Cyclic ether and anhydride ring opening copolymerisation delivering new ABB sequences in poly(ester- alt -ethers) †

Poly(ester-alt-ethers) are interesting as they combine the ester linkage rigidity and potential for hydrolysis with ether linkage flexibility. This work describes a generally applicable route to their synthesis applying commercial monomers and yielding poly(ester-alt-ethers) with variable compositions and structures. The ring-opening copolymerisation of anhydrides (A), epoxides (B) and cyclic ethers (C), using a Zr(iv) catalyst, produces either ABB or ABC type poly(ester-alt-ethers). The catalysis is effective using a range of commercial anhydrides (A), including those featuring aromatic, unsaturated or tricyclic monomers, and with different alkylene oxides (epoxides, B), including those featuring aliphatic, alkene or ether substituents. The range of effective cyclic ethers (C) includes tetrahydrofuran, 2,5-dihydrofuran (DHF) or 1,4-bicyclic ether (OBH). In these investigations, the catalyst:anhydride loadings are generally held constant and deliver copolymers with degrees of copolymerisation of 25, with molar mass values from 4 to 11 kg mol−1 and mostly with narrow dispersity molar mass distributions. All the new copolymers are amorphous, they show the onset of thermal decomposition between 270 and 344 °C and variable glass transition temperatures (−50 to 48 °C), depending on their compositions. Several of the new poly(ester-alt-ethers) feature alkene substituents which are reacted with mercaptoethanol, by thiol–ene processes, to install hydroxyl substituents along the copolymer chain. This strategy affords poly(ether-alt-esters) featuring 30, 70 and 100% hydroxyl substituents (defined as % of monomer repeat units featuring a hydroxyl group) which moderate physical properties such as hydrophilicity, as quantified by water contact angles. Overall, the new sequence selective copolymerisation catalysis is shown to be generally applicable to a range of anhydrides, epoxides and cyclic ethers to produce new families of poly(ester-alt-ethers). In future these copolymers should be explored for applications in liquid formulations, electrolytes, surfactants, plasticizers and as components in adhesives, coatings, elastomers and foams

Enantioselective N-heterocyclic carbene catalyzed formal [3+2] cycloaddition using α-aroyloxyaldehydes and oxaziridines

We thank the EPSRC Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT, grant code EP/L016419/1) (R.W.F.K.) for funding. The European Research Council under the European Union’s Seventh Framework Programme (FP7/2007–2013) ERC Grant Agreement No. 279850 is also acknowledged. A.D.S. thanks the Royal Society for a Wolfson Research Merit Award.An enantioselective N-heterocyclic carbene catalysed formal [3+2] cycloaddition has been developed for the synthesis of oxazolindin-4-one products. The reaction of oxaziridines and α-aroyloxyaldehydes under N-heterocyclic carbene catalysis provides the formal cycloaddition products with excellent control of the diastereo- and enantioselectivity (12 examples, up to >95:5 dr, >99:1 er). A matched-mismatched effect between the enantiomer of the catalyst and oxaziridine was identified, and preliminary mechanistic studies have allowed the proposal of a model to explain these observations.Publisher PDFPeer reviewe

Catalytic Synergy Using Al(III) and Group 1 Metals to Accelerate Epoxide and Anhydride Ring-Opening Copolymerizations

The controlled synthesis of polyesters via epoxide/anhydride ring-opening copolymerization is a versatile and generally applicable method to make many sustainable polymers, but catalyst activities are limited and the required catalyst loadings are typically high. Here, novel heterodinuclear complexes, featuring Al(III)/M(I) (M = Na, K, Rb, Cs), show exceptional activities for phthalic anhydride and cyclohexene oxide copolymerization (catalyst = Al(III)/K(I), turnover frequency = 1072 h–1, 0.25 mol % catalyst loading vs anhydride, 100 °C). The Al(III)/K(I) catalyst is also tolerant to low loadings, maintaining a good performance at 0.025 mol % catalyst vs anhydride loading and 0.005 mol % vs epoxide. It rapidly polymerizes other epoxide/anhydride combinations yielding various semi-aromatic, rigid, and/or functionalizable polyesters and also shows activity in carbon dioxide/epoxide copolymerizations. The results of structure–activity, X-ray crystallography, polymerization kinetics, and density functional theory investigations support a mechanism with chain growth alternation between the metals. The rate-limiting step is proposed to involve epoxide coordination at Al(III) with K(I) carboxylate attack. Future exploitation of abundant and inexpensive Group 1 metals to deliver synergic polymerization catalysts is recommended

