Formation and structural chemistry of the unusual cyanide-bridged dinuclear species [Ru-2(NN)(2)(CN)(7)](3-)(NN=2,2 '-bipyridine or 1,10-phenanthroline)

Crystallisation of simple cyanoruthenate complex anions [Ru(NN)(CN)(4)](2) (NN = 2,2'-bipyridine or 1,10-phenanthroline) in the presence of Lewis-acidic cations such as Ln(III) or guanidinium cations results, in addition to the expected [Ru(NN)(CN)(4)](2) salts, in the formation of small amounts of salts of the dinuclear species [Ru-2(NN)(2)(CN)(7)](3). These cyanide-bridged anions have arisen from the combination of two monomer units [Ru(NN)(CN)(4)](2) following the loss of one cyanide, presumably as HCN. The crystal structures of [Nd(H2O)(5.5)][Ru-2(bipy)(2)(CN)(7)] center dot 11H(2)O and [Pr(H2O)(6)][Ru-2(phen)(2)(CN)(7)] center dot 9H(2)O show that the cyanoruthenate anions form Ru-CN-Ln bridges to the Ln(III) cations, resulting in infinite coordination polymers consisting of fused Ru(2)Ln(2)(mu-CN)(4) squares and Ru(4)Ln(2)(mu-CN)(6) hexagons, which alternate to form a one-dimensional chain. In [CH6N3](3)[Ru-2(bipy)(2)(CN)(7)] center dot 2H(2)O in contrast the discrete complex anions are involved in an extensive network of hydrogen-bonding involving terminal cyanide ligands, water molecules, and guanidinium cations. In the [Ru-2(NN)(2)(CN)(7)](3) anions themselves the two NN ligands are approximately eclipsed, lying on the same side of the central Ru-CN-Ru axis, such that their peripheries are in close contact. Consequently, when NN = 4,4'-Bu-t(2)-2,2'-bipyridine the steric bulk of the t-butyl groups prevents the formation of the dinuclear anions, and the only product is the simple salt of the monomer, [CH6N3](2)[Ru((t)Bu(2)bipy)(CN)(4)] center dot 2H(2)O. We demonstrated by electrospray mass spectrometry that the dinuclear by-product [Ru-2(phen)(2)(CN)(7)](3) could be formed in significant amounts during the synthesis of monomeric [Ru(phen)(CN)(4)](2) if the reaction time was too long or the medium too acidic. In the solid state the luminescence properties of [Ru-2(bipy)(2)(CN)(7)](3) (as its guanidinium salt) are comparable to those of monomeric [Ru(bipy)(CN)(4)](2), with a (MLCT)-M-3 emission at 581 nm

A longitudinal study of the diabetic skin and wound microbiome

© 2017 Gardiner et al. Type II diabetes is a chronic health condition which is associated with skin conditions including chronic foot ulcers and an increased incidence of skin infections. The skin microbiome is thought to play important roles in skin defence and immune functioning. Diabetes affects the skin environment, and this may perturb skin microbiome with possible implications for skin infections and wound healing. This study examines the skin and wound microbiome in type II diabetes. Methods. Eight type II diabetic subjects with chronic foot ulcers were followed over a time course of 10 weeks, sampling from both foot skin (swabs) and wounds (swabs and debrided tissue) every two weeks. A control group of eight control subjects was also followed over 10 weeks, and skin swabs collected from the foot skin every two weeks. Samples were processed for DNA and subject to 16S rRNA gene PCR and sequencing of the V4 region. Results. The diabetic skin microbiome was significantly less diverse than control skin. Community composition was also significantly different between diabetic and control skin, however the most abundant taxa were similar between groups, with differences driven by very low abundant members of the skin communities. Chronic wounds tended to be dominated by the most abundant skin Staphylococcus, while other abundant wound taxa differed by patient. No significant correlations were found between wound duration or healing status and the abundance of any particular taxa. Discussion. The major difference observed in this study of the skin microbiome associated with diabetes was a significant reduction in diversity. The long-term effects of reduced diversity are not yet well understood, but are often associated with disease conditions

The adoption of an electronic health record did not improve A1c values in Type 2 diabetes

