There remains considerable debate over the active form of gold under operating conditions of a recently validated gold catalyst for acetylene hydrochlorination. We have performed an in situ x-ray ...absorption fine structure study of gold/carbon (Au/C) catalysts under acetylene hydrochlorination reaction conditions and show that highly active catalysts comprise single-site cationic Au entities whose activity correlates with the ratio of Au(I):Au(III) present. We demonstrate that these Au/C catalysts are supported analogs of single-site homogeneous Au catalysts and propose a mechanism, supported by computational modeling, based on a redox couple of Au(I)-Au(III) species.
SummaryA hallmark of infection with the gram-negative pathogen Porphyromonas gingivalis is the induction of a chronic inflammatory response. P. gingivalis induces a local chronic inflammatory ...response that results in oral inflammatory bone destruction, which manifests as periodontal disease. In addition to chronic inflammation at the initial site of infection, mounting evidence has accumulated supporting a role for P. gingivalis-mediated periodontal disease as a risk factor for several systemic diseases including, diabetes, preterm birth, stroke, and atherosclerotic cardiovascular disease. A growing number of in vitro studies have demonstrated that P. gingivalis infection stimulates cell activation commensurate with expected responses paralleling inflammatory atherosclerotic-type responses. Furthermore, various mouse models have been used to examine the ability of P. gingivalis to stimulate chronic inflammatory plaque accumulation and recent studies have pointed to a pivotal role for innate immune signaling via the Toll-like receptors in the chronic inflammation associated with P. gingivalis infection. In this review we discuss the pathogen and host cell specificity of these responses and discuss possible mechanisms by which this oral pathogen can induce and maintain a chronic state of inflammation at sites distant from oral infection.
Thermal inversions have long been predicted to exist in the atmospheres of ultra-hot Jupiters. However, the detection of two species thought to be responsible – titanium oxide and vanadium oxide – ...remains elusive. We present a search for TiO and VO in the atmosphere of the ultra-hot Jupiter WASP-121b (
T
eq
≳ 2400 K), an exoplanet with evidence of VO in its atmosphere at low resolution which also exhibits water emission features in its dayside spectrum characteristic of a temperature inversion. We observed its transmission spectrum with the UV-Visual Echelle Spectrograph at the Very Large Telescope and used the cross-correlation method – a powerful tool for the unambiguous identification of the presence of atomic and molecular species – in an effort to detect whether TiO or VO were responsible for the observed temperature inversion. No evidence for the presence of TiO or VO was found at the terminator of WASP-121b. By injecting signals into our data at varying abundance levels, we set rough detection limits of VO ≲−7.9 and TiO ≲−9.3. However, these detection limits are largely degenerate with scattering properties and the position of the cloud deck. Our results may suggest that neither TiO or VO are the main drivers of the thermal inversion in WASP-121b; however, until a more accurate line list is developed for VO, we cannot conclusively rule out its presence. Future works will consist of a search for other strong optically-absorbing species that may be responsible for the excess absorption in the red-optical.
The aim of this comprehensive systematic review was to identify the most effective behavioural models and behaviour change strategies, underpinning preschool‐ and school‐based interventions aimed at ...preventing obesity in 4–6‐year‐olds. Searching was conducted from April 1995 to April 2010 using MEDLINE, EMBASE, CINAHL, PsycINFO and The Cochrane Library. Epidemiological studies relevant to the research question with controlled assignment of participants were included in the review, if they had follow‐up periods of 6 months or longer. Outcomes included markers of weight gain; markers of body composition; physical activity behaviour changes and dietary behaviour changes. Twelve studies were included in the review. The most commonly used model was social cognitive theory (SCT)/social learning theory (SLT) either as a single model or in combination with other behavioural models. Studies that used SCT/SLT in the development of the intervention had significant favourable changes in one, or more, outcome measures. In addition, interventions that (i) combined high levels of parental involvement and interactive school‐based learning; (ii) targeted physical activity and dietary change; and (iii) included long‐term follow‐up, appeared most effective. It is suggested that interventions should also be focused on developing children's (and parents') perceived competence at making dietary and physical changes.
Access to healthcare is a requirement for human well-being that is constrained, in part, by the allocation of healthcare resources relative to the geographically dispersed human population
. ...Quantifying access to care globally is challenging due to the absence of a comprehensive database of healthcare facilities. We harness major data collection efforts underway by OpenStreetMap, Google Maps and academic researchers to compile the most complete collection of facility locations to date. Leveraging the geographically variable strengths of our facility datasets, we use an established methodology
to characterize travel time to healthcare facilities in unprecedented detail. We produce maps of travel time with and without access to motorized transport, thus characterizing travel time to healthcare for populations distributed across the wealth spectrum. We find that just 8.9% of the global population (646 million people) cannot reach healthcare within one hour if they have access to motorized transport, and that 43.3% (3.16 billion people) cannot reach a healthcare facility by foot within one hour. Our maps highlight an additional vulnerability faced by poorer individuals in remote areas and can help to estimate whether individuals will seek healthcare when it is needed, as well as providing an evidence base for efficiently distributing limited healthcare and transportation resources to underserved populations both now and in the future.