Ultrarapid cerium(III)–NHC catalysts for high molar mass cyclic polylactide

The EPSRC are acknowledged for research funding through the Centre for Doctoral Training in Critical Resource Catalysis (CRITICAT, EP/ L016419/1, R. W. F. K., P. M. D. A. E.), EP/J018139/1, the UK Catalysis Hub (EP/K014714/1, P. L. A., C. K. W., S. K. R.), EP/M010554/1 (P. L. A.) and EP/S018603/1 (C. K. W.). This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No 740311, P.L.A.).Cyclic polyesters could improve the properties of degradable plastics, but routes to them that provide a product with faster rates, higher molar mass, and greater selectivity for cyclic vs linear polymer are needed. Here, homogeneous Ce(III)–N-heterocyclic carbene (NHC) catalysts show outstanding activities (turn-over-frequency (TOF) > 864 000 h–1), excellent control, and selectivity for cyclic polylactide (PLA) topology (>95%), yielding high molar mass PLA (60 < Mn < 250 kg mol–1). They efficiently produce cyclic PLA from rac-lactide or l-lactide and aliphatic cyclic polyesters from ε-caprolactone or β-butyrolactone. The enhanced performances are only achievable from combining cooperative Lewis acidic cerium(III) and hemilabile N-heterocyclic carbene functionalities.PostprintPostprintPeer reviewe

Prospects of Detecting Non-thermal Protons in Solar Flares via Lyman Line Spectroscopy: Revisiting the Orrall-Zirker Effect

Solar flares are efficient particle accelerators, with a substantial fraction of the energy released manifesting as non-thermal particles. While the role that non-thermal electrons play in transporting flare energy is well studied, the properties and importance of non-thermal protons is rather less well understood. This is in large part due to the paucity of diagnostics, particularly at the lower-energy (deka-keV) range of non-thermal proton distributions in flares. One means to identify the presence of deka-keV protons is by an effect originally described by \cite{1976ApJ...208..618O}. In the Orrall-Zirker effect, non-thermal protons interact with ambient neutral hydrogen, and via charge exchange produce a population of energetic neutral atoms (ENAs) in the chromosphere. These ENAs subsequently produce an extremely redshifted photon in the red wings of hydrogen spectral lines. We revisit predictions of the strength of this effect using modern interaction cross-sections, and numerical models capable of self-consistently simulating the flaring non-equilibrium ionization stratification, and the non-thermal proton distribution (and, crucially, their feedback on each other). We synthesize both the thermal and non-thermal emission from \lya\ and \lyb, the most promising lines that may exhibit a detectable signal. These new predictions are are weaker and more transient than prior estimates, but the effects should be detectable in fortuitous circumstances. We degrade the \lyb\ emission to the resolution of the Spectral Imaging of the Coronal Environment (SPICE) instrument on board Solar Orbiter, demonstrating that though likely difficult, it should be possible to detect the presence of non-thermal protons in flares observed by SPICE.Comment: Accepted for publication in The Astrophysical Journa

Exact Solution for the Exterior Field of a Rotating Neutron Star

A four-parameter class of exact asymptotically flat solutions of the Einstein-Maxwell equations involving only rational functions is presented. It is able to describe the exterior field of a slowly or rapidly rotating neutron star with poloidal magnetic field.Comment: Accepted for publication in Phys. Rev. D as Rapid Communication. 8 pages, 2 eps figure

Thrombolysis ImPlementation in Stroke (TIPS): evaluating the effectiveness of a strategy to increase the adoption of best evidence practice – protocol for a cluster randomised controlled trial in acute stroke care

BACKGROUND Stroke is a leading cause of death and disability internationally. One of the three effective interventions in the acute phase of stroke care is thrombolytic therapy with tissue plasminogen activator (tPA), if given within 4.5 hours of onset to appropriate cases of ischaemic stroke. OBJECTIVES To test the effectiveness of a multi-component multidisciplinary collaborative approach compared to usual care as a strategy for increasing thrombolysis rates for all stroke patients at intervention hospitals, while maintaining accepted benchmarks for low rates of intracranial haemorrhage and high rates of functional outcomes for both groups at three months. METHODS AND DESIGN A cluster randomised controlled trial of 20 hospitals across 3 Australian states with 2 groups: multi- component multidisciplinary collaborative intervention as the experimental group and usual care as the control group. The intervention is based on behavioural theory and analysis of the steps, roles and barriers relating to rapid assessment for thrombolysis eligibility; it involves a comprehensive range of strategies addressing individual-level and system-level change at each site. The primary outcome is the difference in tPA rates between the two groups post-intervention. The secondary outcome is the proportion of tPA treated patients in both groups with good functional outcomes (modified Rankin Score (mRS <2) and the proportion with intracranial haemorrhage (mRS ≥2), compared to international benchmarks. DISCUSSION TIPS will trial a comprehensive, multi-component and multidisciplinary collaborative approach to improving thrombolysis rates at multiple sites. The trial has the potential to identify methods for optimal care which can be implemented for stroke patients during the acute phase. Study findings will include barriers and solutions to effective thrombolysis implementation and trial outcomes will be published whether significant or not. TRIAL REGISTRATION Australian New Zealand Clinical Trials Registry: ACTRN12613000939796

