Structuring reductive media containing protic ionic liquids and their application to the formation of metallic nanoparticles

Herein, we present a facile method for the formation of monodispersed metal nanoparticles (NPs) at room temperature from M^(III)Cl₃ (with M = Au, Ru, Mn, Fe or V) in different media based on N,N-dimethylformamide (DMF) or water solutions containing a protic ionic liquid (PIL), namely the octylammonium formate (denoted OAF) or the bis(2-ethyl-hexyl)ammonium formate (denoted BEHAF). These two PILs present different structures and redox-active structuring properties that influence their interactions with selected molecular compounds (DMF or water), as well as the shape and the size of formed metal NPs in these solutions. Herein, the physical properties, such as the thermal, transport and micellar properties, of investigated PIL solutions were firstly investigated in order to understand the relation between PILs structure and their properties in solutions with DMF or water. The formation of metal NPs in these solutions was then characterized by using UV–vis spectroscopy, transmission electron microscopy (TEM), scanning electron microscopy (SEM) and dynamic light scattering (DLS) measurements. From our investigations, it appears that the PILs structure and their aggregation pathways in selected solvents affect strongly the formation, growths, the shape and the size of metal NPs. In fact by using this approach, the shape-/size-controlled metal NPs can be generated under mild condition. This approach suggests also a wealth of potential for these designer nanomaterials within the biomedical, materials, and catalysis communities by using designer and safer media based on PILs.

Scales and Hierarchies: A Cross-Disciplinary Perspective

The volume advances our understanding of the role of scales and hierarchies across the linguistic sciences. Although scales and hierarchies are widely assumed to play a role in the modelling of linguistic phenomena, their status remains controversial, and it is these controversies that the present volume tackles head-on.

Plant community assembly at small scales: spatial versus environmental factors in a central European grassland

Dispersal limitation and environmental conditions are crucial drivers of plant species distribution and establishment. As these factors operate at different spatial scales, we asked: Do the environmental factors known to determine community assembly at broad scales operate at fine scales (few meters)? How much do these factors account for community variation at fine scales? In which way do biotic and abiotic interactions drive changes in species composition? We surveyed the plant community within a dry grassland along a very steep gradient of soil characteristics like pH and nutrients. We used a spatially explicit sampling design, based on three replicated macroplots of 15x15, 12x12 and 12x12 meters in extent. Soil samples were taken to quantify several soil properties (carbon, nitrogen, plant available phosphorus, pH, water content and dehydrogenase activity as a proxy for overall microbial activity). We performed variance partitioning to assess the effect of these variables on plant composition and statistically controlled for spatial autocorrelation via eigenvector mapping. We also applied null model analysis to test for non-random patterns in species co-occurrence using randomization schemes that account for patterns expected under species interactions. At a fine spatial scale, environmental factors explained 18% of variation when controlling for spatial autocorrelation in the distribution of plant species, whereas purely spatial processes accounted for 14% variation. Null model analysis showed that species spatially segregated in a non-random way and these spatial patterns could be due to a combination of environmental filtering and biotic interactions. Our grassland study suggests that environmental factors found to be directly relevant in broad scale studies are present also at small scales, but are supplemented by spatial processes and more direct interactions like competition.

How the mollusc got its scales: Convergent evolution of the molluscan scleritome

Radiation of dramatically disparate forms among the phylum Mollusca remains a key question in metazoan evolution, and requires careful evaluation of homology of hard parts throughout the deep fossil record. Enigmatic early Cambrian taxa such as Halkieria and Wiwaxia (in the clade Halwaxiida) have been proposed to represent stem-group aculiferan molluscs (Caudofoveata+Solenogastres+Polyplacophora), as complex scleritomes were considered to be unique to aculiferans among extant molluscs. The 'scaly-foot gastropod' (Neomphalina: Peltospiridae) from hydrothermal vents of the Indian Ocean, however, also carries dermal sclerites and thus challenges this inferred homology. Despite superficial similarities to various mollusc sclerites, the scaly-foot gastropod sclerites are secreted in layers covering outpockets of epithelium and are largely proteinaceous, while chiton (Polyplacophora: Chitonida) sclerites are secreted to fill an invaginated cuticular chamber and are largely calcareous. Marked differences in the underlying epithelium of the scaly-foot gastropod sclerites and operculum suggest that the sclerites do not originate from multiplication of the operculum. This convergence in different classes highlights the ability of molluscs to adapt mineralized dermal structures, as supported by the extensive early fossil record of molluscs with scleritomes. Sclerites of halwaxiids are morphologically variable, undermining the assumed affinity of specific taxa with chitons, or the larger putative clade Aculifera. Comparisons with independently derived similar structures in living molluscs are essential for determining homology among fossils and their position with respect to the enigmatic evolution of molluscan shell forms in deep time.

