Elemental Anisotropic Growth and Atomic-Scale Structure of Shape-Controlled Octahedral Pt–Ni–Co Alloy Nanocatalysts

Multimetallic shape-controlled nanoparticles offer great opportunities to tune the activity, selectivity, and stability of electrocatalytic surface reactions. However, in many cases, our synthetic control over particle size, composition, and shape is limited requiring trial and error. Deeper atomic-scale insight in the particle formation process would enable more rational syntheses. Here we exemplify this using a family of trimetallic PtNiCo nanooctahedra obtained via a low-temperature, surfactant-free solvothermal synthesis. We analyze the competition between Ni and Co precursors under coreduction “one-step” conditions when the Ni reduction rates prevailed. To tune the Co reduction rate and final content, we develop a “two-step” route and track the evolution of the composition and morphology of the particles at the atomic scale. To achieve this, scanning transmission electron microscopy and energy dispersive X-ray elemental mapping techniques are used. We provide evidence of a heterogeneous element distribution caused by element-specific anisotropic growth and create octahedral nanoparticles with tailored atomic composition like Pt1.5M, PtM, and PtM1.5 (M = Ni + Co). These trimetallic electrocatalysts have been tested toward the oxygen reduction reaction (ORR), showing a greatly enhanced mass activity related to commercial Pt/C and less activity loss than binary PtNi and PtCo after 4000 potential cycles.

The internal consistency and construct validity of the partners in health scale : validation of a patient rated chronic condition self-management measure

PURPOSE: The purpose of this study was to test the internal consistency and construct validity of the revised 12-item self-rated Partners in Health (PIH) scale used to assess patients' chronic condition self-management knowledge and behaviours. METHODS: Baseline PIH data were collected for a total of 294 patients with a range of co-morbid chronic conditions including diabetes, cardiovascular disease and arthritis. Scale data for the initial sample of 176 patients were analysed for internal consistency and construct validity using Reliability Analysis and Factor Analysis. Construct validity was tested in a separate sample of 118 patients using confirmatory factor analysis and a structural equation model. RESULTS: Good internal consistency was indicated with a Cronbach's alpha coefficient of 0.82 in the initial sample. Factor analysis for this sample revealed four key factors (knowledge, coping, management of condition and adherence to treatment) across the twelve items of the scale. These four key factors were then confirmed by applying the exploratory structural equation model to the separate sample. CONCLUSION: The PIH scale exhibits construct validity and internal consistency. It therefore is both a generic self-rated clinical tool for assessing self-management in a range of chronic conditions as well as an outcome measure to compare populations and change in patient self-management knowledge and behaviour over time. The four domains of self-management provide a valid measure of patient competency in relation to the self-management of their chronic condition(s).

A continental-scale analysis of feral cat diet in Australia

Aim Reducing the impacts of feral cats (Felis catus) is a priority for conservation managers across the globe, and success in achieving this aim requires a detailed understanding of the species’ ecology across a broad spectrum of climatic and environmental conditions. We reviewed the diet of the feral cat across Australia and on Australian territorial islands, seeking to identify biogeographical patterns in dietary composition and diversity, and use the results to consider how feral cats may best be managed. Location Australia and its territorial islands. Methods Using 49 published and unpublished data sets, we modelled trophic diversity and the consumption of eight food groups against latitude, longitude, mean temperature, precipitation, environmental productivity and climate-habitat regions. Results We recorded 400 vertebrate species that feral cats feed on or kill in Australia, including 28 IUCN Red List species. We found evidence of continental- scale prey-switching from rabbits to small mammals, previously recorded only at the local scale. The consumption of arthropods, reptiles, rabbits, rodents and medium-sized native mammals varied with different combinations of latitude, longitude, mean annual precipitation, temperature and environmental productivity. The frequency of rodents and dasyurids in cats’ diets increased as rabbit consumption decreased. Main conclusions The feral cat is an opportunistic, generalist carnivore that consumes a diverse suite of vertebrate prey across Australia. It uses a facultative feeding strategy, feeding mainly on rabbits when they are available, but switching to other food groups when they are not. Control programmes aimed at culling rabbits could potentially decrease the availability of a preferred food source for cats and then lead to greater predation pressure on native mammals. The interplay between cat diet and prey species diversity at a continental scale is complex, and thus cat management is likely to be necessary and most effective at the local landscape level.

