevant adlayer motifs, i.e., model development is based entirely on theoretical considerations. The MC simulation guides additional DFT analysis and iterative model refinement. Given their complexity, development of optimal models is also aided by strategies from supervised machine learning. The model for S successfully captures ordering motifs over a broader range of coverage than achieved by previous models, and models for Se and Te capture the features of ordering, which are distinct from those for S. More specifically, the modeling for all three chalcogens successfully explains the linear adatom rows (also subtle differences between them) observed at low coverages of ∼0.1 monolayer. The model for S also leads to a new possible explanation for the experimentally observed phase with a (5 × 5)-type low energy electron diffraction (LEED) pattern at 0.28 ML and to predictions for LEED patterns that would be observed with Se and Te at this coverage.

Characteristics of sulfur atoms adsorbed on Ag(100), Ag(110), and Ag(111) as probed with scanning tunneling microscopy: experiment and theory.

In this paper, we report that S atoms on Ag(100) and Ag(110) exhibit a distinctive range of appearances in scanning tunneling microscopy (STM) images, depending on the sample bias voltage, VS. Progressing from negative to positive VS, the atomic shape can be described as a round protrusion surrounded by a dark halo (sombrero) in which the central protrusion shrinks, leaving only a round depression. This progression resembles that reported previously for S atoms on Cu(100). We test whether DFT can reproduce these shapes and the transition between them, using a modified version of the Lang-Tersoff-Hamann method to simulate STM images. The sombrero shape is easily reproduced, but the sombrero-depression transition appears only for relatively low tunneling current and correspondingly realistic tip-sample separation, dT, of 0.5-0.8 nm. Achieving these conditions in the calculations requires sufficiently large separation (vacuum) between slabs, together with high energy cutoff, to ensure appropriate exponential decay of electron density into vacuum. From DFT, we also predict that an analogous transition is not expected for S atoms on Ag(111) surfaces. The results are explained in terms of the through-surface conductance, which defines the background level in STM, and through-adsorbate conductance, which defines the apparent height at the point directly above the adsorbate. With increasing VS, for Ag(100) and Ag(110), we show that through-surface conductance increases much more rapidly than through-adsorbate conductance, so the apparent adsorbate height drops below background. In contrast, for Ag(111) the two contributions increase at more comparable rates, so the adsorbate level always remains above background and no transition is seen.

Sulfur adsorption on coinage metal(100) surfaces: propensity for metal-sulfur complex formation relative to (111) surfaces.

Experimental data from low-temperature Scanning Tunneling Microscopy (LTSTM) studies on coinage metal surfaces with very low coverages of S is providing new insights into metal-S interactions. A previous LTSTM study for Cu(100), and a new analysis reported here for Ag(100), both indicate no metal-sulfur complex formation, but an Au4S5 complex was observed previously on Au(100). In marked contrast, various complexes have been proposed and/or observed on Ag(111) and Cu(111), but not on Au(111). Also, exposure to trace amounts of S appears to enhance mass transport far more dramatically on (111) than on (100) surfaces for Cu and Ag, a feature tied to the propensity for complex formation. Motivated by these observations, we present a comprehensive assessment at the level of DFT to assess the existence and stability of complexes on (100) surfaces, and compare results with previous analyses for (111) surfaces. Consistent with experiment, our DFT analysis finds no stable complexes on Ag(100) and Cu(100), but several exist for Au(100). In addition, we systematically relate stability for adsorbed and gas-phase species within the framework of Hess's law. We thereby provide key insight into the various energetic contributions to stability which in turn elucidates the difference in behavior between (100) and (111) surfaces.

Medical engagement and organizational characteristics in general practice.

