Confirming the existence of π-allyl-palladium intermediates during the reaction of meta photocycloadducts with palladium(ii) compounds

The transient existence of π-allyl-palladium intermediates formed by the reaction of Pd(OAc)2 and anisole-derived meta photocycloadducts has been demonstrated using NMR techniques. The intermediates tended to be short-lived and underwent rapid reductive elimination of palladium metal to form allylic acetates, however this degradation process could be delayed by changing the reaction solvent from acetonitrile to chloroform

The synthesis of brominated-boron-doped PAHs by alkyne 1,1-bromoboration: mechanistic and functionalisation studies

The research leading to these results has received funding from the European Research Council under the Horizon 2020 Research and Innovation Program (Grant no. 769599), the Leverhulme Trust (RPG-2014-340) and the EPSRC (EP/P010482/1). C. Si thanks the China Scholarship Council (201806890001).The synthesis of a range of brominated-Bn-containing (n = 1, 2) polycyclic aromatic hydrocarbons (PAHs) is achieved simply by reacting BBr3 with appropriately substituted alkynes via a bromoboration/electrophilic C-H borylation sequence. The brominated-Bn-PAHs were isolated as either the borinic acid or B-mesityl-protected derivatives, with the latter having extremely deep LUMOs for the B2-doped PAHs (with one example having a reduction potential of E1/2 = -0.96 V versus Fc+/Fc, Fc = ferrocene). Mechanistic studies revealed the reaction sequence proceeds by initial alkyne 1,1-bromoboration. 1,1-bromoboration also was applied to access a number of unprecedented 1-bromo-2,2-diaryl substituted vinylboronate esters direct from internal alkynes. Bromoboration/C-H borylation installs useful C-Br units onto the Bn-PAHs, which were utilised in Negishi coupling reactions, including for the installation of two triarylamine donor (D) groups onto a B2-PAH. The resultant D-A-D molecule has a low optical gap with an absorption onset at 750 nm and emission centered at 810 nm in the solid state.Publisher PDFPeer reviewe

Confirming the existence of π-allyl-palladium intermediates during the reaction of meta photocycloadducts with palladium(ii) compounds

The transient existence of π-allyl-palladium intermediates formed by the reaction of Pd(OAc)2 and anisole-derived meta photocycloadducts has been demonstrated using NMR techniques. The intermediates tended to be short-lived and underwent rapid reductive elimination of palladium metal to form allylic acetates, however this degradation process could be delayed by changing the reaction solvent from acetonitrile to chloroform

Supporting good practice in the provision of services to people with comorbid mental health and alcohol and other drug problems in Australia: describing key elements of good service models

<p>Abstract</p> <p>Background</p> <p>The co-occurrence of mental illness and substance use problems (referred to as "comorbidity" in this paper) is common, and is often reported by service providers as the expectation rather than the exception. Despite this, many different treatment service models are being used in the alcohol and other drugs (AOD) and mental health (MH) sectors to treat this complex client group. While there is abundant literature in the area of comorbidity treatment, no agreed overarching framework to describe the range of service delivery models is apparent internationally or at the national level. The aims of the current research were to identify and describe elements of good practice in current service models of treatment of comorbidity in Australia. The focus of the research was on models of service delivery. The research did not aim to measure the client outcomes achieved by individual treatment services, but sought to identify elements of good practice in services.</p> <p>Methods</p> <p>Australian treatment services were identified to take part in the study through a process of expert consultation. The intent was to look for similarities in the delivery models being implemented across a diverse set of services that were perceived to be providing good quality treatment for people with comorbidity problems.</p> <p>Results</p> <p>A survey was designed based on a concept map of service delivery devised from a literature review. Seventeen Australian treatment services participated in the survey, which explored the context in which services operate, inputs such as organisational philosophy and service structure, policies and procedures that guide the way in which treatment is delivered by the service, practices that reflect the way treatment is provided to clients, and client impacts.</p> <p>Conclusions</p> <p>The treatment of people with comorbidity of mental health and substance use disorders presents complex problems that require strong but flexible service models. While the treatment services included in this study reflected the diversity of settings and approaches described in the literature, the research found that they shared a range of common characteristics. These referred to: service linkages; workforce; policies, procedures and practices; and treatment.</p

Motivators and barriers for dog and cat owners and veterinary surgeons in the United Kingdom to using preventative medicines

Routine use of preventative medicines is advocated as part of responsible dog and cat ownership. However, it has been suggested that the number of owners in the United Kingdom (UK) using preventative medicines to protect their pets is in decline. The aim of this novel study was to use a qualitative methodology to explore the attitudes of pet owners and veterinary surgeons in the UK to using preventative medicine products in dogs and cats. Preventative medicine was defined as “a drug or any other preparation used to prevent disease, illness or injury.” Semi-structured interviews were conducted by telephone with owners and veterinary surgeons who had recently participated in a preventative healthcare consultation. Thematic analysis of transcribed recordings of these interviews identified four themes. This paper reports the theme related to motivators and barriers to using preventative medicines. Owners’ understanding varied widely about the importance of preventative medicines for pets, as did their confidence in the safety of prescription products. A good relationship with their veterinary surgeon or practice, seeing adverts on the television about specific diseases, advice from a breeder and having personally seen infected animals appeared to be motivators for owners to use preventative medicines. Concern about adverse events and uncertainty about the necessity of using preventative medicines were barriers. Owners who trusted their veterinary surgeons to advise them on preventative medicine products described little use of alternative information sources when making preventative medicine choices. However, owners who preferred to do their own research described reading online opinions, particular in relation to the safety of preventative medicines, which they found confusing. In contrast, veterinary surgeons described broad confidence in the safety and efficacy of prescription preventative medicines and described protection of pet health as a strong motivator for their use. Several expressed some concern about being seen to “sell” products, which may present a barrier to their advocacy. Veterinary surgeons were unsure about owners’ level of understanding of the necessity of preventative medicines, particularly in relation to vaccinations, and few recalled instigating conversations with owners about product safety. Owner uncertainties about preventative medicine products may not be adequately addressed in the consulting room. This first qualitative study to investigate dog and cat preventative medicines suggests strategies are needed to increase discussion between pet owners and veterinary surgeons in the UK about the necessity, safety, efficacy and cost of preventative medicines

