115 research outputs found

    The semiquinone radical anion of 1,10-phenanthroline-5,6-dione: synthesis and rare earth coordination chemistry

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    Reduction of 1,10-phenanthroline-5,6-dione (pd) with CoCpR2 resulted in the first molecular compounds of the pd˙− semi-quinone radical anion, [CoCpR2]+[pd]˙− (R = H, (1); R = Me4, (2)). Furthermore compounds 1 and 2 were reacted with [Y(hfac)3(thf)2] (hfac = 1,1,1-5,5,5-hexafluoroacetylacetonate) to synthesise the rare earth-transition metal heterometallic compounds, [CoCpR2]+[Y(hfac)3(N,N′-pd)]˙− (R = H, (3); R = Me4, (4))

    The modular synthesis of rare earth-transition metal heterobimetallic complexes utilizing a redox-active ligand

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    We report a robust and modular synthetic route to heterometallic rare earth-transition metal complexes. We have used the redox-active bridging ligand 1,10-phenathroline-5,6-dione (pd), which has selective N,N′ or O,O′ binding sites as the template for this synthetic route. The coordination complexes [Ln(hfac)3(N,N’-pd)] (Ln = Y [1], Gd [2]; hfac = hexafluoroacetylacetonate) were synthesised in high yield. These complexes have been fully characterised using a range of spectroscopic techniques. Solid state molecular structures of 1 and 2 have been determined by X-ray crystallography and display different pd binding modes in coordinating and non-coordinating solvents. Complexes 1 and 2 are unusually highly coloured in coordinating solvents, for example the vis-NIR spectrum of 1 in acetonitrile displays an electronic transition centred at 587 nm with an extinction coefficient consistent with significant charge transfer. The reaction between 1 and 2 and VCp2 or VCpt2 (Cpt = tetramethylcyclopentadienyl) resulted in the isolation of the heterobimetallic complexes, [Ln(hfac)3(N,N′-O,O′-pd)VCp2] (Ln = Y [3], Gd [4]) or [Ln(hfac)3(N,N′-O,O′-pd)VCpt2] (Ln = Y [5], Gd [6]). The solid state molecular structures of 3, 5 and 6 have been determined by X-ray crystallography. The spectroscopic data on 3–6 are consistent with oxidation of V(II) to V(IV) and reduction of pd to pd2− in the heterobimetallic complexes. The spin-Hamiltonian parameters from low temperature X-band EPR spectroscopy of 3 and 5 describe a 2A1 ground state, with a V(IV) centre. DFT calculations on 3 are in good agreement with experimental data and confirm the SOMO as the dx2−y2 orbital localised on vanadium

    Astronomical Sky Quality Near Eureka, in the Canadian High Arctic

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    Nighttime visible-light sky brightness and transparency are reported for the Polar Environment Research Laboratory (PEARL), located on a 610-m high ridge near the Eureka research station, on Ellesmere Island, Canada. Photometry of Polaris obtained in V band with the PEARL All Sky Imager (PASI) over two winters is supported by standard meteorological measurements and visual estimates of sky conditions from sea level. These data show that during the period of the study, October through March of 2008/09 and 2009/10, the sky near zenith had a mean surface brightness of 19.7 mag/square-arcsec when the sun was more than 12 deg below the horizon, reaching 20.7 mag/square-arcsec during astronomical darkness with no moon. Skies were without thick cloud and potentially usable for astronomy 86% of the time (extinction <2 mag). Up to 68% of the time was spectroscopic (<0.5 mag), attenuated by ice crystals, or clear with stable atmospheric transparency. Those conditions can persist for over 100 hours at a time. Further analysis suggests the sky was entirely free of ice crystals (truly photometric) 48+/-3% of the time at PEARL in winter, and that a higher elevation location nearby may be better.Comment: 14 pages, 1 table, 11 figures; accepted for publication in PAS

    The Properties of Poor Groups of Galaxies: III. The Galaxy Luminosity Function

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    We obtain R-band photometry for galaxies in six nearby poor groups for which we have spectroscopic data, including 328 new galaxy velocities. For the five groups with luminous X-ray halos, the composite group galaxy luminosity function (GLF) is fit adequately by a Schechter function with Mstar = -21.6 +/- 0.4 + 5log h and alpha = -1.3 +/- 0.1. We also find that (1) the ratio of dwarfs to giants is significantly larger for the five groups with luminous X-ray halos than for the one marginally X-ray detected group, (2) the composite GLF for the luminous X-ray groups is consistent in shape with that for rich clusters, (3) the composite group GLF rises more steeply at the faint end than that of the field, (4) the shape difference between the field and composite group GLF's results mostly from the population of non-emission line galaxies, whose dwarf-to-giant ratio is larger in the denser group environment than in the field, and (5) the non-emission line dwarfs are more concentrated about the group center than the non-emission line giants. This last result indicates that the dwarfs and giants occupy different orbits (i.e., have not mixed completely) and suggests that the populations formed at a different times. Our results show that the shape of the GLF varies with environment and that this variation is due primarily to an increase in the dwarf-to-giant ratio of quiescent galaxies in higher density regions, at least up to the densities characteristic of X-ray luminous poor groups. This behavior suggests that, in some environments, dwarfs are more biased than giants with respect to dark matter. This trend conflicts with the prediction of standard biased galaxy formation models. (Abridged)Comment: 36 pages, AASLaTeX with 8 figures. Table 1 also available at http://atropos.as.arizona.edu/aiz/papers/all_grp_lf_ascii.dat.final . To appear in Ap