BACKGROUND: Medical engagement is a mutual concept of the active and positive contribution of doctors to maintaining and enhancing the performance of their health care organization, which itself recognizes this commitment in supporting and encouraging high quality care. A Medical Engagement Scale (MES) was developed by Applied Research Ltd (2008) on the basis of emerging evidence that medical engagement is critical for implementing radical improvements. OBJECTIVES: To study the importance of medical engagement in general practice and to analyse patterns of association with individual and organizational characteristics. DESIGN AND SETTING: A cross-sectional study using a sampled survey questionnaire and the official register from the Danish General Practitioners' Organization comprising all registered Danish GPs. METHOD: The Danish version of the MES Questionnaire was distributed and the survey results were analysed in conjunction with the GP register data. RESULTS: Statistically adjusted analyses revealed that the GPs' medical engagement varied substantially. GPs working in collaboration with colleagues were more engaged than GPs from single-handed practices, older GPs were less engaged than younger GPs and female GPs had higher medical engagement than their male colleagues. Furthermore, GPs participating in vocational training of junior doctors were more engaged than GPs not participating in vocational training. CONCLUSION: Medical engagement in general practice varies a great deal and this is determined by a complex interaction between both individual and organizational characteristics. Working in collaboration, having staff and being engaged in vocational training of junior doctors are all associated with enhanced levels of medical engagement among GPs.

Defining the structure of undergraduate medical leadership and management teaching and assessment in the UK.

Medical leadership and management (MLM) skills are essential in preventing failings of healthcare; it is unknown how these attitudes can be developed during undergraduate medical education. This paper aims to quantify interest in MLM and recommends preferred methods of teaching and assessment at UK medical schools. Two questionnaires were developed, one sent to all UK medical school faculties, to assess executed and planned curriculum changes, and the other sent to medical students nationally to assess their preferences for teaching and assessment. Forty-eight percent of UK medical schools and 260 individual student responses were recorded. Student responses represented 60% of UK medical schools. 65% of schools valued or highly valued the importance of teaching MLM topics, compared with 93.2% of students. Students' favoured teaching methods were seminars or lectures (89.4%) and audit and quality improvement (QI) projects (77.8%). Medical schools preferred portfolio entries (55%) and presentations (35%) as assessment methods, whilst simulation exercises (76%) and audit reports (61%) were preferred by students. Preferred methods encompass experiential learning or simulation and a greater emphasis should be placed on encouraging student audit and QI projects. The curriculum changes necessary could be achieved via further integration into future editions of Tomorrow's Doctors.

Emergency Care Handover (ECHO study) across care boundaries: the need for joint decision making and consideration of psychosocial history.

BACKGROUND: Inadequate handover in emergency care is a threat to patient safety. Handover across care boundaries poses particular problems due to different professional, organisational and cultural backgrounds. While there have been many suggestions for standardisation of handover content, relatively little is known about the verbal behaviours that shape handover conversations. This paper explores both what is communicated (content) and how this is communicated (verbal behaviours) during different types of handover conversations across care boundaries in emergency care. METHODS: Three types of interorganisational (ambulance service to emergency department (ED) in 'resuscitation' and 'majors' areas) and interdepartmental handover conversations (referrals to acute medicine) were audio recorded in three National Health Service EDs. Handover conversations were segmented into utterances. Frequency counts for content and language forms were derived for each type of handover using Discourse Analysis. Verbal behaviours were identified using Conversation Analysis. RESULTS: 203 handover conversations were analysed. Handover conversations involving ambulance services were predominantly descriptive (60%-65% of utterances), unidirectional and focused on patient presentation (75%-80%). Referrals entailed more collaborative talk focused on the decision to admit and immediate care needs. Across all types of handover, only 1.5%-5% of handover conversation content related to the patient's social and psychological needs. CONCLUSIONS: Handover may entail both descriptive talk aimed at information transfer and collaborative talk aimed at joint decision-making. Standardisation of handover needs to accommodate collaborative aspects and should incorporate communication of information relevant to the patient's social and psychological needs to establish appropriate care arrangements at the earliest opportunity.

Is management essential to improving the performance and sustainability of health care systems and organizations? A systematic review and a roadmap for future studies.

