72 research outputs found

    To what extent is behaviour a problem in English schools?:Exploring the scale and prevalence of deficits in classroom climate

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    The working atmosphere in the classroom is an important variable in the process of education in schools, with several studies suggesting that classroom climate is an important influence on pupil attainment. There are wide differences in the extent to which classroom climate is considered to be a problem in English schools. Some ‘official’ reports suggest that behaviour in schools is ‘satisfactory or better’ in the vast majority of schools; other sources have pointed to behaviour being a serious and widespread problem. The paper details four studies conducted over the past decade which aimed to explore these disparities. The aim of the research was to gain a more accurate insight into the extent to which deficits in classroom climate limit educational attainment and equality of educational opportunity in English schools. The findings question the suggestion that behaviour is satisfactory or better in 99.7% of English schools and the concluding section suggests ways in which deficits in classroom climate might be addressed. Although the study is limited to classrooms in England, OECD studies suggest that deficits in the working atmosphere in classrooms occur in many countries. The study therefore has potential relevance for education systems in other countries

    Expanding the Toolbox for Label-Free Enzyme Assays: A Dinuclear Platinum(II) Complex/DNA Ensemble with Switchable Near-IR Emission

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    Switchable luminescent bioprobes whose emission can be turned on as a function of specific enzymatic activity are emerging as important tools in chemical biology. We report a promising platform for the development of label-free and continuous enzymatic assays in high-throughput mode based on the reversible solvent-induced self-assembly of a neutral dinuclear Pt(II) complex. To demonstrate the utility of this strategy, the switchable luminescence of a dinuclear Pt(II) complex was utilized in developing an experimentally simple, fast (10 min), low cost, and label-free turn-on luminescence assay for the endonuclease enzyme DNAse I. The complex displays a near-IR (NIR) aggregation-induced emission at 785 nm in aqueous solution that is completely quenched upon binding to G-quadruplex DNA from the human c-myc oncogene. Luminescence is restored upon DNA degradation elicited by exposure to DNAse I. Correlation between near-IR luminescence intensity and DNAse I concentration in human serum samples allows for fast and label-free detection of DNAse I down to 0.002 U/mL. The Pt(II) complex/DNA assembly is also effective for identification of DNAse I inhibitors, and assays can be performed in multiwell plates compatible with high-throughput screening. The combination of sensitivity, speed, convenience, and cost render this method superior to all other reported luminescence-based DNAse I assays. The versatile response of the Pt(II) complex to DNA structures promises broad potential applications in developing real-time and label-free assays for other nucleases as well as enzymes that regulate DNA topology

    Salts and Co-Crystalline Assemblies of Tetra(4-Pyridyl)Ethylene with Di-Carboxylic Acids

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    Tetraarylethylene derivatives are emerging as an increasingly important family of supramolecular building blocks in both solution phase and the solid state. The utility of tetraarylethylenes stems from appealing structural features (rigidity and symmetry) and their propensity to exhibit aggregation induced emission (AIE). In an effort to investigate the luminescent sensing ability of heteroaromatic tetraarylethylenes, we previously prepared tetra(4-pyridyl)ethylene and characterized its solution phase AIE properties. We here report the successful incorporation of tetra(4-pyridyl)ethylene into three distinct salts and co-crystalline assemblies with three organic di-carboxylic acids (oxalic acid, malonic acid, and fumaric acid). Interactions between the tetra(pyridyl)ethylene and di-acid components were found to vary from conventional to charge-assisted hydrogen bonding according to the extent of proton transfer between the acid and pyridine groups. Notably, the formation of pyridinium-carboxylate adducts in the salts does not appear to be strongly correlated with acid pKa. Three distinct network topologies were observed, and all featured the bridging of two or three tetra(pyridyl)ethylene groups through di-acid linkers. Crystalline assemblies also retained the AIE activity of tetra(pyridyl)ethylene and were luminescent under UV light. As tetra(4-pyridyl)ethylene features four Lewis basic and potentially metal ligating pyridine rings in a relatively well-defined geometry, this compound represents an attractive building block for the design of additional crystalline organic and metal–organic functional materials

    Intramolecular Addition of Stabilized Enolates to (Ρ 6

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    Intramolecular Cyclization Manifolds of 4‑Alkylpyridines Bearing Ambiphilic Side Chains: Construction of Spirodihydropyridines or Benzylic Cyclization via Anhydrobase Intermediates

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    4-Alkylpyridines possessing nucleophilic β-dicarbonyl side chains have been converted to spirodihydropyridines upon treatment with ethyl chloroformate and sub-stoichiometric amounts of Ti­(O<sup><i>i</i></sup>Pr)<sub>4</sub>. Alternatively, inclusion of mild base in the reaction medium was found to facilitate generation of anhydrobase intermediates. Subsequent aldol-like condensations with electrophilic side chain moieties followed by hydrolysis delivered benzylically cyclized pyridines in good yield. In situ hydrogenation of cyclized anhydrobase intermediates afforded 4-substituted piperidines

    Construction of 1,2,4-Triazole Derivatives via Cyclocondensation of Alkylidene Dihydropyridines and Aryldiazonium Salts

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    Alkylidene dihydropyridines (anhydrobases) prepared via dearomatization of N-acylated 4-(aminomethyl)­pyridines participate in [3 + 2] cyclocondensation reactions with aryldiazonium cations to afford substituted 1,2,4-triazolium salts or neutral 1,2,4-triazoles in high isolated yield. The reaction proceeds in the presence of a variety of <i>N</i>-acyl groups and aryl-susbtituted diazonium salts and offers a general route to pyridyl-substituted 1,2,4-triazoles
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