Microstructure and hardness characterisation of laser coatings produced with a mixture of AISI 420 stainless steel and Fe-C-Cr-Nb-B-Mo steel alloy powders

Fe-C-Cr-Nb-B-Mo alloy powder and AISI 420 SS powder are deposited using laser cladding to increase the hardness for wear resistant applications. Mixtures from 0 to 100 wt.% were evaluated to understand the effect on the elemental composition, microstructure, phases, and microhardness. The mixture of carbon, boron and niobium in the Fe-C-Cr-Nb-B-Mo alloy powder introduces complex carbides into a Fe-based matrix of AISI 420 SS which increases its hardness. Hardness increased linearly with increasing Fe-C-Cr-Nb-B-Mo alloy, but substantial micro-cracking was observed in the clad layer at additions of 60 wt.% and above; related to a transition from a hypoeutectic alloy containing α-Fe/α' dendrites with an (Fe,Cr)2B and γ-Fe eutectic to primary and continuous carbo-borides M2B (where M represents Fe and Cr) and M23(B,C)6 carbides (where M represents Fe, Cr, Mo) with MC particles (where M represents Nb and Mo). The highest average hardness, for an alloy without micro-cracking, of 952 HV was observed in a 40 wt.% alloy. High stress abrasive scratch testing was conducted on all alloys at various loads (500, 1500, 2500 N). Alloy content was found to have a strong effect on the wear mode and the abrasive wear rate, and the presence of micro-cracks was detrimental to abrasive wear resistance.

Investigating the issue of pollution in the micro-scale design of mega-cities : a case study of Enghelab Street, Tehran

Today there is a growing concern about urbanization and its impact on environmental pollution, which threatens human health and quality of life especially in mega cities. The mega city of Tehran, the capital of Iran, deals with various types of pollution. Although a large body of research has highlighted the significance of study on urban pollution in mega cities, only a few studies have addressed the issue at the micro scale. However, most of the research is restricted to air and noise pollution, whereas visual pollution as an important type of pollution that can be interpreted more deeply on a micro-scale, has been neglected. This study aims to evaluate some of the major issues of environmental pollution in Tehran by focusing on the micro-scale of the street. Therefore, as the central part of Tehran is one of the most affected divisions in the city, Enghelab Street has been selected as the case study for this research. This paper argues that identification and implementation of pollution mitigating strategies in Tehran’s master plan is not responsive enough to the whole city. This study of Enghelab Street reveals that policy making strategies for decreasing pollution should be initiated from micro-scale with further emphasis on psychological health. In the future, the lessons learned from the case study of Enghelab will help other major cities in developing countries to combat pollution through initiating from most affected districts in small scale.

Large-scale screening of a targeted Enterococcus faecalis mutant library identifies envelope fitness factors

Spread of antibiotic resistance among bacteria responsible for nosocomial and community-acquired infections urges for novel therapeutic or prophylactic targets and for innovative pathogen-specific antibacterial compounds. Major challenges are posed by opportunistic pathogens belonging to the low GC% gram-positive bacteria. Among those, Enterococcus faecalis is a leading cause of hospital-acquired infections associated with life-threatening issues and increased hospital costs. To better understand the molecular properties of enterococci that may be required for virulence, and that may explain the emergence of these bacteria in nosocomial infections, we performed the first large-scale functional analysis of E. faecalis V583, the first vancomycin-resistant isolate from a human bloodstream infection. E. faecalis V583 is within the high-risk clonal complex 2 group, which comprises mostly isolates derived from hospital infections worldwide. We conducted broad-range screenings of candidate genes likely involved in host adaptation (e.g., colonization and/or virulence). For this purpose, a library was constructed of targeted insertion mutations in 177 genes encoding putative surface or stress-response factors. Individual mutants were subsequently tested for their i) resistance to oxidative stress, ii) antibiotic resistance, iii) resistance to opsonophagocytosis, iv) adherence to the human colon carcinoma Caco-2 epithelial cells and v) virulence in a surrogate insect model. Our results identified a number of factors that are involved in the interaction between enterococci and their host environments. Their predicted functions highlight the importance of cell envelope glycopolymers in E. faecalis host adaptation. This study provides a valuable genetic database for understanding the steps leading E. faecalis to opportunistic virulence.

Multi-Scale Governance of Sustainable Natural Resource Use—Challenges and Opportunities for Monitoring and Institutional Development at the National and Global Level

In a globalized economy, the use of natural resources is determined by the demand of modern production and consumption systems, and by infrastructure development. Sustainable natural resource use will require good governance and management based on sound scientific information, data and indicators. There is a rich literature on natural resource management, yet the national and global scale and macro-economic policy making has been underrepresented. We provide an overview of the scholarly literature on multi-scale governance of natural resources, focusing on the information required by relevant actors from local to global scale. Global natural resource use is largely determined by national, regional, and local policies. We observe that in recent decades, the development of public policies of natural resource use has been fostered by an “inspiration cycle” between the research, policy and statistics community, fostering social learning. Effective natural resource policies require adequate monitoring tools, in particular indicators for the use of materials, energy, land, and water as well as waste and GHG emissions of national economies. We summarize the state-of-the-art of the application of accounting methods and data sources for national material flow accounts and indicators, including territorial and product-life-cycle based approaches. We show how accounts on natural resource use can inform the Sustainable Development Goals (SDGs) and argue that information on natural resource use, and in particular footprint indicators, will be indispensable for a consistent implementation of the SDGs. We recognize that improving the knowledge base for global natural resource use will require further institutional development including at national and international levels, for which we outline options.