Recent studies have highlighted the importance of management in the health care sector. Positive correlations have been found between clinical and economic performance. Although there is still controversy regarding what kind of management and which managers should lead health care organizations and health systems, we now have interesting evidence to analyze. Starting with a systematic review of the literature, this article presents and discusses the streams of knowledge regarding how management can influence the quality and sustainability of health systems and organizations. Through the analysis of 37 studies, we found that the performance of health care systems and organizations seems to be correlated with management practices, leadership, manager characteristics, and cultural attributes that are associated with managerial values and approaches. There is also evidence that health care organizations run by doctors perform better than others. Finally, we provide a roadmap that indicates how the relationship between the management and performance of health systems and organizations can be further and more effectively investigated.

Australian doctors are more engaged than UK doctors: why is this the case?

BACKGROUND: Despite reports highlighting the need for greater medical engagement and the benefits of being widely understood, very little information is available on the status of medical engagement in Australia, and how this compares to the UK. Answering this question will no doubt assist training bodies, curriculum designers and policy makers better understand relevant issues. METHODS: The medical engagement questionnaire (MES) was emailed to all medical staff working at 159 UK National Health Service Trusts and 18 health service organisations in Australia. The questionnaire consists of 30 predetermined items seeking responses using a 5-point Likert scale. RESULTS: Overall, doctors in the Australian dataset are slightly more engaged, or more positive, than their UK colleagues. Good interpersonal relationships was the only variable that UK doctors scored more positively than their Australian counterparts. At the lower end of the responses, that is the least engaged, we found this even more apparent. Where doctors in Australia are less disengaged, that is still more positive than the UK colleagues. CONCLUSION: While the profiles of medical engagement vary at the sites and also across the MES and subscales, the data illustrate that overall doctors in Australia feel valued and empowered, and they have purpose and direction and work in a collaborate culture. At the most disengaged end of the scale, Australian doctors are markedly less disengaged than their UK counterparts. There may be numerous factors that influence and change how engaged doctors are in both countries. The most prominent of these are appear to be working conditions and lifestyle, driven by funding and other economics issues. This research is likely to be of great interest to regulators and training bodies in both countries.

Improving patient safety incident reporting systems by focusing upon feedback - lessons from English and Welsh trusts.

This paper describes practical implications and learning from a multi-method study of feedback from patient safety incident reporting systems. The study was performed using the Safety Action and Information Feedback from Incident Reporting model, a model of the requirements of the feedback element of a patient safety incident reporting and learning system, derived from a scoping review of research and expert advice from world leaders in safety in high-risk industries. We present the key findings of the studies conducted in the National Health Services (NHS) trusts in England and Wales in 2006. These were a survey completed by risk managers for 351 trusts in England and Wales, three case studies including interviews with staff concerning an example of good practice feedback and an audit of 90 trusts clinical risk staff newsletters. We draw on an Expert Workshop that included 71 experts from the NHS, from regulatory bodies in health care, Royal Colleges, Health and Safety Executive and safety agencies in health care and high-risk industries (commercial aviation, rail and maritime industries). We draw recommendations of enduring relevance to the UK NHS that can be used by trust staff to improve their systems. The recommendations will be of relevance in general terms to health services worldwide.

Identification of an AgS2 Complex on Ag(110).

Adsorbed sulfur has been investigated on the Ag(110) surface at two different coverages, 0.02 and 0.25 monolayers. At the lower coverage, only sulfur adatoms are present. At the higher coverage, there are additional bright features which we identify as linear, independent AgS2 complexes. This identification is based upon density functional theory (DFT) and its comparison with experimental observations including bias dependence and separation between complexes. DFT also predicts the absence of AgS2 complexes at low coverage, and the development of AgS2 complexes around a coverage of 0.25 monolayers of sulfur, as is experimentally observed. To our knowledge, this is the first example of an isolated linear sulfur-metal-sulfur complex.

More students, less capacity? An assessment of the competing demands on academic medical staff.

