Conjugated, rigidified bibenzimidazole ancillary ligands for enhanced photoluminescence quantum yields of orange/red-emitting iridium(III) complexes

EZ-C acknowledges the University of St Andrews for financial support. We thank Umicore AG for the gift of materials. We would like to thank the Engineering and Physical Sciences Research Council for financial support for E.Z-C. (EP/M02105X/1) and for the studentship of A.H. (EP/J500549/1, EP/K503162/1, EP/L505097/1). We thank the EPSRC UK National Mass Spectrometry Facility at Swansea University for analytical services. We also would like to thank EaStCHEM and the School of Chemistry for supporting the computing facilities maintained by Dr. H. Früchtl.A series of six novel [Ir(C^N)2(N^N)](PF6) complexes (C^N is one of two cyclometalating ligands: 2-phenyl-4-(2,4,6-trimethylphenyl)pyridine, MesppyH, or 2- (napthalen-1-yl)-4-(2,4,6-trimethylphenyl)pyridine, MesnpyH; N^N denotes one of four neutral diamine ligands: 4,4’-di-tert-butyl-2,2’-bipyridine, dtbubpy, 1H,1’H-2,2’- bibenzimiazole, H2bibenz, 1,1’-(α,α’-o-xylylene)-2,2’-bibenzimidazole, o-Xylbibenz or 2,2’- biquinoline, biq) were synthesised and their structural, electrochemical and photophysical properties comprehensively characterised. The more conjugated MesnpyH ligands confer a red-shift in the emission compared to MesppyH but maintain high photoluminescence quantum yields due to the steric bulk of the mesityl groups. The H2bibenz and o-Xylbibenz ligands are shown to be electronically indistinct to dtbubpy but give complexes with higher quantum yields than analogous complexes bearing dtbubpy. In particular, the rigidity of the o-Xylbibenz ligand, combined with the steric bulk of the MesnpyH C^N ligands, give a red-emitting complex 4 (λPL = 586, 623 nm) with a very high photoluminescence quantum yield (ΦPL = 44%) for an emitter in that regime of the visible spectrum. These results suggest that employing these ligands is a viable strategy for designing more efficient orange-red emitters for use in a variety of photophysical applications.PostprintPeer reviewe

Characterizing the limited use of point-of-care ultrasound in Colombian emergency medicine residencies

Background: Emergency medicine (EM) is a growing specialty in Colombia with five residency programs in the country. EM leadership is interested in incorporating point-of-care (POC) ultrasound into a standardized national EM residency curriculum. This study is a nationwide survey of Colombian EM residents designed to explore the current state of POC ultrasound use within EM residencies and examine specific barriers preventing its expansion. Methods: We conducted a mix-methodology study of all available current EM residents in the five EM residencies in Colombia. The quantitative survey assessed previous ultrasound experience, current use of various applications, desire for further training, and perceived barriers to expanded use. Focus group discussions (FGDs) were conducted with current EM residents to gather additional qualitative insight into their practice patterns and perceived barriers to clinician-performed ultrasound. Results: Sixty-nine EM residents completed the quantitative survey, a response rate of 85% of all current EM residents in Colombia; 52% of resident respondents had previously used ultrasound during their training. Of these, 58% indicated that they had performed 40 scans. The most frequently used applications indicated by respondents were trauma, obstetrics, and procedures including vascular access. A quarter indicated they had previously received some ultrasound training, but almost all expressed an interest in learning more. Significant barriers included lack of trained teachers (indicated by 78% of respondents), absence of machines (57%), and limited time (41%). In FGDs, the barriers identified were inter-specialty conflicts over the control of ultrasonography, both institutionally and nationally, and program-specific curriculum decisions to include POC ultrasound. Conclusion: While currently limited in their access, EM residents in Colombia have a strong interest in integrating POC ultrasound into their training. Current barriers to expanded use include traditional barriers such as a lack of equipment seen in many developing countries, as well as inter-specialty conflicts typical of developed countries. Further collaboration is underway to help overcome these obstacles and integrate POC ultrasound into Colombian EM residency training

Characterizing the limited use of point-of-care ultrasound in Colombian emergency medicine residencies

Background: Emergency medicine (EM) is a growing specialty in Colombia with five residency programs in the country. EM leadership is interested in incorporating point-of-care (POC) ultrasound into a standardized national EM residency curriculum. This study is a nationwide survey of Colombian EM residents designed to explore the current state of POC ultrasound use within EM residencies and examine specific barriers preventing its expansion. Methods: We conducted a mix-methodology study of all available current EM residents in the five EM residencies in Colombia. The quantitative survey assessed previous ultrasound experience, current use of various applications, desire for further training, and perceived barriers to expanded use. Focus group discussions (FGDs) were conducted with current EM residents to gather additional qualitative insight into their practice patterns and perceived barriers to clinician-performed ultrasound. Results: Sixty-nine EM residents completed the quantitative survey, a response rate of 85% of all current EM residents in Colombia; 52% of resident respondents had previously used ultrasound during their training. Of these, 58% indicated that they had performed <10 scans and 17% reported >40 scans. The most frequently used applications indicated by respondents were trauma, obstetrics, and procedures including vascular access. A quarter indicated they had previously received some ultrasound training, but almost all expressed an interest in learning more. Significant barriers included lack of trained teachers (indicated by 78% of respondents), absence of machines (57%), and limited time (41%). In FGDs, the barriers identified were inter-specialty conflicts over the control of ultrasonography, both institutionally and nationally, and program-specific curriculum decisions to include POC ultrasound. Conclusion: While currently limited in their access, EM residents in Colombia have a strong interest in integrating POC ultrasound into their training. Current barriers to expanded use include traditional barriers such as a lack of equipment seen in many developing countries, as well as inter-specialty conflicts typical of developed countries. Further collaboration is underway to help overcome these obstacles and integrate POC ultrasound into Colombian EM residency training. © 2014 Henwood et al.; licensee Springer