Broad-scale mapping of seafloor habitats in the north-east Atlantic using existing environmental data

If marine management policies and actions are to achieve long-term sustainable use and management of the marine environment and its resources, they need to be informed by data giving the spatial distribution of seafloor habitats over large areas. Broad-scale seafloor habitat mapping is an approachwhich has the benefit of producing maps covering large extents at a reasonable cost. This approach was first investigated by Roff et al. (2003), who, acknowledging that benthic communities are strongly influenced by the physical characteristics of the seafloor, proposed overlaying mapped physical variables using a geographic information system (GIS) to produce an integrated map of the physical characteristics of the seafloor. In Europe the method was adapted to the marine section of the EUNIS (European Nature Information System) classification of habitat types under the MESH project, andwas applied at an operational level in 2011 under the EUSeaMap project. The present study compiled GIS layers for fundamental physical parameters in the northeast Atlantic, including (i) bathymetry, (ii) substrate type, (iii) light penetration depth and (iv) exposure to near-seafloor currents andwave action. Based on analyses of biological occurrences, significant thresholds were fine-tuned for each of the abiotic layers and later used in multi-criteria raster algebra for the integration of the layers into a seafloor habitat map. The final result was a harmonised broad-scale seafloor habitat map with a 250 m pixel size covering four extensive areas, i.e. Ireland, the Bay of Biscay, the Iberian Peninsula and the Azores. The map provided the first comprehensive perception of habitat spatial distribution for the Iberian Peninsula and the Azores, and fed into the initiative for a pan- European map initiated by the EUSeaMap project for Baltic, North, Celtic and Mediterranean seas.

Is the human population a large-scale indicator of the species richness of ground beetles?

Aim Positive regional correlations between biodiversity and human population have been detected for several taxonomic groups and geographical regions. Such correlations could have important conservation implications and have been mainly attributed to ecological factors, with little testing for an artefactual explanation: more populated regions may show higher biodiversity because they are more thoroughly surveyed. We tested the hypothesis that the correlation between people and herptile diversity in Europe is influenced by survey effort

Spatial scale effects of sampling on the interpolation of species distribution models in the southwestern Amazon.

Knowledge of the geographical distribution of timber tree species in the Amazon is still scarce. This is especially true at the local level, thereby limiting natural resource management actions. Forest inventories are key sources of information on the occurrence of such species. However, areas with approved forest management plans are mostly located near access roads and the main industrial centers. The present study aimed to assess the spatial scale effects of forest inventories used as sources of occurrence data in the interpolation of potential species distribution models. The occurrence data of a group of six forest tree species were divided into four geographical areas during the modeling process. Several sampling schemes were then tested applying the maximum entropy algorithm, using the following predictor variables: elevation, slope, exposure, normalized difference vegetation index (NDVI) and height above the nearest drainage (HAND). The results revealed that using occurrence data from only one geographical area with unique environmental characteristics increased both model overfitting to input data and omission error rates. The use of a diagonal systematic sampling scheme and lower threshold values led to improved model performance. Forest inventories may be used to predict areas with a high probability of species occurrence, provided they are located in forest management plan regions representative of the environmental range of the model projection area.

Bayesian outlier analysis in binary regression

We propose alternative approaches to analyze residuals in binary regression models based on random effect components. Our preferred model does not depend upon any tuning parameter, being completely automatic. Although the focus is mainly on accommodation of outliers, the proposed methodology is also able to detect them. Our approach consists of evaluating the posterior distribution of random effects included in the linear predictor. The evaluation of the posterior distributions of interest involves cumbersome integration, which is easily dealt with through stochastic simulation methods. We also discuss different specifications of prior distributions for the random effects. The potential of these strategies is compared in a real data set. The main finding is that the inclusion of extra variability accommodates the outliers, improving the adjustment of the model substantially, besides correctly indicating the possible outliers.