Thrombolysis ImPlementation in Stroke (TIPS): evaluating the effectiveness of a strategy to increase the adoption of best evidence practice – protocol for a cluster randomised controlled trial in acute stroke care

BACKGROUND: Stroke is a leading cause of death and disability internationally. One of the three effective interventions in the acute phase of stroke care is thrombolytic therapy with tissue plasminogen activator (tPA), if given within 4.5 hours of onset to appropriate cases of ischaemic stroke. OBJECTIVES: To test the effectiveness of a multi-component multidisciplinary collaborative approach compared to usual care as a strategy for increasing thrombolysis rates for all stroke patients at intervention hospitals, while maintaining accepted benchmarks for low rates of intracranial haemorrhage and high rates of functional outcomes for both groups at three months. METHODS AND DESIGN: A cluster randomised controlled trial of 20 hospitals across 3 Australian states with 2 groups: multi- component multidisciplinary collaborative intervention as the experimental group and usual care as the control group. The intervention is based on behavioural theory and analysis of the steps, roles and barriers relating to rapid assessment for thrombolysis eligibility; it involves a comprehensive range of strategies addressing individual-level and system-level change at each site. The primary outcome is the difference in tPA rates between the two groups post-intervention. The secondary outcome is the proportion of tPA treated patients in both groups with good functional outcomes (modified Rankin Score (mRS <2) and the proportion with intracranial haemorrhage (mRS ≥2), compared to international benchmarks. DISCUSSION: TIPS will trial a comprehensive, multi-component and multidisciplinary collaborative approach to improving thrombolysis rates at multiple sites. The trial has the potential to identify methods for optimal care which can be implemented for stroke patients during the acute phase. Study findings will include barriers and solutions to effective thrombolysis implementation and trial outcomes will be published whether significant or not. TRIAL REGISTRATION: Australian New Zealand Clinical Trials Registry: ACTRN1261300093979

Thrombolysis ImPlementation in Stroke (TIPS): Evaluating the effectiveness of a strategy to increase the adoption of best evidence practice - protocol for a cluster randomised controlled trial in acute stroke care

Background: Stroke is a leading cause of death and disability internationally. One of the three effective interventions in the acute phase of stroke care is thrombolytic therapy with tissue plasminogen activator (tPA), if given within 4.5 hours of onset to appropriate cases of ischaemic stroke.Objectives: To test the effectiveness of a multi-component multidisciplinary collaborative approach compared to usual care as a strategy for increasing thrombolysis rates for all stroke patients at intervention hospitals, while maintaining accepted benchmarks for low rates of intracranial haemorrhage and high rates of functional outcomes for both groups at three months.Methods and design: A cluster randomised controlled trial of 20 hospitals across 3 Australian states with 2 groups: multi- component multidisciplinary collaborative intervention as the experimental group and usual care as the control group. The intervention is based on behavioural theory and analysis of the steps, roles and barriers relating to rapid assessment for thrombolysis eligibility; it involves a comprehensive range of strategies addressing individual-level and system-level change at each site. The primary outcome is the difference in tPA rates between the two groups post-intervention. The secondary outcome is the proportion of tPA treated patients in both groups with good functional outcomes (modified Rankin Score (mR

Has Behavioral Science Tumbled Through the Biological Looking Glass? Will Brief, Evidence-Based Training Return It From the Rabbit Hole?

Time constraints and professional demands leave practicing professionals unlikely to enroll in extended training such as a semester-long graduate course. Thus, the three-hour continuing education format has become a standard for those in practice. One may ask what sorts of training strategies optimize that format. To explore that, a three hour training program for seventy-six practicing mental health professionals, most of whom self-identified as psychologists, was devised. It made use of primarily antecedent techniques that have been shown to bring about changed perceptions on a number of topics. Content focused on two areas of importance to behavior analysts, the culture’s increasing acceptance of the biological causation model of disorders such as attentiondeficit hyperactivity disorder (ADHD), unipolar depression, anxiety disorders, and schizophrenia, and the field’s increasing reliance on medications, often to the exclusion of behavioral methods. Pre-post assessment showed that participants had changed their thinking regarding the two content areas. The authors caution that participants’ changed opinions may serve as setting events to changes in practice, but those changes are verbal. One must not assume changes in practice techniques will automatically occur