Electronic structure of lanthanide-doped bismuth vanadates: A systematic study by x-ray photoelectron and optical spectroscopies

Monoclinic BiVO 4 has emerged in recent years as one of the most promising materials for photocatalytic evolution of oxygen under solar irradiation. However, it is in itself unable to phototcatalyze reduction of water to hydrogen due to the placement of the conduction band edge below the potential required for H 2 O/H 2 reduction. As a consequence, BiVO 4 only finds application in a hybrid system. Very recently, tetragonal lanthanide-doped BiVO 4 powders have been shown to be able to both reduce and to oxidize water under solar irradiation, but to date there has been no comprehensive study of the electronic properties of lanthanide-doped bismuth vanadates aimed at establishing the systematic trends in the electronic structure in traversing the lanthanide series. Here, the accessible family of lanthanide-doped BiVO 4 quaternary oxides of stoichiometry Bi 0.5 Ln 0.5 VO 4 (Ln = La to Lu, excluding Pm) has been studied by X-ray powder diffraction, X-ray photoemission spectroscopy, and diffuse reflectance optical spectroscopy. The compounds all adopt the tetragonal zircon structure, and lattice parameters decrease monotonically in traversing the lanthanide series. At the same time, there is an increased peak broadening in the diffraction patterns as the mismatch in ionic radius between Bi 3+ and the Ln 3+ ions increases across the series. Valence band X-ray photoemission spectra show that the final state 4f n-1 structure associated with ionization of lanthanide 4f n states is superimposed on the valence band structure of BiVO 4 in the quaternary materials: in the case of the Ce-, Pr- and Tb-doped BiVO 4 , 4f-related states appear above the top of the main valence band of BiVO 4 and account for the small bandgap in the Ce compound. In all cases, the 4f structure is characteristic of the lanthanide element in the Ln(III) oxidation state. Vanadium 2p and lanthanide 3d or 4d core level photoelectron spectra of those compounds where the lanthanide may in principle adopt a higher (Ln = Ce, Pr, Tb) or lower (Ln = Eu, Yb) oxidation state further confirm the prevalence of the Ln(III) valence state throughout. The visible region optical properties of all samples were studied by diffuse reflectance spectroscopy, with a particular focus on the optical bandgap and the details of transitions associated with localized 4f states. Taken together, the results demonstrate the remarkable tunability of optical and electronic properties for these quaternary materials

Linking marine ecosystems with the services they supply: what are the relevant service providing units?

Marine ecosystems support supply of ecosystem services (ESs) through processes and functions carried out by diverse biological elements. Managing sustainability of ES use requires linking services to the parts of ecosystems supplying them. We specified marine service providing units (SPUs) as plausible combinations of a biotic group (e.g., bacteria, seabirds) with an associated major habitat (e.g., sublittoral sediment). We developed a network model for large marine ecosystems, documenting 2,916 links between 153 SPUs with 31 services. Coastal habitats and their taxa accounted for 48% of links, but all habitats with their taxa contribute to at least 20 ESs. Through network analysis, we showed some services link to certain key habitats, while others are less clearly defined in space, being supported by a variety of habitats and their taxa. Analysis highlighted large‐scale flows across marine habitats that are essential in underpinning continued supply of certain ESs, for example, seed dispersal. If we only protect habitats where services are used, we will not fully protect the supply of services reliant on mobile taxa moving between habitats. This emerged because we considered habitats and their taxa together. We recommend using combinations of habitats and taxa as SPUs when informing marine ecosystem management and conservation

On ‘Organized Crime’ in the illicit antiquities trade: moving beyond the definitional debate

The extent to which ‘organized crime’ is involved in illicit antiquities trafficking is unknown and frequently debated. This paper explores the significance and scale of the illicit antiquities trade as a unique transnational criminal phenomenon that is often said to be perpetrated by and exhibit traits of so-called ‘organized crime.’ The definitional debate behind the term ‘organized crime’ is considered as a potential problem impeding our understanding of its existence or extent in illicit antiquities trafficking, and a basic progression-based model is then suggested as a new tool to move beyond the definitional debate for future research that may help to elucidate the actors, processes and criminal dynamics taking place within the illicit antiquities trade from source to market. The paper concludes that researchers should focus not on the question of whether organized criminals- particularly in a traditionally conceived, mafia-type stereotypical sense- are involved in the illicit antiquities trade, but instead on the structure and progression of antiquities trafficking itself that embody both organized and criminal dynamics