Nano-scale morphology and electron spectrum of defect states in low-k SiOCH films

Results of experimental investigations on the relationship between nanoscale morphology of carbon doped hydrogenated silicon-oxide (SiOCH) low-k films and their electron spectrum of defect states are presented. The SiOCH films have been deposited using trimethylsilane (3MS) - oxygen mixture in a 13.56 MHz plasma enhanced chemical vapor deposition (PECVD) system at variable RF power densities (from 1.3 to 2.6 W/cm2) and gas pressures of 3, 4, and 5 Torr. The atomic structure of the SiOCH films is a mixture of amorphous-nanocrystalline SiO2-like and SiC-like phases. Results of the FTIR spectroscopy and atomic force microscopy suggest that the volume fraction of the SiC-like phase increases from ∼0.2 to 0.4 with RF power. The average size of the nanoscale surface morphology elements of the SiO2-like matrix can be controlled by the RF power density and source gas flow rates. Electron density of the defect states N(E) of the SiOCH films has been investigated with the DLTS technique in the energy range up to 0.6 eV from the bottom of the conduction band. Distinct N(E) peaks at 0.25 - 0.35 eV and 0.42 - 0.52 eV below the conduction band bottom have been observed. The first N(E) peak is identified as originated from E1-like centers in the SiC-like phase. The volume density of the defects can vary from 1011 - 1017 cm-3 depending on specific conditions of the PECVD process.

Nucleobase-metal hybrid materials: Preparation of submicrometer-scale, spherical colloidal particles of adenine-gold(III) via a supramolecular hierarchical self-assembly approach

We report a simple and effective supramolecular route for facile synthesis of submicrometer-scale, hierarchically self-assembled spherical colloidal particles of adenine - gold(III) hybrid materials at room temperature. Simple mixture of the precursor aqueous solutions of adenine and HAuCl4 at room temperature could result in spontaneous formation of the hybrid colloidal particles. Optimization of the experimental conditions could yield uniform-sized, self-assembled products at 1:4 molar ration of adenine to HAuCl4. Transmission electron microscopy results reveal the formation of hierarchical self-assembled structure of the as-prepared colloidal particles. Concentration dependence, ratio dependence, time dependence, and kinetic measurements have been investigated. Moreover, spectroscopic evidence [i.e., Fourier transform infrared (FTIR) and UV-vis spectra and wide-angle X-ray scattering data] of the interaction motives causing the formation of the colloidal particles is also presented.

The effect of the causative algae of large-scale HAB in the East China Sea on egg hatching of Argopecten irradians, and population growth of Brachionus plicatilis and Moina mongolica

The impacts of Prorocentrum donghaiense Lu and Alexandrium catenella Balech, causative species of the large-scale HAB in the East China Sea, were studied under laboratory conditions. According to bloom densities, the effects of monoculture and mixture of the two species were examined on the egg-hatching success of Argopecten irradians Lamarck, and the population growth of Brachionus plicatilis Muller and Moina mongolica Daday. The results showed that monoculture of A. catenella had a significant inhibition on the egg hatching success of A. irradians, and the population growth of B. plicatilis and M. mongolica. The median effective densities ( EDSo) inhibiting the egg hatching success of A. irradians for 24 h and the population growth of B. plicatilis and M. mongolica for 96 h were 800, 630, and 2 400 cells/cm(3), respectively. Monoculture of P. donghaiense has no such inhibitory effect on the egg hatching success of A. irradians; P. donghaiense at lower suitable densities could sustain the population growth of B. plicatilis (1 x 10(4) similar to 3 x 10(4)cells/cm(3)) and M. mongolica (2 x 10(4) similar to 5 x 10(4) cells/cm(3)); P. doaghaiense at higher densities had significantly adverse effect on the population growth of B. plicatilis (4 x 10(4) similar to 10 x 10(4) cells/cm(3)) and M. mongolica (10 x 10(4) cells/cm(3)). When the two algae were mixed according to bloom densities, P. donghaiense at suitable densities to some extent could decrease the toxicity of A. catenella to B. plicatilis and M. mongolica. The results indicated that the large-scale HAB in the East China Sea could have adverse effect on zooplankton, and might further influence the marine ecosystem, especially when there was also Alexandrium bloom.

Evaluation via multivariate techniques of scale factor variability in the rietveld method applied to quantitative phase analysis with X ray powder diffraction

ABSTRACT: The present work uses multivariate statistical analysis as a form of establishing the main sources of error in the Quantitative Phase Analysis (QPA) using the Rietveld method. The quantitative determination of crystalline phases using x ray powder diffraction is a complex measurement process whose results are influenced by several factors. Ternary mixtures of Al2O3, MgO and NiO were prepared under controlled conditions and the diffractions were obtained using the Bragg-Brentano geometric arrangement. It was possible to establish four sources of critical variations: the experimental absorption and the scale factor of NiO, which is the phase with the greatest linear absorption coefficient of the ternary mixture; the instrumental characteristics represented by mechanical errors of the goniometer and sample displacement; the other two phases (Al2O3 and MgO); and the temperature and relative humidity of the air in the laboratory. The error sources excessively impair the QPA with the Rietveld method. Therefore it becomes necessary to control them during the measurement procedure.