Orange Zinc Germanate with Metallic Ge-Ge Bonds as a Chromophore-Like Center for Visible-Light-Driven Water Splitting

The efficiency of solar-energy-conversion devices depends on the absorption region and intensity of the photon collectors. Organic chromophores, which have been widely stabilized on inorganic semiconductors for light trapping, are limited by the interface between the chromophore and semiconductor. Herein we report a novel orange zinc germanate (Zn-Ge-O) with a chromophore-like structure, by which the absorption region can be dramatically expanded. Structural characterizations and theoretical calculations together reveal that the origin of visible-light response can be attributed to the unusual metallic Ge-Ge bonds which act in a similar way to organic chromophores. Benefiting from the enhanced light harvest, the orange Zn-Ge-O demonstrates superior capacity for solar-driven hydrogen production.

Spatial variation in adult sex ratio across multiple scales in the invasive golden apple snail, Pomacea canaliculata

Adult sex ratio (ASR) has critical effects on behavior and life history and has implications for population demography, including the invasiveness of introduced species. ASR exhibits immense variation in nature, yet the scale dependence of this variation is rarely analyzed. In this study, using the generalized multilevel models, we investigated the variation in ASR across multiple nested spatial scales and analyzed the underlying causes for an invasive species, the golden apple snail Pomacea canaliculata. We partitioned the variance in ASR to describe the variations at different scales and then included the explanatory variables at the individual and group levels to analyze the potential causes driving the variation in ASR. We firstly determined there is a significant female-biased ASR for this species when accounting for the spatial and temporal autocorrelations of sampling. We found that, counter to nearly equal distributed variation at plot, habitat and region levels, ASR showed little variation at the town level. Temperature and precipitation at the region level were significantly positively associated with ASR, whereas the individual weight, the density characteristic, and sampling time were not significant factors influencing ASR. Our study suggests that offspring sex ratio of this species may shape the general pattern of ASR in the population level while the environmental variables at the region level translate the unbiased offspring sex ratio to the female-biased ASR. Future research should consider the implications of climate warming on the female-biased ASR of this invasive species and thus on invasion pattern.

A closer look at Carver and White's BIS/BAS scales: Factor analysis and age group differences

The Behavioural Inhibition and Behavioural Activation System (BIS/BAS) scales were developed by Carver and White (1994) and comprise four scales which measure individual differences in personality (Gray 1982, 1991). More recent modifications, namely the five-factor model derived from Gray and McNaughton's (2000) revised Reward Sensitivity Theory (RST) suggests that Anxiety and Fear are separable components of inhibition. This study employed exploratory and confirmatory factor analyses on the scales in order to test whether the four or five-factor model was the better fit in a sample of 994 participants aged 11–30 years. Consistent with RST, superior model fit was shown for the five-factor model with all variables correlated. Significant age effects were observed for BIS Fear and BIS Anxiety, with scores peaking in middle and late adolescence respectively. The BAS subscales showed differential effects of age group. Significantly increasing scores from early to mid and from mid to late adolescence were found for Drive, but the effect of age on Fun Seeking and Reward Responsiveness was not significant.

Abstract: Psychometric properties of two self-report clinical competence scales for nursing students.

Abstract: Psychometric properties of two self-report clinical competence scales for nursing students.
Background: It is important to assess the clinical competence of nursing students to gauge their professional development and educational needs. This can be measured by self-assessment tools. Anema and McCoy (2010) contended that the currently available measures need further psychometric testing.
Aim: To test the psychometric properties of Nursing Competencies Questionnaire (NCQ) and Self-Efficacy in Clinical Performance (SECP) clinical competence scales.

