An investigation of possible mechanisms of the water-gas shift reaction over a ZrO2-supported Pt catalyst

The present work investigates the reactivity of the surface species observable by in situ DRIFTS formed over a Pt/ZrO2 during the water-gas shift (WGS) reaction. A DRIFTS cell/mass spectrometer system was operated at the chemical steady state during isotopic transients to yield information about the true nature (i.e., main reaction intermediate or spectators) of adsorbates. Only carbonyl and formate species were observed by DRIFTS under reaction conditions; the surface coverage of carbonate species was negligible. Isotopic transient kinetic analyses revealed that formates exchanged uniformly according to a first-order law, suggesting that most formates observed by DRIFTS were of the same reactivity. In addition, the time scale of the exchange of the reaction product CO2 was significantly shorter than that of the surface formates. Therefore, a formate route based on the formates as detected by DRIFTS can be ruled out as the main reaction pathway in the present case. The number of precursors of the reaction product CO2 was smaller than the number of surface Pt atoms, suggesting that carbonyl species or some \

Steam reforming of model compounds and fast pyrolysis bio-oil on supported noble metal catalysts

The production of hydrogen by steam reforming of bio-oils obtained from the fast pyrolysis of biomass requires the development of efficient catalysts able to cope with the complex chemical nature of the reactant. The present work focuses on the use of noble metal-based catalysts for the steam reforming of a few model compounds and that of an actual bio-oil. The steam reforming of the model compounds was investigated in the temperature range 650-950 degrees C over Pt, Pd and Rh supported on alumina and a ceria-zirconia sample. The model compounds used were acetic acid, phenol, acetone and ethanol. The nature of the support appeared to play a significant role in the activity of these catalysts. The use of ceria-zirconia, a redox mixed oxide, lead to higher H-2 yields as compared to the case of the alumina-supported catalysts. The supported Rh and Pt catalysts were the most active for the steam reforming of these compounds, while Pd-based catalysts poorly performed. The activity of the promising Pt and Rh catalysts was also investigated for the steam reforming of a bio-oil obtained from beech wood fast pyrolysis. Temperatures close to, or higher than, 800 degrees C were required to achieve significant conversions to COx and H-2 (e.g., H-2 yields around 70%). The ceria-zirconia materials showed a higher activity than the corresponding alumina samples. A Pt/ceria-zirconia sample used for over 9 h showed essentially constant activity, while extensive carbonaceous deposits were observed on the quartz reactor walls from early time on stream. In the present case, no benefit was observed by adding a small amount of O-2 to the steam/bio-oil feed (autothermal reforming, ATR), probably partly due to the already high concentration of oxygen in the bio-oil composition. (c) 2005 Elsevier B.V. All rights reserved.

Rotating Brains / Beating Heart:International collaborative performance with Stelarc, the virtual reality ensemble Avatar Orchestra Metaverse, Pauline Oliveros, Martin Parker and saxophonist Franziska Schroeder.

The work ROTATING BRAINS / BEATING HEART was specifically developed for the opening performance of the 2010 DRHA conference. The conference’s theme ‘Sensual Technologies: Collaborative Practices of Interdisciplinarity explored collaborative relationships between the body and sensual/sensing technologies across various disciplines, looking to new approaches offered by various emerging fields and practices that incorporate new and existing technologies. The conference had a specific focus on SecondLife with roundtable events and discussions, led by performance artist Stelarc, as well as international participation via SecondLife.
The collaboration between Stelarc, the Avatar Orchestra Metaverse (AOM) and myself as the DRHA2010 conference program chair was a unique occurrence for this conference.

A Computer Music Retrospective

A composer who has worked in the field of computer music for the last 25 years reflects on how technological developments during that time have affected his work in computer music, instrumental music and hybrid combinations of the two. The compositional trajectories traced here often run parallel to opportunities afforded by the evolution of computer technology suitable for the generation of digital audio.

