A hydrothermally stable transition alumina by condensation-enhanced self-assembly and pyrolysis crystallization:application in the steam reforming of methane

The preparation of a steam-based hydrothermally stable transition alumina is reported. The gel was derived from a synthetic sol-gel route where Al-tri-sec-butoxide is hydrolysed in the presence of a non-ionic surfactant (EO20PO70EO20), HCl as the catalyst and water (H2O/Al = 6); the condensation was enhanced by treating the hydrolysed gel with tetrabutylammonium hydroxide (TBAOH), after which it was dried at 60 °C by solvent evaporation. The so-obtained mesophase was crystallized under argon at 1200 °C (1 h) producing a transition alumina containing δ/α, and possibly θ, alumina phases. Due to its surface acidity, the pyrolysis conditions transform the block copolymer into a cross-linked char structure that embeds the alumina crystallites. Calcination at 650 °C generates a fully porous material by burning the char; a residual carbon of 0.2 wt.% was found, attributed to the formation of surface (oxy)carbides. As a result, this route produces a transition alumina formed by nanoparticles of about 30 nm in size on average, having surface areas in the range of 59-76 m2 g-1 with well-defined mesopores centered at 14 nm. The material withstands steam at 900 °C with a relative surface area rate loss lower than those reported for δ-aluminas, the state-of-the-art MSU-X γ-alumina and other pure γ-aluminas. The hydrothermal stability was confirmed under relevant CH4 steam reforming conditions after adding Ni; a much lower surface area decay and higher CH4 conversion compared to a state-of-the-art MSU-X based Ni catalyst were observed. Two effects are important in explaining the properties of such an alumina: the char protects the particles against sintering, however, the dominant effect is provided by the TBAOH treatment that makes the mesophase more resistant to coarsening and sintering. This journal is © the Partner Organisations 2014.

Stabilization of self-assembled alumina mesophases

An efficient route to stabilize alumina mesophases derived from evaporation-induced self-assembly is reported after investigating various aspects in-depth: influence of the solvent (EtOH, s-BuOH, and t-BuOH) on the textural and structural properties of the mesophases based on aluminum tri-sec-butoxide (ATSB), synthesis reproducibility, role of nonvolatile acids, and the crystallization and thermal stability of the crystalline counterparts. Mesophase specific surface area and pore uniformity depend notably on the solvent; s-BuOH yields the highest surface area and pore uniformity. The optimal mesophase synthesis is reproducible with standard deviations in the textural parameters below 5%. The most pore-uniform mesophases from the three solvents were thermally activated at 1023 K to crystallize them into γ-alumina. The s-BuOH mesophase is remarkably thermally stable, retaining the mesoscopic wormhole order with 300 m2/g (0.45 cm3/g) and an increased acidic site density. These features are not obtained with EtOH or t-BuOH, where agglomerated γ-Al2O3 crystallites are formed with lower surface areas and broader pore size distributions. This was rationalized by the increase of the hydrolysis rate using EtOH and t-BuOH. t-BuOH dehydrates under the synthesis conditions or reacts with HCl, situations that increase the water concentration and rate of hydrolysis. It was found that EtOH exchanges rapidly, producing a highly reactive Al-ethoxide, thus enhancing the hydrolysis rate as well. Particle heterogeneity with random packing of fibrous and wormhole morphologies, attributed to the high hydrolysis rate, was observed for mesophases derived from both solvents. Such a low particle coordination favors coarsening with enlargement of the pore size distribution upon thermal treatment, explaining the lower thermal stability. Controlled hydrolysis and formation of low-polymerized Al species in s-BuOH are possibly responsible for the adequate assembly onto the surfactant. This was verified by the formation of a regular distribution of relatively size-uniform nanoparticles in the mesophase; high particle coordination prevents coarsening, favors densification, and maintains a relatively uniform pore size distribution upon thermal treatment. The acid removal in the evaporation is another key factor to promote network condensation in this route. © 2013 American Chemical Society.

The financial stability and access to financing of SMEs in Hungary

The present study was prepared within the framework of cooperation between the Competitiveness Research Centre, operating within the Institute of Business Economics of Corvinus University of Budapest, and the National Association of Entrepreneurs, based on a commission from the latter. Th e goal of the study was to survey the self-financing capabilities and borrowing opportunities of majority Hungarian-owned small and medium-sized enterprises (SMEs), and to identify potential problems. The results of the research revealed that the high proportion of owner’s equity in the financing structure is not due to difficulties with borrowing, but because enterprises that cover their fi nancing primarily from their own resources have other financing opportunities at their disposal. Although general satisfaction with banks shows a diminishing tendency, it can still be interpreted favourably. The majority of companies have not encountered serious borrowing difficulties. With regard to the system of competitive tenders, company managers have sensed some improvement, but general satisfaction is still lacking. Although the research results suggest that the primary obstacle to growth in 2013 was not the lack of credit or external funding, it is important to emphasize that start-ups, young enterprises and micro-enterprises, which struggle the most with financing worries, were not represented in the analysed database.