Method: A non-randomly selected sample of n=248 2nd year nursing students completed NCQ, SECP and demographic questionnaires (June and September 2013). Mokken Scaling Analysis (MSA) was used to test the structural validity and scale properties, convergent and discriminant validity and reliability were subsequently tested.

Results: The NCQ provided evidence of a unidimensional scale which had strong scale scalability coefficients Hs =0.581; but limited evidence of item rankability HT =0.367. MSA undertaken with the SECP scale identified two potential unidimensional scales the SECP28 and SECP7, each with adequate evidence of good/reasonable scalablity psychometric properties as a summed scale but no/very limited evidence of scale rankability (SECP28: Hs = 0.55, HT=0.211; SECP7: Hs = 0.61, HT=0.049). Analysis of between cohort differences and NCQ/ SECP scale scores produced evidence of convergent and discriminant validity and good internal reliability: NCQ α = 0.93, SECP28 α = 0.96, and SECP7 α=0.89.

Discussion: The NCQ was verified to have evidence of reliability and validity; however, as the SECP findings are new, and the sample small, with reference to Straat and colleagues (2014), the SECP results should be interpreted with caution and verified on a second sample.

Conclusions: Measurement of perceived self-competence could inform the development of nursing competence and could start early in a nursing programme. Further testing of the NCQ and SECP scales with larger samples and from different years is indicated.


References:
Anema, M., G and McCoy, JK. (2010) Competency-Based Nursing Education: Guide to Achieving Outstanding Learner Outcomes. New York: Springer.
Straat, JH., van der Ark, LA and Sijtsma, K. (2014) Minimum Sample Size Requirements for Mokken Scale Analysis Educational and Psychological Measurement 74 (5), 809-822.

Appropriate complexity for the prediction of coastal and estuarine geomorphic behaviour at decadal to centennial scales

Coastal and estuarine landforms provide a physical template that not only accommodates diverse ecosystem functions and human activities, but also mediates flood and erosion risks that are expected to increase with climate change. In this paper, we explore some of the issues associated with the conceptualisation and modelling of coastal morphological change at time and space scales relevant to managers and policy makers. Firstly, we revisit the question of how to define the most appropriate scales at which to seek quantitative predictions of landform change within an age defined by human interference with natural sediment systems and by the prospect of significant changes in climate and ocean forcing. Secondly, we consider the theoretical bases and conceptual frameworks for determining which processes are most important at a given scale of interest and the related problem of how to translate this understanding into models that are computationally feasible, retain a sound physical basis and demonstrate useful predictive skill. In particular, we explore the limitations of a primary scale approach and the extent to which these can be resolved with reference to the concept of the coastal tract and application of systems theory. Thirdly, we consider the importance of different styles of landform change and the need to resolve not only incremental evolution of morphology but also changes in the qualitative dynamics of a system and/or its gross morphological configuration. The extreme complexity and spatially distributed nature of landform systems means that quantitative prediction of future changes must necessarily be approached through mechanistic modelling of some form or another. Geomorphology has increasingly embraced so-called ‘reduced complexity’ models as a means of moving from an essentially reductionist focus on the mechanics of sediment transport towards a more synthesist view of landform evolution. However, there is little consensus on exactly what constitutes a reduced complexity model and the term itself is both misleading and, arguably, unhelpful. Accordingly, we synthesise a set of requirements for what might be termed ‘appropriate complexity modelling’ of quantitative coastal morphological change at scales commensurate with contemporary management and policy-making requirements: 1) The system being studied must be bounded with reference to the time and space scales at which behaviours of interest emerge and/or scientific or management problems arise; 2) model complexity and comprehensiveness must be appropriate to the problem at hand; 3) modellers should seek a priori insights into what kind of behaviours are likely to be evident at the scale of interest and the extent to which the behavioural validity of a model may be constrained by its underlying assumptions and its comprehensiveness; 4) informed by qualitative insights into likely dynamic behaviour, models should then be formulated with a view to resolving critical state changes; and 5) meso-scale modelling of coastal morphological change should reflect critically on the role of modelling and its relation to the observable world.