Hospitalisation without delirium is not associated with cognitive decline in a population-based sample of older people-results from a nested, longitudinal cohort study

Background: Acute hospitalisation and delirium have individually been shown to adversely affect trajectories of cognitive decline but have not previously been considered together. This work aimed to explore the impact on cognition of hospital admission with and without delirium, compared to a control group with no hospital admissions. // Methods: The Delirium and Cognitive Impact in Dementia (DECIDE) study was nested within the Cognitive Function and Ageing Study II (CFAS II)–Newcastle cohort. CFAS II participants completed two baseline interviews, including the Mini-Mental State Examination (MMSE). During 2016, surviving participants from CFAS II–Newcastle were recruited to DECIDE on admission to hospital. Participants were reviewed daily to determine delirium status. During 2017, all DECIDE participants and age, sex and years of education matched controls without hospital admissions during 2016 were invited to repeat the CFAS II interview. Delirium was excluded in the control group using the Informant Assessment of Geriatric Delirium Scale (i-AGeD). Linear mixed effects modelling determined predictors of cognitive decline. // Results: During 2016, 82 of 205 (40%) DECIDE participants had at least one episode of delirium. At 1 year, 135 of 205 hospitalised participants completed an interview along with 100 controls. No controls experienced delirium (i-AGeD>4). Delirium was associated with a faster rate of cognitive decline compared to those without delirium (β = −2.2, P < 0.001), but number of hospital admissions was not (P = 0.447). // Conclusions: These results suggest that delirium during hospitalisation rather than hospitalisation per se is a risk factor for future cognitive decline, emphasising the need for dementia prevention studies that focus on delirium intervention

Icebergs in the North Atlantic: Modelling circulation changes and glacio-marine deposition

In order to investigate meltwater events in the North Atlantic, a simple iceberg generation, drift, and melting routine was implemented in a high-resolution OGCM. Starting from the modelled last glacial state, every 25th day cylindrical model icebergs 300 meters high were released at 32 specific points along the coasts. Icebergs launched at the Barents Shelf margin spread a light meltwater lid over the Norwegian and Greenland Seas, shutting down the deep convection and the anti-clockwise circulation in this area. Due to the constraining ocean circulation, the icebergs produce a tongue of relatively cold and fresh water extending eastward from Hudson Strait that must develop at this location, regardless of iceberg origin. From the total amount of freshwater inferred by the icebergs, the thickness of the deposited IRD could be calculated in dependance of iceberg sediment concentration. In this way, typical extent and thickness of Heinrich layers could be reproduced, running the model for 250 years of steady state with constant iceberg meltwater inflow

Characterization of a novel mouse model of multiple myeloma and its use in preclinical therapeutic assessment.

To aid preclinical development of novel therapeutics for myeloma, an in vivo model which recapitulates the human condition is required. An important feature of such a model is the interaction of myeloma cells with the bone marrow microenvironment, as this interaction modulates tumour activity and protects against drug-induced apoptosis. Therefore NOD/SCIDγc(null) mice were injected intra-tibially with luciferase-tagged myeloma cells. Disease progression was monitored by weekly bioluminescent imaging (BLI) and measurement of paraprotein levels. Results were compared with magnetic resonance imaging (MRI) and histology. Assessment of model suitability for preclinical drug testing was investigated using bortezomib, melphalan and two novel agents. Cells engrafted at week 3, with a significant increase in BLI radiance occurring between weeks 5 and 7. This was accompanied by an increase in paraprotein secretion, MRI-derived tumour volume and CD138 positive cells within the bone marrow. Treatment with known anti-myeloma agents or novel agents significantly attenuated the increase in all disease markers. In addition, intra-tibial implantation of primary patient plasma cells resulted in development of myeloma within bone marrow. In conclusion, using both myeloma cell lines and primary patient cells, we have developed a model which recapitulates human myeloma by ensuring the key interaction of tumour cells with the microenvironment

Regulation of mammary gland branching morphogenesis by the extracellular matrix and its remodeling enzymes.