The relationship between self-esteem and job performance

The purpose of this study was to conduct a meta-analysis of the relationship between self-esteem and job performance. Overall, 49 studies were gathered and coded by their sample size, correlation estimate, and the reliability of the two measures being correlated. The data was processed using the interactive meta-analysis program called INTNL, which takes into account interactive effects between the artifacts (i.e., unreliability in the independent and dependent measures as well as sampling error). Analyses of four potential moderators were examined--type of self-esteem, the source of job performance, the type of setting and the type of self-esteem measures. Results indicated that the relationship between self-esteem and job performance is positive. However, there was only a weak support for moderating influences. Procedures to enhance employees' self-esteem are recommended. ^

Clash of identities in South Florida: An examination of the complexity of racial and national identity and their impact on ethnic solidarity between black Americans and Jamaicans

Immigrants from the West Indies and other nations challenge the simple United States dichotomy of blacks versus whites. Many apparently black Caribbean immigrants proclaim that they did not know they were “black” until they arrived in the U.S. They seek to maintain their national identity and resist identity and solidarity with Black Americans. In response, many Black Americans respond that the immigrants are simply being naive, that U.S. society demands simple racial identity. Regardless of one's self-identity and personal history, in the U.S., if you look black, you are black, was their thinking. ^ This study examines the contemporary struggle of identity and solidarity among and between Black Americans and Jamaicans living in South Florida (Broward and Miami-Dade counties). Even though the primary focus of this study is to examine the relationship between Black Americans and Jamaicans, other West Indian nationals will be addressed more generally. The primary research problem of this study is to determine why the existence of common ancestry and physical traits are insufficient for an assumption of ethnic solidarity between Black Americans and Jamaicans. ^ In examining this problem, I felt that depth rather than breadth would provide insight into the current state of polarization between Black Americans and Jamaicans. To this end, a qualitative study was designed. A non-random snowball sample consisting of forty-seven informants was selected for this study. Realizing that such a technique presents problems with generalizations beyond the sample, this approach was, nonetheless, the most suitable for the current research problem. One of the initial challenges of this research was the use of the label “black” in discussing Caribbean immigrants. Unlike America, where distinctions based on skin color were at the bedrock of America's formation, this was not the case in the Caribbean. In the Caribbean skin color was an important marker as an indicator of class, rather than of race. Therefore, I refrained from using the label, “black Jamaicans,” but rather used Jamaicans throughout. ^

The thermodynamics and statistical mechanics of protein folding

The physics of self-organization and complexity is manifested on a variety of biological scales, from large ecosystems to the molecular level. Protein molecules exhibit characteristics of complex systems in terms of their structure, dynamics, and function. Proteins have the extraordinary ability to fold to a specific functional three-dimensional shape, starting from a random coil, in a biologically relevant time. How they accomplish this is one of the secrets of life. In this work, theoretical research into understanding this remarkable behavior is discussed. Thermodynamic and statistical mechanical tools are used in order to investigate the protein folding dynamics and stability. Theoretical analyses of the results from computer simulation of the dynamics of a four-helix bundle show that the excluded volume entropic effects are very important in protein dynamics and crucial for protein stability. The dramatic effects of changing the size of sidechains imply that a strategic placement of amino acid residues with a particular size may be an important consideration in protein engineering. Another investigation deals with modeling protein structural transitions as a phase transition. Using finite size scaling theory, the nature of unfolding transition of a four-helix bundle protein was investigated and critical exponents for the transition were calculated for various hydrophobic strengths in the core. It is found that the order of the transition changes from first to higher order as the strength of the hydrophobic interaction in the core region is significantly increased. Finally, a detailed kinetic and thermodynamic analysis was carried out in a model two-helix bundle. The connection between the structural free-energy landscape and folding kinetics was quantified. I show how simple protein engineering, by changing the hydropathy of a small number of amino acids, can enhance protein folding by significantly changing the free energy landscape so that kinetic traps are removed. The results have general applicability in protein engineering as well as understanding the underlying physical mechanisms of protein folding. ^

Specificity, stability and comparative physiology of coral-Symbiodinium mutualisms: Evaluating the potential for acclimation and/or adaptation in reef corals

