Sn-modification of Pt7/alumina model catalysts: Suppression of carbon deposition and enhanced thermal stability.

An atomic layer deposition process is used to modify size-selected Pt7/alumina model catalysts by Sn addition, both before and after Pt7 cluster deposition. Surface science methods are used to probe the effects of Sn-modification on the electronic properties, reactivity, and morphology of the clusters. Sn addition, either before or after cluster deposition, is found to strongly affect the binding properties of a model alkene, ethylene, changing the number and type of binding sites, and suppressing decomposition leading to carbon deposition and poisoning of the catalyst. Density functional theory on a model system, Pt4Sn3/alumina, shows that the Sn and Pt atoms are mixed, forming alloy clusters with substantial electron transfer from Sn to Pt. The presence of Sn also makes all the thermally accessible structures closed shell, such that ethylene binds only by π-bonding to a single Pt atom. The Sn-modified catalysts are quite stable in repeated ethylene temperature programmed reaction experiments, suggesting that the presence of Sn also reduces the tendency of the sub-nano-clusters to undergo thermal sintering

Insights into electrochemiluminescent enhancement through electrode surface modification

The electrochemiluminescent (ECL) properties of a luminescent metal centre, [Ru(bpy)(3)](2+), can be significantly modulated through its electronic interaction with neighbouring centres and the polymer backbone used to confine it on an electrode surface. From the perspective of ECL based sensing devices, an increase in the ECL efficiency of a metallopolymer film can result in enhanced sensor sensitivity and selectivity. This work probes the ECL properties of both conjugated, [Ru(bpy)(2)(PPyBBIM)(10)](2+), and non-conjugated, [Ru(bpy)(2)(PVP)(10)](2+), ruthenium based metallopolymer films based on a well documented reaction with sodium oxalate, where bpy is 2,2'-bipyridyl, PPYBBIM is poly[2-(2-pyridyl)-bibenzimidazole] and PVP is poly(4-vinylpyridine). Through a combination of ground state electrochemical studies and ECL measurements, the ECL efficiency for each film is determined. This study reveals that despite a dramatic influence in charge transfer rates between metal centres, as observed for the conducting polymer, mediated through the conducting polymer backbone, a corresponding increase in ECL efficiency is not always observed. The degree of communication between the adjacent excited state metal centres are an important consideration for ECL enhancement however self quenching, luminophore distribution and film porosity must also be considered

Temporal Integration of Movement: The Time-Course of Motion Streaks Revealed by Masking

Temporal integration in the visual system causes fast-moving objects to leave oriented ‘motion streaks’ in their wake, which could be used to facilitate motion direction perception. Temporal integration is thought to occur over 100 ms in early cortex, although this has never been tested for motion streaks. Here we compare the ability of fast-moving (‘streaky’) and slow-moving fields of dots to mask briefly flashed gratings either parallel or orthogonal to the motion trajectory. Gratings were presented at various asynchronies relative to motion onset (from to ms) to sample the time-course of the accumulating streaks. Predictions were that masking would be strongest for the fast parallel condition, and would be weak at early asynchronies and strengthen over time as integration rendered the translating dots more streaky and grating-like. The asynchrony where the masking function reached a plateau would correspond to the temporal integration period. As expected, fast-moving dots caused greater masking of parallel gratings than orthogonal gratings, and slow motion produced only modest masking of either grating orientation. Masking strength in the fast, parallel condition increased with time and reached a plateau after 77 ms, providing an estimate of the temporal integration period for mechanisms encoding motion streaks. Interestingly, the greater masking by fast motion of parallel compared with orthogonal gratings first reached significance at 48 ms before motion onset, indicating an effect of backward masking by motion streaks

Economic growth and inequality : the role of fiscal policies

This paper analyses the impact of different instruments of fiscal policy on economic growth as well as on income inequality, using an unbalanced panel of 43 upper-middle and high income countries for the period 1972-2006. We consider and estimate two individual equations explaining growth and inequality in order to assess the incidence of different fiscal policies. Firstly, our approach considers imposing orthogonal assumptions between growth and inequality in both equations, and secondly, it allows growth to be included in the inequality equation, and inequality to be included in the growth equation. The empirical results suggest that an increase in the size of government measured through current expenditures and direct taxes diminishes economic growth while reducing inequality, being public investment the only fiscal policy that may break this trade-off between efficiency and equity, since increases in this item reduces inequality without harming output. Therefore, the results reflect that the trade-off between efficiency and equity that governments often confront when designing their fiscal policies may be avoided

Decreasing rates of natural deaths in a remote Australian Aboriginal community, 1996-2010

Objective: To examine the trends of all-cause natural mortality for people aged 15 years and over in a remote Australian Aboriginal community between 1996 and 2010. Methods: The annual population in the community by gender and age group was obtained from the Australian Bureau of Statistics (ABS). All known deaths and all records of start of renal replacement therapy (RRT) for renal failure were recorded between 1996 and 2010. Five-year aggregated death rates were calculated and the changes in natural mortality over the interval were evaluated. Mortality was compared with those of the Northern Territory (NT) Indigenous and non-Indigenous people as a whole from 1998 to 2006. Results: Rates of natural deaths were lower in the third interval 2006-2010 relative to the first interval 1996-2000, with higher, but more rapidly falling rates for females than males. Reductions were prominent for both sexes in the 65 and over age groups, but death rates in females of earlier middle age also trended lower. The trends applied whether or not the starting of RRT was considered as a natural death. There was a similar trend in rates of natural death in the aggregate Indigenous population of NT. Conclusions: The downward trends probably reflect improvements in risk factor status since the 1960s, all-of-life health interventions, as well as better chronic disease management in the last two decades. The higher death rates in females than males in this community remain unexplained, but the rapid rate of decline of female death rates predicts that this gap will soon be minimised

Socioeconomic disparities in physical health among Aboriginal and Torres Strait Islander children in Western Australia

Objective. Few empirical studies have specifically examined the relationship between socio-economic status (SES) and health in Indigenous populations of Australia. We sought to provide insights into the nature of this relationship by examining socio-economic disparities in physical health outcomes among Aboriginal and Torres Strait Islander children in Western Australia. Design. We used a diverse set of health and SES indicators from a representative survey conducted in 20002002 on the health and development of 5289 Indigenous children aged 017 years in Western Australia. Analysis was conducted using multivariate logistic regression within a multilevel framework. Results. After controlling for age and sex, we found statistically significant socio- economic disparities in health in almost half of the associations that were investigated, although the direction, shape and magnitude of associations differed. For ear infections, recurring chest infections and sensory function problems, the patterns were generally consistent with a positive socio-economic gradient where better health was associated with higher SES. The reverse pattern was found for asthma, accidents and injuries, and oral health problems, although this was primarily observed for area-level SES indicators. Conclusion. Conventional notions of social position and class have some influence on the physical health of Indigenous children, although the diversity of results implies that there are other ways of conceptualising and measuring SES that are important for Indigenous populations. We need to consider factors that relate specifically to Indigenous circumstances and culture in the past and present day, and give more thought to how we measure social position in the Indigenous community, to gain a better understanding of the pathways from SES to Indigenous child health