A considerable body of research indicates that mammary gland branching morphogenesis is dependent, in part, on the extracellular matrix (ECM), ECM-receptors, such as integrins and other ECM receptors, and ECM-degrading enzymes, including matrix metalloproteinases (MMPs) and their inhibitors, tissue inhibitors of metalloproteinases (TIMPs). There is some evidence that these ECM cues affect one or more of the following processes: cell survival, polarity, proliferation, differentiation, adhesion, and migration. Both three-dimensional culture models and genetic manipulations of the mouse mammary gland have been used to study the signaling pathways that affect these processes. However, the precise mechanisms of ECM-directed mammary morphogenesis are not well understood. Mammary morphogenesis involves epithelial 'invasion' of adipose tissue, a process akin to invasion by breast cancer cells, although the former is a highly regulated developmental process. How these morphogenic pathways are integrated in the normal gland and how they become dysregulated and subverted in the progression of breast cancer also remain largely unanswered questions

Suitability of PSA-detected localised prostate cancers for focal therapy: Experience from the ProtecT study

This article is available through a Creative Commons Attribution-NonCommercial-Share Alike 3.0 Unported License. Copyright @ 2011 Cancer Research UK.Background: Contemporary screening for prostate cancer frequently identifies small volume, low-grade lesions. Some clinicians have advocated focal prostatic ablation as an alternative to more aggressive interventions to manage these lesions. To identify which patients might benefit from focal ablative techniques, we analysed the surgical specimens of a large sample of population-detected men undergoing radical prostatectomy as part of a randomised clinical trial. Methods: Surgical specimens from 525 men who underwent prostatectomy within the ProtecT study were analysed to determine tumour volume, location and grade. These findings were compared with information available in the biopsy specimen to examine whether focal therapy could be provided appropriately. Results: Solitary cancers were found in prostatectomy specimens from 19% (100 out of 525) of men. In addition, 73 out of 425 (17%) men had multiple cancers with a solitary significant tumour focus. Thus, 173 out of 525 (33%) men had tumours potentially suitable for focal therapy. The majority of these were small, well-differentiated lesions that appeared to be pathologically insignificant (38–66%). Criteria used to select patients for focal prostatic ablation underestimated the cancer's significance in 26% (34 out of 130) of men and resulted in overtreatment in more than half. Only 18% (24 out of 130) of men presumed eligible for focal therapy, actually had significant solitary lesions. Conclusion: Focal therapy appears inappropriate for the majority of men presenting with prostate-specific antigen-detected localised prostate cancer. Unifocal prostate cancers suitable for focal ablation are difficult to identify pre-operatively using biopsy alone. Most lesions meeting criteria for focal ablation were either more aggressive than expected or posed little threat of progression.National Institute for Health Researc

Medication usage change in older people (65+) in England over 20 years: Findings from CFAS I and CFAS II

BACKGROUND: medical practice has changed over the last decades reflecting the ageing population, when multi-morbidity requiring multiple medications is more common. OBJECTIVE: describe and quantify self-reported medicine use including both prescription and over the counter medicines in two comparable population-based studies of older people (65+) in England and to assess the nature and scale of polypharmacy. METHODS: data used were from two separate population-based studies; the Cognitive Function Ageing Study I and II. Descriptive analyses were performed to summarise and quantify general medicine use. Negative binomial regression models were fitted to determine factors associated with the number of medicines used. RESULTS: medication use, including both prescribed medicines and over the counter products has increased dramatically over the last 2 decades. The number of people taking five or more items quadrupled from 12 to 49%, while the proportion of people who did not take any medication has decreased from around 1 in 5 to 1 in 13. Cardiovascular drugs were the most frequently taken medication. Polypharmacy is associated with increases in the number of diagnosed long-term conditions. CONCLUSIONS: comparison between CFAS I and II reveals marked increases in medication usage and polypharmacy in the older population. The influence of healthcare organisation, introduction of new guidelines and technology changes leading to diagnosis of earlier, milder chronic diseases and treatment may be contributing to this changing pattern. Further research is needed to develop practical solutions to optimise medication management in older people, reducing the harming associated with medication.CFAS II has been supported by a major award from the UK Medical Research council (MRC) and received support from the National Institute for Health Research (NIHR) comprehensive clinical research networks in West Anglia and Trent, and the dementias and neurodegenerative disease research network in Newcastle. MRC CFAS (including CFAS I areas) was funded by the MRC and the National Health Service (NHS)