Outlier Loci Detect Intraspecific Biodiversity amongst Spring and Autumn Spawning Herring across Local Scales

Herring, Clupea harengus, is one of the ecologically and commercially most important species in European northern seas, where two distinct ecotypes have been described based on spawning time; spring and autumn. To date, it is unknown if these spring and autumn spawning herring constitute genetically distinct units. We assessed levels of genetic divergence between spring and autumn spawning herring in the Baltic Sea using two types of DNA markers, microsatellites and Single Nucleotide Polymorphisms, and compared the results with data for autumn spawning North Sea herring. Temporally replicated analyses reveal clear genetic differences between ecotypes and hence support reproductive isolation. Loci showing non-neutral behaviour, so-called outlier loci, show convergence between autumn spawning herring from demographically disjoint populations, potentially reflecting selective processes associated with autumn spawning ecotypes. The abundance and
exploitation of the two ecotypes have varied strongly over space and time in the Baltic Sea, where autumn spawners have faced strong depression for decades. The results therefore have practical implications by highlighting the need for specific management of these co-occurring ecotypes to meet requirements for sustainable exploitation and ensure optimal livelihood for coastal communities.

Utility of US Norms for the Bayley Scales of Infant Development (III) in UK and Irish Children

The aim of this paper is to explore the utility of the United States norms for United Kingdom and Republic of Ireland populations. The Bayley Scales of Infant Development (BSID III) is a globally used developmental assessment for typically developing and clinical samples of children aged 1 to 42 months. A UK norming exercise (REF) confirmed the suitability of US norms for UK based research and practice. However, debate has continued concerning the utility of the US norms in other countries. This paper further explores the utility of the US norms for the UK and ROI populations using BSID III developmental outcome data from two samples of over one thousand typically developing children.

Paramountcy, family rights and contested adoption: does contact with birth relatives balance the scales?

This article combines practitioner insight and research evidence to chart how principles of partnership and paramountcy have led to birth family contact becoming the expected norm following contested adoption from care in Northern Ireland. The article highlights how practice has adapted to the delay in proposed reforms to adoption legislation resulting in the evolution of increasingly open adoption practices. Adoption represents an irrevocable transfer of parental responsibility from birth to adoptive parents and achieves permanence and legal security for children in care who cannot return to their birth family. Its enduring effect, however, makes public adoption a contentious field of child welfare practice, particularly when contested by birth parents. This article explores how post-adoption contact may be viewed as reconciling the uneasy interface between paramountcy principles and parental rights to respect for family life. The article highlights the complexity of adoptive kinship relationships following contested adoption from care, and how contact presents unique challenges that mitigate against meaningful and sustainable connections between the child and their birth relatives. In conclusion, a call is made for sensitive negotiation and support of contact arrangements, and the development of practice models that are informed by an understanding of the workings of adoptive kinship.

Calculus of variations on time scales and discrete fractional calculus

Estudamos problemas do cálculo das variações e controlo óptimo no contexto das escalas temporais. Especificamente, obtemos condições necessárias de optimalidade do tipo de Euler–Lagrange tanto para lagrangianos dependendo de derivadas delta de ordem superior como para problemas isoperimétricos. Desenvolvemos também alguns métodos directos que permitem resolver determinadas classes de problemas variacionais através de desigualdades em escalas temporais. No último capítulo apresentamos operadores de diferença fraccionários e propomos um novo cálculo das variações fraccionário em tempo discreto. Obtemos as correspondentes condições necessárias de Euler– Lagrange e Legendre, ilustrando depois a teoria com alguns exemplos.

Fractional calculus on time scales - Cálculo fraccional em escalas temporais

Introduzimos um cálculo das variações fraccional nas escalas temporais ℤ e (hℤ)!. Estabelecemos a primeira e a segunda condição necessária de optimalidade. São dados alguns exemplos numéricos que ilustram o uso quer da nova condição de Euler–Lagrange quer da nova condição do tipo de Legendre. Introduzimos também novas definições de derivada fraccional e de integral fraccional numa escala temporal com recurso à transformada inversa generalizada de Laplace.