Theoretical and experimental correlations of gas dissolution, diffusion, and thermodynamic properties in determination of gas permeability and selectivity in supported ionic liquid membranes

Supported ionic liquid membranes (SILMs) has the potential to be a new technological platform for gas/organic vapour separation because of the unique non-volatile nature and discriminating gas dissolution properties of room temperature ionic liquids (ILs). This work starts with an examination of gas dissolution and transport properties in bulk imidazulium cation based ionic liquids [C_nmim][NTf2] (n = 2.4, 6, 8.10) from simple gas H₂, N₂, to polar CO₂, and C₂H₆, leading to a further analysis of how gas dissolution and diffusion are influenced by molecular specific gas-SILMs interactions, reflected by differences in gas dissolution enthalpy and entropy. These effects were elucidated again during gas permeation studies by examining how changes in these properties and molecular specific interactions work together to cause deviations from conventional solution–diffusion theory and their impact on some remarkably contrasting gas perm-selectivity performance. The experimental perm-selectivity for all tested gases showed varied and contrasting deviation from the solution–diffusion, depending on specific gas-IL combinations. It transpires permeation for simpler non-polar gases (H₂, N₂) is diffusion controlled, but strong molecular specific gas-ILs interactions led to a different permeation and selectivity performance for C₂H₆ and CO₂. With exothermic dissolution enthalpy and large order disruptive entropy, C₂H₆ displayed the fastest permeation rate at increased gas phase pressure in spite of its smallest diffusivity among the tested gases. The C₂H₆ gas molecules “peg” on the side alkyl chain on the imidazulium cation at low concentration, and are well dispersed in the ionic liquids phase at high concentration. On the other hand strong CO₂-ILs affinity resulted in a more prolonged “residence time” for the gas molecule, typified by reversed CO₂/N₂ selectivity and slowest CO₂ transport despite CO₂ possess the highest solubility and comparable diffusivity in the ionic liquids. The unique transport and dissolution behaviour of CO₂ are further exploited by examining the residing state of CO₂ molecules in the ionic liquid phase, which leads to a hypothesis of a condensing and holding capacity of ILs towards CO₂, which provide an explanation to slower CO₂ transport through the SILMs. The pressure related exponential increase in permeations rate is also analysed which suggests a typical concentration dependent diffusion rate at high gas concentration under increased gas feed pressure. Finally the strong influence of discriminating and molecular specific gas-ILs interactions on gas perm-selectivity performance points to future specific design of ionic liquids for targeted gas separations.

Bridging the Gap between CO Adsorption Studies on Gold Model Surfaces and Supported Nanoparticles

A happy medium: Volumetric adsorption of carbon monoxide at 308 K and UHR-HAADF-STEM, HREM, and computer modeling techniques were compared. Experimental CO/Au ratios at saturation coverage for two supported gold catalysts were shown to fit very well the predictions of a nanostructural model that considers CO adsorption on gold sites with coordination numbers of less than eight.

Job Strain and Alcohol Intake:A Collaborative Meta-Analysis of Individual-Participant Data from 140 000 Men and Women

BACKGROUND: The relationship between work-related stress and alcohol intake is uncertain. In order to add to the thus far inconsistent evidence from relatively small studies, we conducted individual-participant meta-analyses of the association between work-related stress (operationalised as self-reported job strain) and alcohol intake. METHODOLOGY AND PRINCIPAL FINDINGS: We analysed cross-sectional data from 12 European studies (n?=?142 140) and longitudinal data from four studies (n?=?48 646). Job strain and alcohol intake were self-reported. Job strain was analysed as a binary variable (strain vs. no strain). Alcohol intake was harmonised into the following categories: none, moderate (women: 1-14, men: 1-21 drinks/week), intermediate (women: 15-20, men: 22-27 drinks/week) and heavy (women: >20, men: >27 drinks/week). Cross-sectional associations were modelled using logistic regression and the results pooled in random effects meta-analyses. Longitudinal associations were examined using mixed effects logistic and modified Poisson regression. Compared to moderate drinkers, non-drinkers and (random effects odds ratio (OR): 1.10, 95% CI: 1.05, 1.14) and heavy drinkers (OR: 1.12, 95% CI: 1.00, 1.26) had higher odds of job strain. Intermediate drinkers, on the other hand, had lower odds of job strain (OR: 0.92, 95% CI: 0.86, 0.99). We found no clear evidence for longitudinal associations between job strain and alcohol intake. CONCLUSIONS: Our findings suggest that compared to moderate drinkers, non-drinkers and heavy drinkers are more likely and intermediate drinkers less likely to report work-related stress.