CONTEXT: Medical student numbers in England have increased by more than 60% over the last decade. The capacity of universities and the National Health Service (NHS) to deliver education and training to these expanded cohorts is not clear. METHODS: We carried out an interview study in three English medical schools, involving 60 academic, administrative, clinical and managerial staff, sampled across disciplines. RESULTS: Given the expansion in medical student numbers, capacity in medical schools must increase. This requirement has become even more immediate in light of the shift towards more resource-intensive curricula. However, the aims of the Research Assessment Exercise and NHS policies are at odds with attempts to build teaching capacity. Although monies have been made available to recruit new staff and to backfill clinical time spent teaching, the success of these strategies is questioned by interviewees. Other initiatives, such as the new consultant contract and educational quality assurance processes, have the potential to promote the importance of teaching but are presently perceived as being inadequate so to do. As was consistently expressed by interviewees, within the competing triad of research, service delivery and teaching, the latter is perceived as taking a poor third place. CONCLUSIONS: That research, service delivery and education are in competition will come as no surprise to UK academic staff. However, our results show a striking uniformity of opinion. We would question whether existing NHS and higher education policies enable medical schools and health care organisations to deliver education of the highest quality to the enlarged student population.

Sulfur Atoms Adsorbed on Cu(100) at Low Coverage: Characterization and Stability against Complexation.

Using scanning tunneling microscopy, we characterize the size and bias-dependent shape of sulfur atoms on Cu(100) at low coverage (below 0.1 monolayers) and low temperature (quenched from 300 to 5 K). Sulfur atoms populate the Cu(100) terraces more heavily than steps at low coverage, but as coverage approaches 0.1 monolayers, close-packed step edges become fully populated, with sulfur atoms occupying sites on top of the step. Density functional theory (DFT) corroborates the preferential population of terraces at low coverage as well as the step adsorption site. In experiment, small regions with p(2 × 2)-like atomic arrangements emerge on the terraces as sulfur coverage approaches 0.1 monolayer. Using DFT, a lattice gas model has been developed, and Monte Carlo simulations based on this model have been compared with the observed terrace configurations. A model containing eight pairwise interaction energies, all repulsive, gives qualitative agreement. Experiment shows that atomic adsorbed sulfur is the only species on Cu(100) up to a coverage of 0.09 monolayers. There are no Cu-S complexes. In contrast, prior work has shown that a Cu2S3 complex forms on Cu(111) under comparable conditions. On the basis of DFT, this difference can be attributed mainly to stronger adsorption of sulfur on Cu(100) as compared with Cu(111).

The Relationships Between Use of Quality-of-Care Feedback Reports on Chronic Diseases and Medical Engagement in General Practice.

BACKGROUND: There is a limited knowledge on how medical engagement influences quality of care provided in primary care. The extent of the use of feedback reports from a national quality-of-care database can be considered as a measure of process quality. This study explores relationships between the use of feedback reports and medical engagement among general practitioners, general practitioner demographics, clinic characteristics, and services. METHODS: A cross-sectional combined questionnaire and register study in a sample of 352 single-handed general practitioners in 2013. Logistic regression analysis was used to explore associations between the use of feedback reports for diabetes and chronic obstructive pulmonary disease and medical engagement. RESULTS: For both diabetes and chronic obstructive pulmonary disease, a higher degree of medical engagement was associated with an increased use of feedback reports. Furthermore, we identified positive associations between using feedback reports and general practitioner services (spirometry, influenza vaccinations, performing annual reviews for patients with chronic diseases) and a negative association between usage of quality-of-care feedback reports and the number of consultations per patient. CONCLUSION: Using feedback reports for chronic diseases in general practice was positively associated with medical engagement and also with the provision of services in general practice.

Implications of bond disorder in a S=1 kagome lattice.

Strong hydrogen bonds such as F···H···F offer new strategies to fabricate molecular architectures exhibiting novel structures and properties. Along these lines and, to potentially realize hydrogen-bond mediated superexchange interactions in a frustrated material, we synthesized [H2F]2[Ni3F6(Fpy)12][SbF6]2 (Fpy = 3-fluoropyridine). It was found that positionally-disordered H2F+ ions link neutral NiF2(Fpy)4 moieties into a kagome lattice with perfect 3-fold rotational symmetry. Detailed magnetic investigations combined with density-functional theory (DFT) revealed weak antiferromagnetic interactions (J ~ 0.4 K) and a large positive-D of 8.3 K with ms = 0 lying below ms = ±1. The observed weak magnetic coupling is attributed to bond-disorder of the H2F+ ions which leads to disrupted Ni-F···H-F-H···F-Ni exchange pathways. Despite this result, we argue that networks such as this may be a way forward in designing tunable materials with varying degrees of frustration.

