1,003 research outputs found

    Effect of core cross-linking on the physical properties of poly(dimethylsiloxane)-based diblock copolymer worms prepared in silicone oil

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    A trithiocarbonate-capped poly(dimethylsiloxane) (PDMS) precursor is chain-extended via reversible addition–fragmentation chain transfer dispersion polymerization of 2-(dimethylamino)ethyl methacrylate (DMA) in decamethylcyclopentasiloxane (D5) silicone oil at 90 °C. For a fixed mean degree of polymerization (DP) of 66 for the PDMS steric stabilizer block, targeting core-forming PDMA block DPs of between 105 and 190 enables the preparation of either well-defined worms or vesicles at a copolymer concentration of 25% w/w. The as-synthesized linear PDMS66–PDMA100 worms exhibit thermoresponsive behavior in D5, undergoing a worm-to-sphere transition on heating to 100 °C. Variable temperature 1H NMR spectroscopy indicates that this thermal transition is driven by reversible solvent plasticization of the PDMA cores. This change in copolymer morphology is characterized by transmission electron microscopy (TEM) studies, variable temperature dynamic light scattering and small-angle X-ray scattering experiments. Oscillatory rheology studies indicate that degelation occurs at 32 °C, but shear-induced polarized light imaging measurements suggest that full conversion of worms into spheres requires significantly higher temperatures (∼110 °C). 1,2-Bis(2-iodoethoxy)ethane (BIEE) is evaluated as a cross-linker for PDMS66–PDMAx diblock copolymer nano-objects in D5. This bifunctional reagent quaternizes the tertiary amine groups on the DMA residues within the worm cores, introducing cross-links via the Menshutkin reaction. TEM studies confirm that such covalently-stabilized worms no longer undergo a worm-to-sphere transition when heated to 100 °C. Kinetic studies performed on PDMS66–PDMA176 vesicles suggest that cross-linking requires approximately 13 h at 20 °C to ensure that these nano-objects remain intact when dispersed in chloroform, which is a good solvent for both blocks. Oscillatory rheology studies of a PDMS66–PDMA100 worm gel indicated that covalent stabilization using a BIEE/DMA molar ratio of 0.15 increased its dynamic elastic modulus (G′) by almost two orders of magnitude. Furthermore, such cross-linked worms exhibit a much lower critical gelation concentration (∼2% w/w) compared to that of the linear precursor worms (∼12% w/w)

    Sequencing data discovery with MetaSeek

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    Sequencing data resources have increased exponentially in recent years, as has interest in large-scale meta-analyses of integrated next-generation sequencing datasets. However, curation of integrated datasets that match a user's particular research priorities is currently a time-intensive and imprecise task. MetaSeek is a sequencing data discovery tool that enables users to flexibly search and filter on any metadata field to quickly find the sequencing datasets that meet their needs. MetaSeek automatically scrapes metadata from all publicly available datasets in the Sequence Read Archive, cleans and parses messy, user-provided metadata into a structured, standard-compliant database and predicts missing fields where possible. MetaSeek provides a web-based graphical user interface and interactive visualization dashboard, as well as a programmatic API to rapidly search, filter, visualize, save, share and download matching sequencing metadata

    Audit of paediatric cardiac services in South Africa

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    Objective: To evaluate paediatric cardiac services in South Africa with respect to referral base, services provided and human resources.Study design: A descriptive study design was used. An audit of the referral base, personnel and activity of paediatric cardiac units throughout South Africa was conducted by means of a questionnaire. A specialist from each centre was asked to provide the relevant data. Where accurate data was not available, estimates were provided by practitioners within each centre.Results: All identified units participated in the audit. Three were private sector units while the other five were primarily public sector units. Twenty four paediatric cardiologists, equally distributed between public and private sector units, were practicing in the country as at end 2008, with a further eight paediatricians undergoing training in paediatric cardiology. This is significantly less than the 88 paediatric cardiologists required for the population of South Africa. Eight paediatric cardiac surgeons were operating predominantly on children in public hospitals and five in private institutions. An estimated 1370 operations for congenital heart disease were performed over a one year period, with 800 of these in the public sector. Extrapolating from accepted estimates of congenital heart disease incidence, this represents conservatively, less that 40% of operations required for the population. Additionally, only 26% of the estimated 114 simple transposition of great arteries born annually were operated on, indicating serious deficiencies in the ability to adequately detect and intervene in serious congenital heart disease presenting in the neonatal period. Conclusion: The infrastructure and resources to detect and manage heart disease in children in South Africa, particularly within the public sector, are grossly inadequate

    Structural characterisation of MBE grown zinc-blende Ga1-xMnxN/GaAs(001) as a function of Ga flux

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    Ga1-xMnxN films grown on semi-insulating GaAs(001) substrates at 680°C with fixed Mn flux and varied Ga flux demonstrated a transition from zinc-blende/wurtzite mixed phase growth for low Ga flux (N-rich conditions) to zinc-blende single phase growth with surface Ga droplets for high Ga flux (Ga-rich conditions). N-rich conditions were found favourable for Mn incorporation in GaN lattice. α-MnAs inclusions were identified extending into the GaAs buffer layer

    Optimal paediatric cardiac services in South Africa – what do we need?