Job strain as a risk factor for coronary heart disease:a collaborative meta-analysis of individual participant data

BACKGROUND: Published work assessing psychosocial stress (job strain) as a risk factor for coronary heart disease is inconsistent and subject to publication bias and reverse causation bias. We analysed the relation between job strain and coronary heart disease with a meta-analysis of published and unpublished studies. METHODS: We used individual records from 13 European cohort studies (1985-2006) of men and women without coronary heart disease who were employed at time of baseline assessment. We measured job strain with questions from validated job-content and demand-control questionnaires. We extracted data in two stages such that acquisition and harmonisation of job strain measure and covariables occurred before linkage to records for coronary heart disease. We defined incident coronary heart disease as the first non-fatal myocardial infarction or coronary death. FINDINGS: 30?214 (15%) of 197?473 participants reported job strain. In 1·49 million person-years at risk (mean follow-up 7·5 years [SD 1·7]), we recorded 2358 events of incident coronary heart disease. After adjustment for sex and age, the hazard ratio for job strain versus no job strain was 1·23 (95% CI 1·10-1·37). This effect estimate was higher in published (1·43, 1·15-1·77) than unpublished (1·16, 1·02-1·32) studies. Hazard ratios were likewise raised in analyses addressing reverse causality by exclusion of events of coronary heart disease that occurred in the first 3 years (1·31, 1·15-1·48) and 5 years (1·30, 1·13-1·50) of follow-up. We noted an association between job strain and coronary heart disease for sex, age groups, socioeconomic strata, and region, and after adjustments for socioeconomic status, and lifestyle and conventional risk factors. The population attributable risk for job strain was 3·4%. INTERPRETATION: Our findings suggest that prevention of workplace stress might decrease disease incidence; however, this strategy would have a much smaller effect than would tackling of standard risk factors, such as smoking. FUNDING: Finnish Work Environment Fund, the Academy of Finland, the Swedish Research Council for Working Life and Social Research, the German Social Accident Insurance, the Danish National Research Centre for the Working Environment, the BUPA Foundation, the Ministry of Social Affairs and Employment, the Medical Research Council, the Wellcome Trust, and the US National Institutes of Health.

Enabling Social Work Students to Deal with the Consequences of Political Conflict: Engaging with Victim/Survivor Service Users and a ‘Pedagogy of Discomfort’

This paper describes the evaluation of an educational project, delivered in a Bachelor in Social Work degree (BSW) program in Northern Ireland. The project aimed to equip social work students to be more culturally competent in this divided society, with a central focus on including victim/survivor service users in social work training. A number of pedagogical approaches are noted, with particular consideration of Boler's ‘pedagogy of discomfort’ as a model that includes the multidimensional nature of the learning process when topics carry a high emotional tariff. The evaluation of the students' experience indicated that: there was strong support among students for the project; the unique contribution of service users was affirmed; and the project appeared to increase students' awareness and capacity to practice in a divided society. The evaluation of the trainers' experience highlighted key processes in the delivery of collaborative training. The authors argue that the lessons learned are broadly applicable to other forms of service user and carer involvement in social work training and in other societies in which health and social care professionals have to deal with the legacies of political conflict.