Working hours of surgical residence: perspective of a group of surgeons in a regional hospital in Hong Kong.

BACKGROUND: The Accreditation Council for Graduate Medical Education and European working time directive have restricted residents' workweek to 80 and 48 hours, respectively. Impacts on resident's training and health services are under evaluation in western countries. However, relevant studies are deficient in Hong Kong. METHODS: Surgeons in a regional hospital of Hong Kong were recruited. Opinions were collected by semi-structured questionnaire. RESULTS: Response rate was 82%. Most respondents agreed that residents' work hours should be limited. Seventy-two percent thought that the addition of physician assistants, nurse practitioners and ancillary staff could help decrease the workload of residents. More than 60% thought that residents should have post-call afternoon off. Seventy-two percent worried that the number of operations residents performed would decrease. Only half agreed that long work hours was part of resident training and 56.3% agreed that the training period should be lengthened because of limiting work hours. Ninety-four percent agreed that sleep-deprived residents would create more medical errors; 72% thought that long work hours would impair quality of care. Surprisingly, only 28% thought that limiting work hours would compromise continued patient care. CONCLUSION: Most respondents opine that resident work hours should be regulated and welcome minor rescheduling of residents' workflow. The impacts on residents' training and patient care require further evaluation.

Organizational interventions to promote risk management in primary care: the experience in Warwickshire, England.

Primary care organizations are under-represented in research on quality improvement and risk management (RM), yet the potential for improving patient safety is possibly greater given the extent that clinical judgement is required to achieve a service tailored to the individual's personal health and lifestyle. This paper examines how a health authority in England promoted interventions to improve RM in General Practice that included the practices' own initiatives, significant event audit (SEA) and the Medical Defence Union's workshops which included SEA. All 75 practices were approached before the programmes and when they were finished, eight months later. The practice manager from each practice completed an audit of RM activities, from which a RM competence score was derived. Up to six staff per practice completed the Learning organization Culture Questionnaire (LCQ) at both times. There was evidence of improved competence in RM over the period of the study, particularly through a widening breadth of staff involved and in formal recording systems. There was little evidence that these improvements were mediated by organizational culture. It is argued that future interventions should more closely target specific competences (e.g. recording systems for adverse events, root cause analysis to understand error generation) and enable staff to see tangible personal and organizational benefits for the extra effort involved.

Are we nearly there yet? A study of the English National Health Service as professional bureaucracies.

Purpose The purpose of this paper is to explore issues of medical engagement in the management and leadership of health services in the English National Health Service (NHS). The literature suggests that this is an important component of high performing health systems, although the NHS has traditionally struggled to engage doctors and has been characterised as a professional bureaucracy. This study explored the ways in which health care organisations structure and operate medical leadership processes to assess the degree to which professional bureaucracies still exist in the English NHS. Design/methodology/approach Drawing on the qualitative component of a research into medical leadership in nine case study sites, this paper reports on findings from over 150 interviews with doctors, general managers and nurses. In doing so, the authors focus specifically on the operation of medical leadership in nine different NHS hospitals. Findings Concerted attention has been focussed on medical leadership and this has led to significant changes to organisational structures and the recruitment and training processes of doctors for leadership roles. There is a cadre of doctors that are substantially more engaged in the leadership of their organisations than previous research has found. Yet, this engagement has tended to only involve a small section of the overall medical workforce in practice, raising questions about the nature of medical engagement more broadly. Originality/value There are only a limited number of studies that have sought to explore issues of medical leadership on this scale in the English context. This represents the first significant study of this kind in over a decade.