The relationship between reef corals and endosymbiotic dinoflagellates is fundamental to the existence of coral reefs. To evaluate the fidelity of coral-Symbiodinium mutualisms, corals maintained in aquaria for years were analyzed by denaturant gradient gel electrophoresis (DGGE). Comparing Symbiodinium populations of captive aquarium colonies with known associations in nature is a practical way of examining partner flexibility. The finding of "normal" symbiont populations in corals existing under highly variable conditions supports the premise that most coral colonies possess stable associations. High sensitivity real-time PCR (rtPCR) was used to evaluate background populations of the putatively stress-tolerant Symbiodinium D in reef corals of the Caribbean. Analyses of samples collected during periods of environmental stability indicate the ability of Symbiodinium D to associate with a wider diversity of host taxa than previously recognized. To gain a broader perspective with regard to the ecology of Symbiodinium D1a, rtPCR and DGGE were used to evaluate the symbiont populations of reef corals from Barbados before and after the 2005 mass coral bleaching. Background populations were observed in 56% of the host genera prior to observations of bleaching. These findings indicate that 'stress', not 'bleaching', caused the displacement of 'natural' symbiont population and the opportunistic proliferation of D1a in many host taxa. Of the 12 host taxa monitored before and after the bleaching event, there was a 40% increase in colonies hosting Symbiodinium D1a. Together, these studies elucidate the mechanism responsible for recent observations reporting the emergence of Symbiodinium D following thermal disturbances. These observations are now most easily explained as the disproportionate growth of existing in hospite symbiont populations, rather than novel symbiont acquisition subsequent to bleaching. To evaluate the comparative "fitness" of corals able to host multiple symbiont types, rates of calcification were measured in P. verrucosa hosting either Symbiodinium C1b-c or D1 at elevated temperature. Rates of calcification decreased significantly for both host-symbiont combinations, but differences attributable to symbiont composition were not detected. This research improves our knowledge of the symbiosis biology and ecology of reef corals and contributes information necessary to most accurately predict the response of these ecosystems to global climate changes.

The Re-Emergence of Suriname’s Désiré (Desi) Bouterse: Political Acumen and Geopolitical Anxiety

This study examines some concerns that derive from Suriname‘s May-July 2010 elections, which resulted in the re-emergence of erstwhile military ruler and convicted drug trafficker, Désiré (Desi) Bouterse, as President of the Republic. The victory reflects Bouterse‘s political acumen in aggregating disparate political interests and in establishing a viable coalition government. But because of his history and profile, this triumph has generated anxiety in some places internationally. In this respect, the study examines anxieties related to three matters: (a) relations with Guyana, where there is an existing territorial dispute and a recently resolved maritime dispute, (b) illegal drug trafficking operations, and (c) foreign policy engagement with Venezuela. There has been a flurry of bilateral activities—including several presidential summits—with Guyana since President Bouterse‘s inauguration, albeit seemingly more about symbolism than substance. Although the maritime dispute was settled by a Tribunal of the United Nations Convention of the Law of the Sea in 2007, the 15,000 km2 New River Triangle is still unresolved. Indeed, in June 2011 President Bouterse reasserted Suriname‘s claim to the Triangle. Suriname has upped the ante in that dispute by portraying internationally the map of Suriname as inclusive of the disputed area. In all likelihood that self-redefinition slowly will become the country‘s cartographic definition in the eyes of the world if Guyana does not successfully rebuff that move or pursue the definitive settlement of the dispute. A geonarcotics assessment shows Suriname to be still heavily implicated in trafficking, because of geography, law enforcement limitations, corruption, and other factors. But despite Bouterse‘s drug-related history and that of former senior military officers, several reasons suggest the inexpediency of a narco-state being created by Bouterse. As well, as part of Suriname‘s pursuit of increased Caribbean and South American engagement, it has boosted relations with Venezuela, which has included it in PetroCaribe and provided housing and agricultural aid. However, the engagement appears to be driven more by pragmatism and less by any ideological affinity with Hugo Chavez.

Content -area teachers' perceptions of the effect of the meta -training on their instructional practices

The purpose of this study was to explore the content-area teachers' perceptions of the effect that compliance with the teacher training for content-area teachers of Limited English Proficient (LEP) students mandated by the Consent Decree had on their instructional practices within the content-area classroom. In order to provide an overview of the factors which had an effect on the content-area teachers' mandated training, various areas were reviewed: history of legislative actions that led up to the Consent Decree; stipulations set forth in the Consent Decree; Miami-Dade County Public Schools District LEP Plan including stipulations for teacher training; research on teacher training for teachers of language minority students; and the process of change. This descriptive study specifically addresses teachers' perceptions of the effectiveness of the mandated teacher training as it relates to language minority students. ^ Content-area teachers who had completed the mandated teacher training were surveyed using self-administered anonymous questionnaires mailed to their school sites. Questions focused on the teachers' perceptions of: students' need of second language instructional strategies within the content-area classroom; teacher training requirements mandated by the Consent Decree; and changes in their instructional practices as a result of the training. ^ Based on the responses of the subjects, the results of this study indicate the overall success of the training implemented to comply with the stipulations set forth in the Consent Decree. In general, the results indicate that the teachers perceive that they are ultimately in agreement with the mandated training. The results also indicate that the teachers perceive a need for second language strategies when working with language minority students. These results can serve as starting point for further research not only into teachers' perceptions of the effectiveness of training for teachers of language minority students but also into the outcomes of this teacher training as it is reflected within the classroom. ^

