628 research outputs found

    UV solar irradiance in observations and the NRLSSI and SATIRE-S models

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    Total solar irradiance and UV spectral solar irradiance have been monitored since 1978 through a succession of space missions. This is accompanied by the development of models aimed at replicating solar irradiance by relating the variability to solar magnetic activity. The NRLSSI and SATIRE-S models provide the most comprehensive reconstructions of total and spectral solar irradiance over the period of satellite observation currently available. There is persistent controversy between the various measurements and models in terms of the wavelength dependence of the variation over the solar cycle, with repercussions on our understanding of the influence of UV solar irradiance variability on the stratosphere. We review the measurement and modelling of UV solar irradiance variability over the period of satellite observation. The SATIRE-S reconstruction is consistent with spectral solar irradiance observations where they are reliable. It is also supported by an independent, empirical reconstruction of UV spectral solar irradiance based on UARS/SUSIM measurements from an earlier study. The weaker solar cycle variability produced by NRLSSI between 300 and 400 nm is not evident in any available record. We show that although the method employed to construct NRLSSI is principally sound, reconstructed solar cycle variability is detrimentally affected by the uncertainty in the SSI observations it draws upon in the derivation. Based on our findings, we recommend, when choosing between the two models, the use of SATIRE-S for climate studies

    Mechanochemical organocatalysis: do high enantioselectivities contradict what we might expect?

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    Ball mills input energy to samples by pulverising the contents of the jar. Each impact on the sample or wall of the jar results in an instantaneous transmission of energy in the form of a temperature and pressure increase (volume reduction). Conversely, enantioselective organocatalytic reactions proceed through perceived delicate and well-organised transition states. Does there exist a dichotomy in the idea of enantioselective mechanochemical organocatalysis? This Review provides a survey of the literature reporting the combination of organocatalytic reactions with mechanochemical ball milling conditions. Where possible, direct comparisons of stirred in solution, stirred neat and ball milled processes are drawn with a particular focus on control of stereoselectivity

    Expedient organocatalytic Aza-Morita–Baylis–Hillman reaction through ball-milling

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    A ball-milling enabled tertiary amine catalyzed aza-Morita–Baylis–Hillman reaction is reported. The reaction process does not require solvent, has significantly shorter reaction times than previous methods and is reported on a range of imines and acrylate Michael acceptors across than 26 examples. A 12-fold scaled-up example is also reported as well as experimental comparisons to solution-based experiments and neat-stirred reactions

    Nickel‐catalyzed intramolecular alkene difunctionalization by ball‐milling

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    A mechanochemical nickel‐catalyzed intramolecular difunctionalization reaction of alkene tethered aryl halides with alkyl halides is herein described. This method allows for synthesis of 3,3‐disubstituted heterocycles, namely oxindoles, with shorter reaction times than solution‐phase counterparts. Additionally, this process is solvent minimized, with DMA used in liquid‐assisted grinding (LAG) quantities and circumvents the need for chemical activation of the terminal reductant (manganese) through mechanical grinding. The process can be scaled up to yield over a gram of product and modest enantioinduction is possible by utilizing a chiral PyrOx ligand. imag

    Mechanical activation of zero-valent metal reductants for nickel-catalyzed cross-electrophile coupling

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    The cross-electrophile coupling of either twisted-amides or heteroaryl halides with alkyl halides, enabled by ball-milling, is herein described. The operationally simple nickel-catalyzed process has no requirement for inert atmosphere or dry solvents and delivers the corresponding acylated or heteroarylated products across a broad range of substrates. Key to negating the necessity of inert reaction conditions is the mechanical activation of the raw metal terminal reductant: manganese in the case of twisted amides and zinc for heteroaryl halides

    The Levellers, political literacy and contemporary citizenship education in England

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    This paper analyses the concept of political literacy (as introduced in the 1998 Crick Report) in relation to Citizenship in the English National Curriculum. It argues that political literacy has not been sufficiently emphasised or facilitated within this foundation subject and that the concept is particularly important for students at a time of considerable political and social conflict in England (and elsewhere). The authors state that engagement with the ideas and practices of the Levellers (a political group writing and agitating at the time of the Civil Wars) could enable students and teachers to explore political literacy (especially the implications of social media) by looking at a political group who utilised mass pamphlettering as a form of political communication. The paper will also investigate the context of Citizenship within the English National Curriculum and some of the philosophical concerns around Citizenship education. It contains a section placing the Levellers in their contemporary and historiographical contexts

    Nonequilibrium clumped isotope signals in microbial methane

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    Methane is a key component in the global carbon cycle with a wide range of anthropogenic and natural sources. Although isotopic compositions of methane have traditionally aided source identification, the abundance of its multiply-substituted “clumped” isotopologues, e.g., 13CH3D, has recently emerged as a proxy for determining methane-formation temperatures; however, the impact of biological processes on methane’s clumped isotopologue signature is poorly constrained. We show that methanogenesis proceeding at relatively high rates in cattle, surface environments, and laboratory cultures exerts kinetic control on 13CH3D abundances and results in anomalously elevated formation temperature estimates. We demonstrate quantitatively that H2 availability accounts for this effect. Clumped methane thermometry can therefore provide constraints on the generation of methane in diverse settings, including continental serpentinization sites and ancient, deep groundwaters.National Science Foundation (U.S.) (EAR-1250394)National Science Foundation (U.S.) (EAR-1322805)Deep Carbon Observatory (Program)Natural Sciences and Engineering Research Council of CanadaDeutsche Forschungsgemeinschaft (Gottfried Wilhelm Leibniz Program)United States. Dept. of Defense (National Defense Science and Engineering Graduate Fellowship)Neil & Anna Rasmussen FoundationGrayce B. Kerr Fund, Inc. (Fellowship)MIT Energy Initiative (Shell-MITEI Graduate Fellowship)Shell International Exploration and Production B.V. (N. Braunsdorf and D. Smit of Shell PTI/EG grant

    Genetics of myocardial interstitial fibrosis in the human heart and association with disease

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    Myocardial interstitial fibrosis is associated with cardiovascular disease and adverse prognosis. Here, to investigate the biological pathways that underlie fibrosis in the human heart, we developed a machine learning model to measure native myocardial T1 time, a marker of myocardial fibrosis, in 41,505 UK Biobank participants who underwent cardiac magnetic resonance imaging. Greater T1 time was associated with diabetes mellitus, renal disease, aortic stenosis, cardiomyopathy, heart failure, atrial fibrillation, conduction disease and rheumatoid arthritis. Genome-wide association analysis identified 11 independent loci associated with T1 time. The identified loci implicated genes involved in glucose transport (SLC2A12), iron homeostasis (HFE, TMPRSS6), tissue repair (ADAMTSL1, VEGFC), oxidative stress (SOD2), cardiac hypertrophy (MYH7B) and calcium signaling (CAMK2D). Using a transforming growth factor ÎČ1-mediated cardiac fibroblast activation assay, we found that 9 of the 11 loci consisted of genes that exhibited temporal changes in expression or open chromatin conformation supporting their biological relevance to myofibroblast cell state acquisition. By harnessing machine learning to perform large-scale quantification of myocardial interstitial fibrosis using cardiac imaging, we validate associations between cardiac fibrosis and disease, and identify new biologically relevant pathways underlying fibrosis.</p
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