    A scoping review of mathematical models of Plasmodium vivax

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    Plasmodium vivax is one of the most geographically widespread malaria parasites in the world due to its ability to remain dormant in the human liver as hypnozoites and subsequently reactivate after the initial infection (i.e. relapse infections). More than 80% of P. vivax infections are due to hypnozoite reactivation. Mathematical modelling approaches have been widely applied to understand P. vivax dynamics and predict the impact of intervention outcomes. In this article, we provide a scoping review of mathematical models that capture P. vivax transmission dynamics published between January 1988 and May 2023 to provide a comprehensive summary of the mathematical models and techniques used to model P. vivax dynamics. We aim to assist researchers working on P. vivax transmission and other aspects of P. vivax malaria by highlighting best practices in currently published models and highlighting where future model development is required. We provide an overview of the different strategies used to incorporate the parasite's biology, use of multiple scales (within-host and population-level), superinfection, immunity, and treatment interventions. In most of the published literature, the rationale for different modelling approaches was driven by the research question at hand. Some models focus on the parasites' complicated biology, while others incorporate simplified assumptions to avoid model complexity. Overall, the existing literature on mathematical models for P. vivax encompasses various aspects of the parasite's dynamics. We recommend that future research should focus on refining how key aspects of P. vivax dynamics are modelled, including the accumulation of hypnozoite variation, the interaction between P. falciparum and P. vivax, acquisition of immunity, and recovery under superinfection

    A model for malaria treatment evaluation in the presence of multiple species

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    Plasmodium (P.) falciparum and P. vivax are the two most common causes of malaria. While the majority of deaths and severe morbidity are due to P. falciparum, P. vivax poses a greater challenge to eliminating malaria outside of Africa due to its ability to form latent liver stage parasites (hypnozoites), which can cause relapsing episodes within an individual patient. In areas where P. falciparum and P. vivax are co-endemic, individuals can carry parasites of both species simultaneously. These mixed infections complicate dynamics in several ways; treatment of mixed infections will simultaneously affect both species, P. falciparum can mask the detection of P. vivax, and it has been hypothesised that clearing P. falciparum may trigger a relapse of dormant P. vivax. When mixed infections are treated for only blood-stage parasites, patients are at risk of relapse infections due to P. vivax hypnozoites. We present a stochastic mathematical model that captures interactions between P. falciparum and P. vivax, and incorporates both standard schizontocidal treatment (which targets blood-stage parasites) and radical treatment (which additionally targets liver-stage parasites). We apply this model to assess the implications of different treatment coverage of radical cure for mixed and P. vivax infections and a so-called "unified radical cure" treatment strategy for P. falciparum, P. vivax and mixed infections. We find that a unified radical cure strategy, with G6PD screening, leads to a substantially lower incidence of malaria cases and deaths overall. We perform a one-way sensitivity analysis to highlight important model parameters

    Measurement of Galaxy Cluster Sizes, Radial Profiles, and Luminosity Functions from SDSS Photometric Data

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    Imaging data from the Sloan Digital Sky Survey is used to measure the empirical size-richness relation for a large sample of galaxy clusters. Using population subtraction methods, we determine the radius at which the cluster galaxy number density is 200/Omega_m times the mean galaxy density, without assuming a model for the radial distribution of galaxies in clusters. If these galaxies are unbiased on Mpc scales, this galaxy-density-based R_200 reflects the characteristic radii of clusters. We measure the scaling of this characteristic radius with richness over an order of magnitude in cluster richness, from rich clusters to poor groups. We use this information to examine the radial profiles of galaxies in clusters as a function of cluster richness, finding that the concentration of the galaxy distribution decreases with richness and is systematically lower than the concentrations measured for dark matter profiles in N-body simulations. Using these scaled radii, we investigate the behavior of the cluster luminosity function, and find that it is well matched by a Schechter function for galaxies brighter than M_r = -18 only after the central galaxy has been removed. We find that the luminosity function varies with richness and with distance from the cluster center, underscoring the importance of using an aperture that scales with cluster mass to compare physically equivalent regions of these different systems. We note that the lowest richness systems in our catalog have properties consistent with those expected of the earliest-forming halos; our cluster-finding algorithm, in addition to reliably finding clusters, may be efficient at finding fossil groups.Comment: 17 pages, 12 figures. Accepted for publication in Ap

    Safetxt: a safer sex intervention delivered by mobile phone messaging on sexually transmitted infections (STI) among young people in the UK - protocol for a randomised controlled trial.