Emergence and Fate of Siloxanes in Waste Streams: Release Mechanisms, Partitioning and Persistence in Three Environmental Compartments

Siloxanes are widely used in personal care and industrial products due to their low surface tension, thermal stability, antimicrobial and hydrophobic properties, among other characteristics. Volatile methyl siloxanes (VMS) have been detected both in landfill gas and biogas from anaerobic digesters at wastewater treatment plants. As a result, they are released to gas phase during waste decomposition and wastewater treatment. During transformation processes of digester or landfill gas to energy, siloxanes are converted to silicon oxides, leaving abrasive deposits on engine components. These deposits cause increased maintenance costs and in some cases complete engine overhauls become necessary. The objectives of this study were to compare the VMS types and levels present in biogas generated in the anaerobic digesters and landfills and evaluate the energetics of siloxane transformations under anaerobic conditions. Siloxane emissions, resulting from disposal of silicone-based materials, are expected to increase by 29% within the next 10 years. Estimated concentrations and the risk factors of exposure to siloxanes were evaluated based on the initial concentrations, partitioning characteristics and persistence. It was determined that D4 has the highest risk factor associated to bioaccumulation in liquid and solid phase, whereas D5 was highest in gas phase. Additionally, as siloxanes are combusted, the particle size range causes them to be potentially hazardous to human health. When inhaled, they may affix onto the alveoli of the lungs and may lead to development of silicosis. Siloxane-based COD-loading was evaluated and determined to be an insignificant factor concerning COD limits in wastewater. Removal of siloxane compounds is recommended prior to land application of biosolids or combustion of biogas. A comparison of estimated costs was made between maintenance practices for removal of siloxane deposits and installation/operation of fixed-bed carbon absorption systems. In the majority of cases, the installation of fixed-bed adsorption systems would not be a feasible option for the sole purpose of siloxane removal. However they may be utilized to remove additional compounds simultaneously.

Mellow Parenting : systematic review and meta-analysis of an intervention to promote sensitive parenting

Acknowledgements For part of the preparation period for this article, AM was supported by an NHS Research Scotland Career Research Fellowship. AM, LT, and PW have been involved in previous research into Mellow Parenting as well as other parenting programmes and have collaborated with the Mellow Parenting charity. PW has had travel and subsistence expenses reimbursed for attendance at a Mellow Parenting conference; otherwise the authors have not received financial recompense for any of these activities. We thank the Mellow Parenting charity for their advice about conducting this review.

Mellow Parenting : systematic review and meta-analysis of an intervention to promote sensitive parenting

Acknowledgements For part of the preparation period for this article, AM was supported by an NHS Research Scotland Career Research Fellowship. AM, LT, and PW have been involved in previous research into Mellow Parenting as well as other parenting programmes and have collaborated with the Mellow Parenting charity. PW has had travel and subsistence expenses reimbursed for attendance at a Mellow Parenting conference; otherwise the authors have not received financial recompense for any of these activities. We thank the Mellow Parenting charity for their advice about conducting this review.

Spatial organisation of groundwater dynamics and streamflow response from different hydropedological units in a montane catchment

Funding was provided by the Leibniz Association (SAW-2012-IGB 4167) within the International Leibniz Graduate School: Aquatic boundaries and linkages- Aqualink. We would like to thank the NRI staff for their help during field work.

Simulation-based education : Understanding the sociocultural complexity of a surgical training “Boot Camp”

Acknowledgements We acknowledge, with thanks the contributions, of the following people who co-designed Boot Camp: Angus JM Watson (Highland Surgical Research Unit, NHSH & UoS), Morag E Hogg (NHSH Raigmore Hospital) and Ailsa Armstrong (NHSH). We also thank Angus JM Watson and Morag E Hogg for helping with the preparation of the funding application which supported this work. Funding Our thanks to the Clinical Skills Managed Educational Network (CSMEN) of Scotland for funding this research.

Discrete choice experiment response rates : A meta-analysis

Funding: Verity Watson acknowledges financial support from the Chief Scientist Office of the Scottish Government Health and Social Care Directorates. The funders had no role in the study design; in the collection, analysis and interpretation of data; in the writing of the report; and in the decision to submit the article for publication. Acknowledgements: We thank Marjon van der Pol, Mandy Ryan and Rainer Schulz for helpful comments and suggestions throughout the project. We also thank Karen Gerard and Tim Bolt for comparing the results of our systematic review with a similar systematic review they are conducting at the same time. We would like to thank Douglas Olley for excellent research assistance.