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    Most children with congenital heart disease have a good outcome if treated appropriately, however the majority of children with heart disease in South Africa do not receive appropriate care. This is related to serious deficiencies in the mechanisms and training for early detection as well as a major shortage of skilled personnel to care for these children at all levels. Most public sector hospitals are unable to cope with the number of patients requiring surgery, mainly due to inadequate theatre time allocation and intensive care facilities. Key interventions to address these deficiencies include: 1. Strategies to improve both the training and the retention of all professionals involved in the care of congenital heart disease. 2. Programmes to increase awareness of both congenital and acquired heart disease in children among health care personnel. 3. Ensuring appropriate infrastructure and equipment designed for children with congenital heart disease are available. 4. Development of congenital heart surgery as an independent subspecialty with dedicated resources and personnel. 5. Dedicated intensive care facilities for paediatric heart surgery. In addition, development of appropriate patterns of referral, stimulation of research and positive private-public partnerships are all necessary to ensure that appropriate care is delivered

    The Cost of Jointness and How to Manage It

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    Although joint programs are typically formed to reduce costs, recent studies have suggested that joint programs experience larger cost growth than non-joint programs. To explain this phenomenon, we present a model that attributes joint program cost growth to agencies’ actions to maintain or regain their autonomy. We use this model to motivate principles for architecting joint programs and outline a process that can be used to identify opportunities for reforming current joint programs or for establishing new ones. Finally, we apply our approach to analyze joint program options for NOAA’s low-earth orbiting weather satellite program and in doing so, identify several risks facing NOAA’s current program and strategies for mitigating them.Massachusetts Institute of Technology (Sandia Corporation Excellence in Engineering Graduate Fellowship)Skolkovo Institute of Science and Technolog

    RAFT dispersion polymerization of benzyl methacrylate in silicone oil using a silicone-based methacrylic stabilizer provides convenient access to spheres, worms, and vesicles

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    Reversible addition–fragmentation chain transfer (RAFT) solution polymerization of 3-[tris(trimethylsiloxy)silyl] propyl methacrylate (SiMA) was conducted in toluene to prepare three PSiMA precursors with mean degrees of polymerization (DP) of 12, 13, or 15. Each precursor was then chain-extended in turn via RAFT dispersion polymerization of benzyl methacrylate (BzMA) in a low-viscosity silicone oil (decamethylcyclopentasiloxane, D5). 1H NMR studies confirmed that such polymerizations were relatively fast, with more than 99% BzMA conversion being achieved within 100 min at 90 °C. Moreover, gel permeation chromatography analysis indicated that these polymerizations were well controlled, with dispersities remaining below 1.25 when targeting PBzMA DPs up to 200. A phase diagram was constructed at a constant copolymer concentration of 20% w/w. Only spherical micelles were accessible when the PSiMA15 stabilizer was utilized, as determined by transmission electron microscopy and small-angle X-ray scattering (SAXS) studies. Nevertheless, these spheres exhibited narrow size distributions and tunable z-average diameters ranging between 19 and 49 nm, as determined by dynamic light scattering. In contrast, spheres, worms, or vesicles could be prepared depending on the target PBzMA DP when utilizing the relatively short PSiMA12 precursor. Moreover, each of these nano-objects could be obtained at copolymer concentrations as low as 5% w/w. To obtain more detailed structural information, these spheres, worms and vesicles were further characterized by SAXS. PSiMA12-PBzMA55 worms formed reasonably transparent free-standing gels when prepared at copolymer concentrations as low as 5% w/w and exhibited an elastic modulus (G′) of 90 Pa at 25 °C, as judged by oscillatory rheology studies. Finally, broadening of the molecular weight distribution was observed during the long-term storage of PSiMA-PBzMA dispersions at ambient temperature. We tentatively suggest that this instability is related to hydroxyl impurities in the SiMA, which leads to cross-linking side reactions. This problem also causes incipient flocculation of the spheres and worms during the long-term storage of such dispersions at 20 °C

    Half-metallicity and Slater-Pauling behavior in the ferromagnetic Heusler alloys

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    Introductory chapter for the book "Halfmetallic Alloys - Fundamentals and Applications" to be published in the series Springer Lecture Notes on Physics, P. H. Dederichs and I. Galanakis (eds). It contains a review of the theoretical work on the half-metallic Heusler alloys.Comment: Introductory chapter for the book "Halfmetallic Alloys - Fundamentals and Applications" to be published in the series Springer Lecture Notes on Physics, P. H. Dederichs and I. Galanakis (eds

    On Yukawa quasi-unification with mu<0

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    Although recent data on the muon anomalous magnetic moment strongly disfavor the constrained minimal supersymmetric standard model with mu<0, they cannot exclude it because of theoretical ambiguities. We consider this model supplemented by a Yukawa quasi-unification condition which allows an acceptable b-quark mass. We find that the cosmological upper bound on the lightest sparticle relic abundance is incompatible with the data on the branching ratio of b-->s gamma, which is evaluated by including all the next-to-leading order corrections. Thus, this scheme is not viable.Comment: 4 pages including 3 figures, Revte
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