The Jahn-Teller active fluoroperovskites ACrF3A\mathrm{CrF_3} A=Na+,K+A=\mathrm{Na^+},\mathrm{K^+}: thermo- and magneto optical correlations as function of the AA-site

Chromium (II) fluoroperovskites $A\mathrm{CrF_3}(A\mathrm{=Na^+,K^+})$ are strongly correlated Jahn-Teller active materials at low temperatures. In this paper, we examine the role that the $A$-site ion plays in this family of fluoroperovskites using both experimental methods (XRD, optical absorption spectroscopy and magnetic fields) and DFT simulations. Temperature-dependent optical absorption experiments show that the spin-allowed transitions $E_2$ and $E_3$ only merge completely for $A$= Na at 2 K. Field-dependent optical absorption measurements at 2 K show that the oscillating strength of the spin-allowed transitions in $\mathrm{NaCrF_3}$ increases with increasing applied field. Direct magneto-structural correlations which suppress the spin-flip transitions are observed for ${\rm KCrF_3}$ below its Ne\'el temperature. In ${\rm NaCrF_3}$ the spin-flip transitions vanish abruptly below 9 K revealing magneto-optical correlations not linked to crystal structure changes. This suggests that as the long range ordering is reduced local JT effects in the individual ${\rm CrF_6^{4-}}$ octahedra take control of the observed behavior. Our results show clear deviation from the pattern found for the isoelectronic $A_x{\rm MnF}_{3+x}$ system. The size of the $A$-site cation is shown to be central in dictating the physical properties and phase transitions in $A{\rm CrF}_3$, opening up the possibility of varying the composition to create novel states of matter with tuneable properties

Glycoprotein IIb/IIIa Inhibitors Use and Outcome after Percutaneous Coronary Intervention for Non-ST Elevation Myocardial Infarction

Aims. We investigate the effect of glycoprotein IIb/IIIa (GP IIb/IIIa) inhibitors on long-term outcomes following percutaneous coronary intervention (PCI) after non-ST elevation myocardial infarction (NSTEMI). Meta-analyses indicate that these agents are associated with improved short-term outcomes. However, many trials were undertaken before the routine use of P2Y12 inhibitors. Recent studies yield conflicting results and registry data have suggested that GP IIb/IIIa inhibitors may cause more bleeding than what trials indicate. Methods and Results. This retrospective observational study involves 3047 patients receiving dual-antiplatelet therapy who underwent PCI for NSTEMI. Primary outcome was all-cause mortality. Major adverse cardiac events (MACE) were a secondary outcome. Mean follow-up was 4.6 years. Patients treated with GP IIb/IIIa inhibitors were younger with fewer comorbidities. Although the unadjusted Kaplan-Meier analysis suggested that GP IIb/IIIa inhibitor use was associated with improved outcomes, multivariate analysis (including propensity scoring) showed no benefit for either survival (P=0.136) or MACE (P=0.614). GP IIb/IIIa inhibitor use was associated with an increased risk of major bleeding (P=0.021). Conclusion. Although GP IIb/IIIa inhibitor use appeared to improve outcomes after PCI for NSTEMI, patients who received GP IIb/IIIa inhibitors tended to be at lower risk. After multivariate adjustment we observed no improvement in MACE or survival and an increased risk of major bleeding

Determination of the nature of the Cu coordination complexes formed in the presence of NO and NH3 within SSZ-13

Ammonia-selective catalytic reduction (NH3-SCR) using Cu zeolites is a well-established strategy for the abatement of NOx gases. Recent studies have demonstrated that Cu is particularly active when exchanged into the SSZ-13 zeolite, and its location in either the 6r or 8r renders it an excellent model system for fundamental studies. In this work, we examine the interaction of NH3-SCR relevant gases (NO and NH3) with the Cu2+ centers within the SSZ-13 structure, coupling powder diffraction (PD), X-ray absorption spectroscopy (XAFS), and density functional theory (DFT). This combined approach revealed that, upon calcination, cooling and gas exposure Cu ions tend to locate in the 8r window. After NO introduction, Cu-ions are seen to coordinate to two framework oxygens and one NO molecule, resulting in a bent Cu-nitrosyl complex with a Cu-N-O bond angle of similar to 150 degrees. Whilst Cu seems to be partially reduced/changed in coordination state, NO is partially oxidized. On exposure to NH3 while the PD data suggest the Cu2+ ion occupies a similar position, simulation and XAFS pointed toward the formation of a Jahn-Teller distorted hexaamine complex [Cu(NH3)(6)](2+) in the center of the cha cage. These results have important implications in terms of uptake and storage of these reactive gases and potentially for the mechanisms involved in the NH3-SCR process