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    INTRODUCTION: Young people aged 16 to 24 have the highest prevalence of genital chlamydia and gonorrhoea compared with other age groups and re-infection rates following treatment are high. Long-term adverse health effects include subfertility and ectopic pregnancy, particularly among those with repeated infections. We developed the safetxt intervention delivered by text message to reduce sexually transmitted infection (STI) by increasing partner notification, condom use and (STI) testing among young people in the UK. METHODS AND ANALYSIS: A single-blind randomised trial to reliably establish the effect of the safetxt intervention on chlamydia and gonorrhoea infection at 1 year. We will recruit 6250 people aged 16 to 24 years who have recently been diagnosed with chlamydia, gonorrhoea or non-specific urethritis from health services in the UK. Participants will be allocated to receive the safetxt intervention (text messages designed to promote safer sexual health behaviours) or to receive the control text messages (monthly messages asking participants about changes in contact details) by an automated remote online randomisation system. The primary outcome will be the cumulative incidence of chlamydia and gonorrhoea infection at 1 year assessed by nucleic acid amplification tests. Secondary outcomes include partner notification, correct treatment of infection, condom use and STI testing prior to sex with new partners. ETHICS AND DISSEMINATION: Ethics approval was obtained from NHS Health Research Authority - London - Riverside Research Ethics Committee (REC reference: 15/LO/1665) and the London School of Hygiene & Tropical Medicine. We will submit the results of the trial for publication in peer-reviewed journals. TRIAL REGISTRATION NUMBER: International Standard Randomised Controlled Trials Number: ISRCTN64390461. Registered on 17th March 2016. WHO trial registration data set available at: http://apps.who.int/trialsearch/Trial2.aspx?TrialID=ISRCTN64390461. TRIAL PROTOCOL VERSION: 12, 19th July 2018

    The star formation histories of Hickson compact group galaxies

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    ABRIDGED: We study the Star Formation History (SFH) of 210 galaxies members of 55 Hickson Compact Groups (HCG) and 309 galaxies from the Catalog of Isolated Galaxies (CIG). The SFH traces the variation of star formation over the lifetime of a galaxy, and yields consequently a snapshot picture of its formation. Comparing the SFHs in these extremes in galaxy density, allows us to determine the main effects of Compact Groups (CG) on the formation of galaxies. We fit our spectra using the spectral synthesis code STARLIGHT and obtain the stellar population contents and mean stellar ages of HCG and CIG galaxies in three different morphological classes: early-type galaxies (EtG), early-type spirals (EtS), and late-type spirals (LtS). We find that EtG and EtS galaxies in HCG show larger contents of old and intermediate stellar populations as well as an important deficit of the young stellar population, what clearly implies an older average stellar age in early galaxies in HCG. For LtS galaxies we find similar mean values for the stellar content and age in the two samples. However, we note that LtS can be split into two subclasses, namely old and young LtS. In HCG we find a higher fraction of young LtS than in the CIG sample, in addition, most of these galaxies belong to groups where most of the galaxies are also young and actively forming stars. The Specific Star Formation Rate (SSFR) of spiral galaxies in the two samples differ. EtS in HCG show lower values of the SSFR, while LtS peak at higher values when comparing with their counterparts in isolation. We have also measured shorter Star Formation Time Scale (SFTS) in HCG galaxies, indicating that they have less prolonged star formation activity than CIG galaxies.Comment: 14 pages, 15 figures. Accepted for publication in A&

    Acute kidney disease and renal recovery : consensus report of the Acute Disease Quality Initiative (ADQI) 16 Workgroup

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    Consensus definitions have been reached for both acute kidney injury (AKI) and chronic kidney disease (CKD) and these definitions are now routinely used in research and clinical practice. The KDIGO guideline defines AKI as an abrupt decrease in kidney function occurring over 7 days or less, whereas CKD is defined by the persistence of kidney disease for a period of > 90 days. AKI and CKD are increasingly recognized as related entities and in some instances probably represent a continuum of the disease process. For patients in whom pathophysiologic processes are ongoing, the term acute kidney disease (AKD) has been proposed to define the course of disease after AKI; however, definitions of AKD and strategies for the management of patients with AKD are not currently available. In this consensus statement, the Acute Disease Quality Initiative (ADQI) proposes definitions, staging criteria for AKD, and strategies for the management of affected patients. We also make recommendations for areas of future research, which aim to improve understanding of the underlying processes and improve outcomes for patients with AKD
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