Conversion of N2O to N2 on TiO2(1 1 0)

In this study, we examine the interaction of N₂O with TiO₂(1 1 0) in an effort to better understand the conversion of NO_x species to N₂ over TiO₂-based catalysts. The TiO₂(1 1 0) surface was chosen as a model system because this material is commonly used as a support and because oxygen vacancies on this surface are perhaps the best available models for the role of electronic defects in catalysis. Annealing TiO₂(1 1 0) in vacuum at high temperature (above about 800 K) generates oxygen vacancy sites that are associated with reduced surface cations (Ti³⁺ sites) and that are easily quantified using temperature programmed desorption (TPD) of water. Using TPD, X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS), we found that the majority of N₂O molecules adsorbed at 90 K on TiO₂(1 1 0) are weakly held and desorb from the surface at 130 K. However, a small fraction of the N₂O molecules exposed to TiO₂(1 1 0) at 90 K decompose to N₂ via one of two channels, both of which are vacancy-mediated. One channel occurs at 90 K, and results in N₂ ejection from the surface and vacancy oxidation. We propose that this channel involves N₂O molecules bound at vacancies with the O-end of the molecule in the vacancy. The second channel results from an adsorbed state of N₂O that decomposes at 170 K to liberate N₂ in the gas phase and deposit oxygen adatoms at non-defect Ti⁴⁺ sites. The presence of these O adatoms is clearly evident in subsequent water TPD measurements. We propose that this channel involves N₂O molecules that are bound at vacancies with the N-end of the molecule in the vacancy, which permits the O-end of the molecule to interact with an adjacent Ti⁴⁺ site. The partitioning between these two channels is roughly 1:1 for adsorption at 90 K, but neither is observed to occur for moderate N₂O exposures at temperatures above 200 K. EELS data indicate that vacancies readily transfer charge to N₂O at 90 K, and this charge transfer facilitates N₂O decomposition. Based on these results, it appears that the decomposition of N₂O to N₂ requires trapping of the molecule at vacancies and that the lifetime of the N₂O–vacancy interaction may be key to the conversion of N₂O to N₂.     

The volitional unit: a functional concept in cortico-motoneuronal connections in humans

AIM: The effect of breathing 100% oxygen on retinal and optic nerve head capillary blood flow in smokers and non-smokers was investigated using scanning laser Doppler flowmetry (SLDF) as a new non-invasive method to visualise and quantify ocular blood flow. METHOD: 10 eyes of 10 young healthy non-smoking volunteers (mean age 26 (SD 3) years) and nine eyes of nine young healthy smoking volunteers (mean age 26 (4) years) were investigated. All participants were asked not to smoke or consume caffeine containing drinks for at least 4 hours before the measurements. Blood flow measurements were performed before and after 100% oxygen was applied to the subjects through a mask over a period of 5 minutes (6 litres per minute). Juxtapapillary retinal and optic nerve head blood flow were determined in arbitrary units using SLDF representing a combination of laser Doppler flowmetry and a scanning laser system allowing visualisation and quantification of the retinal and optic nerve head blood flow. Blood flow was determined in an area of 100 microns x 100 microns. The level of carboxyhaemoglobin was determined in all subjects. A Wilcoxon matched pairs signed ranks test (non-parametric) was used for statistical evaluation. RESULTS: In the non-smoking group, retinal 'flow' was reduced by 33% (p = 0.005), optic nerve head 'flow' by 37% (p = 0.005). In the smoking group retinal flow was reduced by 10% (p = 0.01), optic nerve head flow by 13% (p < 0.008). The difference in reactivity to oxygen breathing between smokers and non-smokers was highly significant (p < 0.00001). Increased carboxyhaemoglobin levels were not found in either of the groups. A significant reduction of the mean arterial blood pressure of 6% (5%) (p < 0.02) was observed in the non-smoking group after administration of oxygen. CONCLUSION: These results indicate that hyperoxia leads to a decrease in capillary blood flow of the retina and optic nerve head secondary to vasoconstriction, and that smokers do not respond to oxygen breathing as non-smokers do. The findings might be based on factors such as long term effects of nicotine on the sympathetic and parasympathetic nervous system.     

Incentive effects of workers' compensation

Economic theory and evidence indicate that workers, employers, and healthcare personnel respond to the incentives built into state workers' compensation systems. Although empirical studies cannot provide precise estimates of the quantitative effects resulting from specific policy changes, research is useful in evaluating the qualitative effects of alternative policies. Studies show that workers' compensation claims are higher the more generous the level of benefits, the shorter the waiting period, and the more readily available is information on benefits to workers. States that decrease real benefit levels and lengthen the period required before workers are compensated for lost earnings can constrain future growth in workers' compensation costs, while continuing to provide partial compensation for workers with the most serious injuries. The most difficult problem facing policymakers is to design and implement reforms that take into account what are often the incompatible incentives of workers, employers, and medical care providers.     

Object identification in context: The visual processing of natural scenes.

Summarizes the research on the visual processing of natural scenes and describes the schema hypothesis (SH). The SH proposes that the semantic category of a scene is quickly apprehended and that predictions about objects from the scene category are then used to facilitate subsequent object identification. Both empirical and theoretical reasons are presented for remaining cautious about the SH. An alternative explanation is presented for the scene results: the local-processing hypothesis (LPH). The central assumptions of the LPH are that object identification is an informational encapsulated module and that attention must be oriented to individual objects for those objects to be identified. The author indicates how the results from previous scene processing studies can be accommodated by the LPH. (French abstract) (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Breast cancer among women exposed to polybrominated biphenyls

We conducted a nested case-control study with 1,925 women enrolled in a polybrominated biphenyl (PBB) registry to examine the association between breast cancer and serum PBBs. Twenty women who developed breast cancer were matched to 290 control subjects on sex, race, and age. Women with serum PBB levels of 2.0-3.0 parts per billion (ppb) [odds ratio (OR) = 3.5; 95% confidence interval (CI) = 0.9-13] or 4.0 ppb or greater (OR = 3.1; 95% CI = 0.8-12) had a higher estimated risk for breast cancer than women with less than 2.0 ppb. The odds ratios were unchanged when available breast cancer risk factors were included in the analysis.     

Ketoconazole and other imidazole derivatives are potent inhibitors of peroxisomal phytanic acid alpha-oxidation

Twelve young adults were treated with either melatonin, 3 mg or 6 mg, or placebo, at two different times before an early evening nap (18.00-20.00 h) according to a balanced double-blind Latin square design. Polysomnographic monitoring revealed that both dosages of melatonin significantly shortened sleep latency and increased total sleep time in comparison to placebo, irrespective of the time of administration. Subjects also tended to assess their sleep as 'deeper' after melatonin treatment. Based on previous data and the present results, it was concluded that exogenous melatonin exerts hypnotic effects only when circulating levels of endogenous melatonin are low.