The Global Impact of Science Gateways, Virtual Research Environments and Virtual Laboratories

Science gateways, virtual laboratories and virtual research environments are all terms used to refer to community-developed digital environments that are designed to meet a set of needs for a research community. Specifically, they refer to integrated access to research community resources including software, data, collaboration tools, workflows, instrumentation and high-performance computing, usually via Web and mobile applications. Science gateways, virtual laboratories and virtual research environments are enabling significant contributions to many research domains, facilitating more efficient, open, reproducible research in bold new ways. This paper explores the global impact achieved by the sum effects of these programs in increasing research impact, demonstrates their value in the broader digital landscape and discusses future opportunities. This is evidenced through examination of national and international programs in this field

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

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

Characterising the interactions of low-dimensional carbon nanostructures with molecules and nanowires.

Since their discovery and isolation graphene and carbon nanotubes have fascinated both the scientific and industrial communities due to their unique physical properties. Many of the properties and potential applications are influenced by the interactions between the graphitic nanostructures and other materials. Some of the important interactions include gas-on-solid adsorption using the carbon nanostructures as hydrogen storage media or gas sensors. In addition filling nanotubes with various materials allows the fundamental study of encapsulated 1D nanowires and their influence on the electronic properties of the nanotubes. Density functional theory has been used to examine the ionization energy, polarizability and quadrupole moments of diatomic molecules, graphene sheets and single wall carbon nanotubes. The theoretical work continues using density functional theory to investigate hydrogen and oxygen physisorption to a graphene plate and segments of the (10, 0) and (9, 0) carbon nanotubes. A range of adsorption sites, both external and internal to the nanotubes, have been studied with the molecular axis oriented parallel or perpendicular to the nanotube wall. It is found that both hydrogen and oxygen bind weakly to the graphitic nanostructures in all adsorption sites studied. The adsorption energies of oxygen to the carbon nanostructures are found to be stronger than hydrogen adsorption energies. In addition binding energies are a factor of two larger for diatomic molecules bound inside the carbon nanotubes than for adsorption outside the nanotubes or on the graphene plate. Hydrogen interaction energies are shown to be enhanced by the addition of a second (10, 0) nanotube segment. Differences in binding energy characteristics are attributed to the curvature of the nanostructure and the interactions between electrons of the nanotube and the adsorbed molecule. The graphitisation and purity of several nanotube powders was examined using the analytical techniques of thermogravimetric analysis, transmission electron microscopy and x- ray photoelectron spectroscopy. A high-quality nanotube sample was successfully filled with a mercury tellurium compound via the molten media method. Preliminary results of the characterisation of the encapsulated nanowires, using scanning tunnelling microscopy, are inconclusive. However dry-deposition techniques were successful in isolating carbon nanotubes from the nanotube ropes of the filled sample

Characterising the interactions of low-dimensional carbon nanostructures with molecules and nanowires.

Since their discovery and isolation graphene and carbon nanotubes have fascinated both the scientific and industrial communities due to their unique physical properties. Many of the properties and potential applications are influenced by the interactions between the graphitic nanostructures and other materials. Some of the important interactions include gas-on-solid adsorption using the carbon nanostructures as hydrogen storage media or gas sensors. In addition filling nanotubes with various materials allows the fundamental study of encapsulated 1D nanowires and their influence on the electronic properties of the nanotubes. Density functional theory has been used to examine the ionization energy, polarizability and quadrupole moments of diatomic molecules, graphene sheets and single wall carbon nanotubes. The theoretical work continues using density functional theory to investigate hydrogen and oxygen physisorption to a graphene plate and segments of the (10, 0) and (9, 0) carbon nanotubes. A range of adsorption sites, both external and internal to the nanotubes, have been studied with the molecular axis oriented parallel or perpendicular to the nanotube wall. It is found that both hydrogen and oxygen bind weakly to the graphitic nanostructures in all adsorption sites studied. The adsorption energies of oxygen to the carbon nanostructures are found to be stronger than hydrogen adsorption energies. In addition binding energies are a factor of two larger for diatomic molecules bound inside the carbon nanotubes than for adsorption outside the nanotubes or on the graphene plate. Hydrogen interaction energies are shown to be enhanced by the addition of a second (10, 0) nanotube segment. Differences in binding energy characteristics are attributed to the curvature of the nanostructure and the interactions between electrons of the nanotube and the adsorbed molecule. The graphitisation and purity of several nanotube powders was examined using the analytical techniques of thermogravimetric analysis, transmission electron microscopy and x- ray photoelectron spectroscopy. A high-quality nanotube sample was successfully filled with a mercury tellurium compound via the molten media method. Preliminary results of the characterisation of the encapsulated nanowires, using scanning tunnelling microscopy, are inconclusive. However dry-deposition techniques were successful in isolating carbon nanotubes from the nanotube ropes of the filled sample