Although photoexcitation has been employed to unlock the low-temperature equilibrium regimes of thermal catalysis, mechanism underlining potential interplay between electron excitations and surface ...chemical processes remains elusive. Here, we report an associative zinc oxide band-gap excitation and copper plasmonic excitation that can cooperatively promote methanol-production at the copper-zinc oxide interfacial perimeter of copper/zinc oxide/alumina (CZA) catalyst. Conversely, selective excitation of individual components only leads to the promotion of carbon monoxide production. Accompanied by the variation in surface copper oxidation state and local electronic structure of zinc, electrons originating from the zinc oxide excitation and copper plasmonic excitation serve to activate surface adsorbates, catalysing key elementary processes (namely formate conversion and hydrogen molecule activation), thus providing one explanation for the observed photothermal activity. These observations give valuable insights into the key elementary processes occurring on the surface of the CZA catalyst under light-heat dual activation.
Insomnia symptoms are widespread in the population and might have effects on many chronic conditions and their risk factors but previous research has focused on select hypothesised ...associations/effects rather than taking a systematic hypothesis-free approach across many health outcomes.
We performed a Mendelian randomisation (MR) phenome-wide association study (PheWAS) in 336,975 unrelated white-British UK Biobank participants. Self-reported insomnia symptoms were instrumented by a genetic risk score (GRS) created from 129 single-nucleotide polymorphisms (SNPs). A total of 11,409 outcomes from UK Biobank were extracted and processed by an automated pipeline (PHESANT) for the MR-PheWAS. Potential causal effects (those passing a Bonferroni-corrected significance threshold) were followed up with two-sample MR in MR-Base, where possible.
Four hundred thirty-seven potential causal effects of insomnia symptoms were observed for a diverse range of outcomes, including anxiety, depression, pain, body composition, respiratory, musculoskeletal and cardiovascular traits. We were able to undertake two-sample MR for 71 of these 437 and found evidence of causal effects (with directionally concordant effect estimates across main and sensitivity analyses) for 30 of these. These included novel findings (by which we mean not extensively explored in conventional observational studies and not previously explored using MR based on a systematic search) of an adverse effect on risk of spondylosis (OR 95%CI = 1.55 1.33, 1.81) and bronchitis (OR 95%CI = 1.12 1.03, 1.22), among others.
Insomnia symptoms potentially cause a wide range of adverse health-related outcomes and behaviours. This has implications for developing interventions to prevent and treat a number of diseases in order to reduce multimorbidity and associated polypharmacy.
We model the time variability of {approx}9000 spectroscopically confirmed quasars in SDSS Stripe 82 as a damped random walk (DRW). Using 2.7 million photometric measurements collected over 10 yr, we ...confirm the results of Kelly et al. and Kozlowski et al. that this model can explain quasar light curves at an impressive fidelity level (0.01-0.02 mag). The DRW model provides a simple, fast (O(N) for N data points), and powerful statistical description of quasar light curves by a characteristic timescale ({tau}) and an asymptotic rms variability on long timescales (SF{sub {infinity}}). We searched for correlations between these two variability parameters and physical parameters such as luminosity and black hole mass, and rest-frame wavelength. Our analysis shows SF{sub {infinity}} to increase with decreasing luminosity and rest-frame wavelength as observed previously, and without a correlation with redshift. We find a correlation between SF{sub {infinity}} and black hole mass with a power-law index of 0.18 {+-} 0.03, independent of the anti-correlation with luminosity. We find that {tau} increases with increasing wavelength with a power-law index of 0.17, remains nearly constant with redshift and luminosity, and increases with increasing black hole mass with a power-law index of 0.21 {+-} 0.07. The amplitude of variability is anti-correlated with the Eddington ratio, which suggests a scenario where optical fluctuations are tied to variations in the accretion rate. However, we find an additional dependence on luminosity and/or black hole mass that cannot be explained by the trend with Eddington ratio. The radio-loudest quasars have systematically larger variability amplitudes by about 30%, when corrected for the other observed trends, while the distribution of their characteristic timescale is indistinguishable from that of the full sample. We do not detect any statistically robust differences in the characteristic timescale and variability amplitude between the full sample and the small subsample of quasars detected by ROSAT. Our results provide a simple quantitative framework for generating mock quasar light curves, such as currently used in LSST image simulations.
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