An Evaluation of the Effectiveness of an FE/HE Partnership in the Delivery of a Preparation for Practice Module within an Undergraduate Social Work Degree Programme

The Preparation for Practice module at the University of Ulster is delivered to 170 first year students via a collaborative arrangement between higher and further education institutions. In each of the five sites, students receive large group and small group teaching facilitated by social work training agency workers and academic tutor dyads. An evaluation of the module sought the perceptions of the agency and academic facilitators regarding the overall collaborative arrangement and the model of co-teaching involving social work academics and agency partners. Respondents were asked to complete a semi-structured questionnaire, which generated data from a Likert scale and also invited qualitative commentary. The Likert scale data were analysed via SPSS and the qualitative information was scrutinised using a manual thematic analysis technique. Findings indicated that continuous communication, consistency in programme content and the acknowledgement of the differences in organisation resources were key to a successful collaborative arrangement. It was also noted that a co-teaching model should be viewed as a positive vehicle for achieving module objectives in a safe learning environment.

Common-sense knowledge for a computer vision system for human action recognition

This work presents a novel approach for human action recognition based on the combination of computer vision techniques and common-sense knowledge and reasoning capabilities. The emphasis of this work is on how common sense has to be leveraged to a vision-based human action recognition so that nonsensical errors can be amended at the understanding stage. The proposed framework is to be deployed in a realistic environment in which humans behave rationally, that is, motivated by an aim or a reason. © 2012 Springer-Verlag.

Social effects of collaborative learning in primary schools

There is conflicting evidence on whether collaborative group work leads to improved classroom relations, and if so how. A before and after design was used to measure the impact on work and play relations of a collaborative learning programme involving 575 students 9e12 years old in single- and mixed-age classes across urban and rural schools. Data were also collected on student interactions and teacher ratings of their group-work skills. Analysis of variance revealed significant gains for both types of relation. Multilevel modelling indicated that better work relations were the product of improving group skills, which offset tensions produced by transactive dialogue, and this effect fed through in turn to play relations. Although before intervention rural children were familiar with each other neither this nor age mix affected outcomes. The results suggest the social benefits of collaborative learning are a separate outcome of group work, rather than being either a pre-condition for, or a direct consequence of successful activity, but that initial training in group skills may serve to enhance these benefits.

Swarm scheduling approaches for work-flow applications with security constraints in distributed data-intensive computing environments

The scheduling problem in distributed data-intensive computing environments has become an active research topic due to the tremendous growth in grid and cloud computing environments. As an innovative distributed intelligent paradigm, swarm intelligence provides a novel approach to solving these potentially intractable problems. In this paper, we formulate the scheduling problem for work-flow applications with security constraints in distributed data-intensive computing environments and present a novel security constraint model. Several meta-heuristic adaptations to the particle swarm optimization algorithm are introduced to deal with the formulation of efficient schedules. A variable neighborhood particle swarm optimization algorithm is compared with a multi-start particle swarm optimization and multi-start genetic algorithm. Experimental results illustrate that population based meta-heuristics approaches usually provide a good balance between global exploration and local exploitation and their feasibility and effectiveness for scheduling work-flow applications. © 2010 Elsevier Inc. All rights reserved.

Episodic Reasoning for Vision-Based Human Action Recognition

Smart Spaces, Ambient Intelligence, and Ambient Assisted Living are environmental paradigms that strongly depend on their capability to recognize human actions. While most solutions rest on sensor value interpretations and video analysis applications, few have realized the importance of incorporating common-sense capabilities to support the recognition process. Unfortunately, human action recognition cannot be successfully accomplished by only analyzing body postures. On the contrary, this task should be supported by profound knowledge of human agency nature and its tight connection to the reasons and motivations that explain it. The combination of this knowledge and the knowledge about how the world works is essential for recognizing and understanding human actions without committing common-senseless mistakes. This work demonstrates the impact that episodic reasoning has in improving the accuracy of a computer vision system for human action recognition. This work also presents formalization, implementation, and evaluation details of the knowledge model that supports the episodic reasoning.