Background: A major justification for the clinical adoption of electronic health records (EHRs) was the expectation that it would improve the quality of medical care. No longitudinal study has tested this assumption.Objective: We used hemoglobin A1c, a recognized clinical quality measure directly related to diabetes outcomes, to assess the effect of EHR use on clinical quality.Methods: We performed a five-and-one-half-year multicentre longitudinal retrospective study of the A1c values of 537 type 2 diabetic patients. The same patients had to have been seen on at least three occasions: once approximately six months prior to EHR adoption (before-EHR), once approximately six monthsafter EHR adoption (after-EHR) and once approximately five years after EHR adoption (five-years), for a total of 1,611 notes.Results: The overall mean confidence interval (CI) A1c values for the before- EHR, after-EHR and five-years were 7.07 (6.91 – 7.23), 7.33 (7.14 – 7.52) and 7.19 (7.06 – 7.32), respectively. There was a small but significant increase in A1c values between before-EHR and after-EHR, p = .04; there were no other significant differences. There was a significant decrease in notes missing at least one A1c value, from 42% before-EHR to 16% five-years (p < .001).Conclusion: We found that based on patient’s A1c values, EHRs did not improve the clinical quality of diabetic care in six months and five years after EHR adoption. To our knowledge, this is the first longitudinal study to directly assess the relationshipbetween the use of an EHR and clinical quality.

Development of CCDs for REXIS on OSIRIS-REx

The Regolith x-ray Imaging Spectrometer (REXIS) is a coded-aperture soft x-ray imaging instrument on the OSIRIS-REx spacecraft to be launched in 2016. The spacecraft will fly to and orbit the near-Earth asteroid Bennu, while REXIS maps the elemental distribution on the asteroid using x-ray fluorescence. The detector consists of a 2×2 array of backilluminated 1k×1k frame transfer CCDs with a flight heritage to Suzaku and Chandra. The back surface has a thin p[superscript +]-doped layer deposited by molecular-beam epitaxy (MBE) for maximum quantum efficiency and energy resolution at low x-ray energies. The CCDs also feature an integrated optical-blocking filter (OBF) to suppress visible and near-infrared light. The OBF is an aluminum film deposited directly on the CCD back surface and is mechanically more robust and less absorptive of x-rays than the conventional free-standing aluminum-coated polymer films. The CCDs have charge transfer inefficiencies of less than 10[superscript -6], and dark current of 1e-/pixel/second at the REXIS operating temperature of –60 °C. The resulting spectral resolution is 115 eV at 2 KeV. The extinction ratio of the filter is ~10[superscript 12] at 625 nm.United States. National Aeronautics and Space Administration. Strategic Astrophysics Technology Program (Grant NNX12AF22G)United States. National Aeronautics and Space Administration (Contract NNG12FD70C)United States. National Aeronautics and Space Administration (IPR NNG12FC01I)United States. National Aeronautics and Space Administration. Strategic Astrophysics Technology Program (IPR NNH12AU04I)United States. Air Force (Contract FA8721-05-C-0002

The use of different sepsis risk stratification tools on the wards and in emergency departments uncovers different mortality risks: results of the three Welsh national multicenter point-prevalence studies

OBJECTIVES: To compare the performance of Sequential Organ Failure Assessment, systemic inflammatory response syndrome, Red Flag Sepsis, and National Institute of Clinical Excellence sepsis risk stratification tools in the identification of patients at greatest risk of mortality from sepsis in nonintensive care environments. DESIGN: Secondary analysis of three annual 24-hour point-prevalence study periods. SETTING: The general wards and emergency departments of 14 acute hospitals across Wales. Studies were conducted on the third Wednesday of October in 2017, 2018, and 2019. PATIENTS: We screened all patients presenting to the emergency department and on the general wards. MEASUREMENTS AND MAIN RESULTS: We recruited 1,271 patients, of which 724 (56.9%) had systemic inflammatory response syndrome greater than or equal to 2, 679 (53.4%) had Sequential Organ Failure Assessment greater than or equal to 2, and 977 (76.9%) had Red Flag Sepsis. When stratified according to National Institute of Clinical Excellence guidelines, 450 patients (35.4%) were in the “High risk” category in comparison with 665 (52.3%) in “Moderate to High risk” and 156 (12.3%) in “Low risk” category. In a planned sensitivity analysis, we found that none of the tools accurately predicted mortality at 90 days, and Sequential Organ Failure Assessment and National Institute of Clinical Excellence tools showed only moderate discriminatory power for mortality at 7 and 14 days. Furthermore, we could not find any significant correlation with any of the tools at any of the mortality time points. CONCLUSIONS: Our data suggest that the sepsis risk stratification tools currently utilized in emergency departments and on the general wards do not predict mortality adequately. This is illustrated by the disparity in mortality risk of the populations captured by each instrument, as well as the weak concordance between them. We propose that future studies on the development of sepsis identification tools should focus on identifying predicator values of both the short- and long-term outcomes of sepsis

