Do managed clinical networks improve quality of diabetes care? : Evidence from a retrospective mixed methods evaluation

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Methodology to estimate ionospheric scintillation risk maps and their contribution to position dilution of precision on the ground

Satellite-based communications, navigation systems and many scientific instruments rely on observations of trans-ionospheric signals. The quality of these signals can be deteriorated by ionospheric scintillation which can have detrimental effects on the mentioned applications. Therefore, monitoring of ionospheric scintillation and quantifying its effect on the ground are of significant interest. In this work, we develop a methodology which estimates the scintillation induced ionospheric uncertainties in the sky and translates their impact to the end-users on the ground. First, by using the risk concept from decision theory and by exploiting the intensity and duration of scintillation events (as measured by the S4 index), we estimate ionospheric risk maps that could readily give an initial impression on the effects of scintillation on the satellite-receiver communication. However, to better understand the influence of scintillation on the positioning accuracy on the ground, we formulate a new weighted dilution of precision (WPDOP) measure that incorporates the ionospheric scintillation risks as weighting factors for the given satellite-receiver constellations. These weights depend implicitly on scintillation intensity and duration thresholds which can be specified by the end-user based on the sensitivity of the application, for example. We demonstrate our methodology by using scintillation data from South America, and produce ionospheric risk maps which illustrate broad scintillation activity, especially at the equatorial anomaly. Moreover, we construct ground maps of WPDOP over a grid of hypothetical receivers which reveal that ionospheric scintillation can also affect such regions of the continent that are not exactly under the observed ionospheric scintillation structures. Particularly, this is evident in cases when only the Global Positioning System (GPS) is available.Comment: Keywords: Ionospheric scintillation risk, dilution of precision, statistics error covariances, weights, South America, S4 index, GNSS positioning uncertaint

Field responsive mechanical metamaterials.

Typically, mechanical metamaterial properties are programmed and set when the architecture is designed and constructed, and do not change in response to shifting environmental conditions or application requirements. We present a new class of architected materials called field responsive mechanical metamaterials (FRMMs) that exhibit dynamic control and on-the-fly tunability enabled by careful design and selection of both material composition and architecture. To demonstrate the FRMM concept, we print complex structures composed of polymeric tubes infilled with magnetorheological fluid suspensions. Modulating remotely applied magnetic fields results in rapid, reversible, and sizable changes of the effective stiffness of our metamaterial motifs

Concussion-related Alterations in Neural Activity During Emotion Recognition: Case Studies of Short-term and Residual Effects

Concussions have recently become an area of concern among the general public, but a clear understanding of their total consequence is still being developed. Symptoms of concussions are wide-ranging, encapsulating a plethora of cognitive and emotional abilities that could be affected. Concussions transiently disrupt neural activation as well as behavioral responses across multiple categories. Skills pertaining to various aspects of emotions are often affected yet have rarely been studied after concussions. We present two case studies of collegiate athletes with a history of multiple concussions. This paper highlights the case of a collegiate athlete who had obtained two previous concussions with the most recent being sustained sixteen days prior to neuroimaging. A second athlete with two lifetime concussions was tested one year after the most recent injury. The current study utilized a novel emotional recognition task to assess the behavioral and neural effects of this injury. A group of five controls responded with high accuracy rates and quick response times to the task. They showed activation in regions of the frontal lobe as well as facial recognition areas of the occipital lobe. The 16-day case subject was impaired in recognizing emotions relative to controls and showed little to no overlap in brain activity for regions involved in emotional face processing. The athlete with a longer post-concussion period also showed residual effects of neural activity alteration when compared to controls with few overlapping active regions. Specific brain regions were activated in this group but not in controls including the sensorimotor cortex, supramarginal gyrus, and lateral occipital cortex. By taking a more individual approach in examination of neural activity post-concussion, we may be able to gain a better understanding of this heterogeneous injury

Rate and equilibrium constants for the addition of triazolium salt derived N-heterocyclic carbenes to heteroaromatic aldehydes

Heteroaromatic aldehydes are often used preferentially or exclusively in a range of NHC-catalysed processes that proceed through the generation of a reactive diaminoenol or Breslow Intermediate (BI), with the reason for their unique reactivity currently underexplored. This manuscript reports measurement of rate and equilibrium constants for the reaction between N-aryl triazolium NHCs and heteroaromatic aldehydes, providing insight into the effect of the NHC and heteroaromatic aldehyde structure up to formation of the BI. Variation in NHC catalyst and heteroaromatic aldehyde structure markedly affect the observed kinetic parameters of adduct formation, decay to starting materials and onward reaction to BI. In particular, large effects are observed with both 3-halogen (Br, F) and 3-methyl substituted pyridine-2-carboxaldehyde derivatives which substantially favour formation of the tetrahedral intermediate relative to benzaldehyde derivatives. Key observations indicate that increased steric hindrance leads to a reduction in both k2 and k−1 for large (2,6-disubstituted)-N-Ar groups within the triazolium scaffold, and sterically demanding aldehyde substituents in the 3-position, but not in the 6-position of the pyridine-2-carboxaldehyde derivatives. As part of this study, the isolation and characterisation of twenty tetrahedral adducts formed upon addition of N-aryl triazolium derived NHCs into heteroaromatic aldehydes are described. These adducts are key intermediates in NHC-catalysed umpolung addition of heteroaromatic aldehydes and are BI precursors

The mechanism of ϕC31 integrase directionality : experimental analysis and computational modelling

Serine integrases, DNA site-specific recombinases used by bacteriophages for integration and excision of their DNA to and from their host genomes, are increasingly being used as tools for programmed rearrangements of DNA molecules for biotechnology and synthetic biology. A useful feature of serine integrases is the simple regulation and unidirectionality of their reactions. Recombination between the phage attP and host attB sites is promoted by the serine integrase alone, giving recombinant attL and attR sites, whereas the 'reverse' reaction (between attL and attR) requires an additional protein, the recombination directionality factor (RDF). Here, we present new experimental data on the kinetics and regulation of recombination reactions mediated by ϕC31 integrase and its RDF, and use these data as the basis for a mathematical model of the reactions. The model accounts for the unidirectionality of the attP × attB and attL × attR reactions by hypothesizing the formation of structurally distinct, kinetically stable integrase-DNA product complexes, dependent on the presence or absence of RDF. The model accounts for all the available experimental data, and predicts how mutations of the proteins or alterations of reaction conditions might increase the conversion efficiency of recombination

Enantioselective isothiourea-catalysed trans-dihydropyridinone synthesis using saccharin-derived ketimines : scope and limitations

The authors thank Syngenta and the EPSRC (grant code EP/K503162/1) (DGS) 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 (CMY). ADS thanks the Royal Society for a Wolfson Research Merit Award. We also thank the EPSRC UK National Mass Spectrometry Facility at Swansea University.The catalytic enantioselective synthesis of a range of trans-dihydropyridinones from aryl-, heteroaryl- and alkenylacetic acids and saccharin-derived ketimines with good to excellent stereocontrol (15 examples, up to >95:5 dr, up to >99:1 er) is reported. After extensive optimisation, HyperBTM proved the optimal isothiourea catalyst for this transformation at −78 °C, giving trans-dihydropyridones with generally excellent levels of diastereo- and enantioselectivity.Publisher PDFPeer reviewe