Impacts of adaptation and responsibility framings on attitudes towards climate change mitigation

It is likely that climate change communications and media coverage will increasingly stress the importance of adaptation, yet little is known about whether or how this may affect attitudes towards mitigation. Despite concerns that communicating adaptation could undermine public support for mitigation, previous research has found it can have the opposite effect by increasing risk salience. It is also unclear whether people respond differently to information about mitigation and adaptation depending on whether action is framed as an individual or government responsibility. Using an experimental design, this study sought to examine how public attitudes towards mitigation are influenced by varying climate change messages, and how this might interact with prior attitudes to climate change. UK-based participants (N = 800) read one of four texts in a 2 × 2 design comparing adaptation versus mitigation information and personal versus governmental action. No main effect was found for adaptation versus mitigation framing, nor for individual action versus government policy, but we did observe a series of interaction effects with prior attitudes to climate change. Mitigation and adaptation information affected participants’ responses differently depending on their pre-existing levels of concern about climate change, suggesting that mitigation framings may be more engaging for those with high levels of concern, whereas adaptation framings may be more engaging for low-concern individuals. Government mitigation action appears to engender particularly polarised attitudes according to prior concern. Implications for climate change communications are considered

Large expert-curated database for benchmarking document similarity detection in biomedical literature search

Document recommendation systems for locating relevant literature have mostly relied on methods developed a decade ago. This is largely due to the lack of a large offline gold-standard benchmark of relevant documents that cover a variety of research fields such that newly developed literature search techniques can be compared, improved and translated into practice. To overcome this bottleneck, we have established the RElevant LIterature SearcH consortium consisting of more than 1500 scientists from 84 countries, who have collectively annotated the relevance of over 180 000 PubMed-listed articles with regard to their respective seed (input) article/s. The majority of annotations were contributed by highly experienced, original authors of the seed articles. The collected data cover 76% of all unique PubMed Medical Subject Headings descriptors. No systematic biases were observed across different experience levels, research fields or time spent on annotations. More importantly, annotations of the same document pairs contributed by different scientists were highly concordant. We further show that the three representative baseline methods used to generate recommended articles for evaluation (Okapi Best Matching 25, Term Frequency-Inverse Document Frequency and PubMed Related Articles) had similar overall performances. Additionally, we found that these methods each tend to produce distinct collections of recommended articles, suggesting that a hybrid method may be required to completely capture all relevant articles. The established database server located at https://relishdb.ict.griffith.edu.au is freely available for the downloading of annotation data and the blind testing of new methods. We expect that this benchmark will be useful for stimulating the development of new powerful techniques for title and title/abstract-based search engines for relevant articles in biomedical research.Peer reviewe

Effectiveness of a national quality improvement programme to improve survival after emergency abdominal surgery (EPOCH): a stepped-wedge cluster-randomised trial

BACKGROUND: Emergency abdominal surgery is associated with poor patient outcomes. We studied the effectiveness of a national quality improvement (QI) programme to implement a care pathway to improve survival for these patients. METHODS: We did a stepped-wedge cluster-randomised trial of patients aged 40 years or older undergoing emergency open major abdominal surgery. Eligible UK National Health Service (NHS) hospitals (those that had an emergency general surgical service, a substantial volume of emergency abdominal surgery cases, and contributed data to the National Emergency Laparotomy Audit) were organised into 15 geographical clusters and commenced the QI programme in a random order, based on a computer-generated random sequence, over an 85-week period with one geographical cluster commencing the intervention every 5 weeks from the second to the 16th time period. Patients were masked to the study group, but it was not possible to mask hospital staff or investigators. The primary outcome measure was mortality within 90 days of surgery. Analyses were done on an intention-to-treat basis. This study is registered with the ISRCTN registry, number ISRCTN80682973. FINDINGS: Treatment took place between March 3, 2014, and Oct 19, 2015. 22 754 patients were assessed for elegibility. Of 15 873 eligible patients from 93 NHS hospitals, primary outcome data were analysed for 8482 patients in the usual care group and 7374 in the QI group. Eight patients in the usual care group and nine patients in the QI group were not included in the analysis because of missing primary outcome data. The primary outcome of 90-day mortality occurred in 1210 (16%) patients in the QI group compared with 1393 (16%) patients in the usual care group (HR 1·11, 0·96-1·28). INTERPRETATION: No survival benefit was observed from this QI programme to implement a care pathway for patients undergoing emergency abdominal surgery. Future QI programmes should ensure that teams have both the time and resources needed to improve patient care. FUNDING: National Institute for Health Research Health Services and Delivery Research Programme