‘Instead of fetching flowers, the youths brought in flakes of snow’: exploring extreme weather history through English parish registers

Parish registers provide organized, dated and located population data and as such, are routinely among the most frequently consulted documents within the holdings of county record offices and archives. Throughout history, extreme weather has had significant impacts on the church, its congregation, and local landscape. It is for these reasons that extreme weather events have been deemed worthy of official note by authors of many registers. Although isolated entries have been used as supporting evidence for the occurrence of a number of historic extreme weather events, the information that parish registers contain relating to weather history has not been studied in its own right. Parish register narratives add new events to existing chronologies of extreme weather events and contribute to our understanding of their impacts at the local level. As public and well used documents they also function to keep the memory of particular events alive. The examples in this paper cover a wide range of weather types, places, and time periods, also enabling recording practice to be explored. Finally, as the number of digitized registers increases, we highlight the risks of weather narratives being obscured, and reflect on how the weather history contained within might be systematically captured

LSST Science Book, Version 2.0

A survey that can cover the sky in optical bands over wide fields to faint magnitudes with a fast cadence will enable many of the exciting science opportunities of the next decade. The Large Synoptic Survey Telescope (LSST) will have an effective aperture of 6.7 meters and an imaging camera with field of view of 9.6 deg^2, and will be devoted to a ten-year imaging survey over 20,000 deg^2 south of +15 deg. Each pointing will be imaged 2000 times with fifteen second exposures in six broad bands from 0.35 to 1.1 microns, to a total point-source depth of r~27.5. The LSST Science Book describes the basic parameters of the LSST hardware, software, and observing plans. The book discusses educational and outreach opportunities, then goes on to describe a broad range of science that LSST will revolutionize: mapping the inner and outer Solar System, stellar populations in the Milky Way and nearby galaxies, the structure of the Milky Way disk and halo and other objects in the Local Volume, transient and variable objects both at low and high redshift, and the properties of normal and active galaxies at low and high redshift. It then turns to far-field cosmological topics, exploring properties of supernovae to z~1, strong and weak lensing, the large-scale distribution of galaxies and baryon oscillations, and how these different probes may be combined to constrain cosmological models and the physics of dark energy.Comment: 596 pages. Also available at full resolution at http://www.lsst.org/lsst/sciboo

Learning spaces: built, natural and digital considerations for learning and learners

The goal of this chapter is to assess research that can inform understandings of places and spaces of learning. The chapter assesses evidence across three types of learning spaces: built spaces, digital spaces, and natural spaces. It looks at the role of these different kinds of spaces for learning, attainment, interpersonal relationships, skills development, wellbeing and behaviours ‒ across four pillars of learning to know, to be, to do and to live together. The chapter also explores how learning spaces can be actively shaped, felt and understood through practices and policies that occur within and around them

Reimagining Education: The International Science and Evidence based Education Assessment.

The goal of this chapter is to assess research that can inform understandings of places and spaces of learning. The chapter assesses evidence across three types of learning spaces: built spaces, digital spaces, and natural spaces. It looks at the role of these different kinds of spaces for learning, attainment, interpersonal relationships, skills development, wellbeing and behaviours ‒ across four pillars of learning to know, to be, to do and to live together. The chapter also explores how learning spaces can be actively shaped, felt and understood through practices and policies that occur within and around them.Additional co-authors: Jo Hickman Dunne, Sarah Howard, John Lupinacci, Jamie Mcphie, Manulani Aluli Meyer, Selena Nemorin, Fikile Nxumalo, Rosie Parnell, Jessica Pykett, Pauliina Rautio, Julian Sefton Green, Neil Selwyn, David Stovall, Erica Southgate, Robert Talbert, Cheryl Teelucksingh, Richard Tucker, Ola Uduku, Alex Wilson, Adam Woo

Social Justice and Technocracy: Tracing the Narratives of Inclusive Education in the United States

Over the past two decades, the percentage of American students with disabilities educated in general classrooms with their nondisabled peers has risen by approximately fifty percent. This gradual but steady policy shift has been driven by two distinct narratives of organisational change. The social justice narrative espouses principles of equality and caring across human differences. The narrative of technocracy creates top-down, administrative pressure through hierarchical systems based on quantitative performance data. This article examines these two primary policy narratives of inclusive education in the United States, exploring the conceptual features of each and initiating an analysis of their application in the public schools