Dual-initiation promoters with intertwined canonical and TCT/TOP transcription start sites diversify transcript processing

Variations in transcription start site (TSS) selection reflect diversity of preinitiation complexes and can impact on post-transcriptional RNA fates. Most metazoan polymerase II-transcribed genes carry canonical initiation with pyrimidine/purine (YR) dinucleotide, while translation machinery-associated genes carry polypyrimidine initiator (5'-TOP or TCT). By addressing the developmental regulation of TSS selection in zebrafish we uncovered a class of dual-initiation promoters in thousands of genes, including snoRNA host genes. 5'-TOP/TCT initiation is intertwined with canonical initiation and used divergently in hundreds of dual-initiation promoters during maternal to zygotic transition. Dual-initiation in snoRNA host genes selectively generates host and snoRNA with often different spatio-temporal expression. Dual-initiation promoters are pervasive in human and fruit fly, reflecting evolutionary conservation. We propose that dual-initiation on shared promoters represents a composite promoter architecture, which can function both coordinately and divergently to diversify RNAs

The abolition of the General Teaching Council for England and the future of teacher discipline

With the abolition of the General Teaching Council for England in the 2011 Education Act, this article considers the future of teacher discipline in England. It provides a critique of the changes to the regulation of teacher misconduct and incompetence that draws on a Foucauldian framework, especially concerning the issue of public displays of discipline and the concomitant movement to more hidden forms. In addition, the external context of accountability that accompanies the reforms to teacher discipline are considered including the perfection of the panoptic metaphor presented by the changes to Ofsted practices such as the introduction of zero-notice inspections. The article concludes that the reforms will further move teachers from being occupational professionals to being organisational professionals marking them apart from comparable professions in medicine and law

Clinically Actionable Insights into Initial and Matched Recurrent Glioblastomas to Inform Novel Treatment Approaches

© 2019 H. P. Ellis et al. Glioblastoma is the most common primary adult brain tumour, and despite optimal treatment, the median survival is 12-15 months. Patients with matched recurrent glioblastomas were investigated to try to find actionable mutations. Tumours were profiled using a validated DNA-based gene panel. Copy number variations (CNVs) and single nucleotide variants (SNVs) were examined, and potentially pathogenic variants and clinically actionable mutations were identified. The results revealed that glioblastomas were IDH-wildtype (IDHWT; n = 38) and IDH-mutant (IDHMUT; n = 3). SNVs in TSC2, MSH6, TP53, CREBBP, and IDH1 were variants of unknown significance (VUS) that were predicted to be pathogenic in both subtypes. IDHWT tumours had SNVs that impacted RTK/Ras/PI(3)K, p53, WNT, SHH, NOTCH, Rb, and G-protein pathways. Many tumours had BRCA1/2 (18%) variants, including confirmed somatic mutations in haemangioblastoma. IDHWT recurrent tumours had fewer pathways impacted (RTK/Ras/PI(3)K, p53, WNT, and G-protein) and CNV gains (BRCA2, GNAS, and EGFR) and losses (TERT and SMARCA4). IDHMUT tumours had SNVs that impacted RTK/Ras/PI(3)K, p53, and WNT pathways. VUS in KLK1 was possibly pathogenic in IDHMUT. Recurrent tumours also had fewer pathways (p53, WNT, and G-protein) impacted by genetic alterations. Public datasets (TCGA and GDC) confirmed the clinical significance of findings in both subtypes. Overall in this cohort, potentially actionable variation was most often identified in EGFR, PTEN, BRCA1/2, and ATM. This study underlines the need for detailed molecular profiling to identify individual GBM patients who may be eligible for novel treatment approaches. This information is also crucial for patient recruitment to clinical trials