Density functional theory study on the activation of molecular oxygen on a stepped gold surface in an aqueous environment: a new approach for simulating reactions in solution

The activation of oxygen molecules is an important issue in the gold-catalyzed partial oxidation of alcohols in aqueous solution. The complexity of the solution arising from a large number of solvent molecules makes it difficult to study the reaction in the system. In this work, O-2 activation on an Au catalyst is investigated using an effective approach to estimate the reaction barriers in the presence of solvent. Our calculations show that O-2 can be activated, undergoing OOH* in the presence of water molecules. The OOH* can readily be formed on Au(211) via four possible pathways with almost equivalent free energy barriers at the aqueous-solid interface: the direct or indirect activation of O-2 by surface hydrogen or the hydrolysis of O-2 following a Langmuir-Hinshelwood mechanism or an Eley-Rideal mechanism. Among them, the Eley-Rideal mechanism may be slightly more favorable due to the restriction of the low coverage of surface H on Au(211) in the other mechanisms. The results shed light on the importance of water molecules on the activation of oxygen in gold-catalyzed systems. Solvent is found to facilitate the oxygen activation process mainly by offering extra electrons and stabilizing the transition states. A correlation between the energy barrier and the negative charge of the reaction center is found. The activation barrier is substantially reduced by the aqueous environment, in which the first solvation shell plays the most important role in the barrier reduction. Our approach may be useful for estimating the reaction barriers in aqueous systems.

“I still can’t question”: issues affecting EFL development in an immersion environment

This study examined the development of EFL proficiency in an immersion environment. Adult Chinese speakers of English were tested at the beginning and end of a ten-month period of immersion in the UK on their acquisition of English question forms using a timed grammaticality judgement task. Participants showed significantly faster response times after ten months, but no significant difference in accuracy of target-like judgements, suggesting that immersion benefits fluency more than accuracy.

Multi-scale sensible heat fluxes in the urban environment from large aperture scintillometry and eddy covariance

Sensible heat fluxes (QH) are determined using scintillometry and eddy covariance over a suburban area. Two large aperture scintillometers provide spatially integrated fluxes across path lengths of 2.8 km and 5.5 km over Swindon, UK. The shorter scintillometer path spans newly built residential areas and has an approximate source area of 2-4 km2, whilst the long path extends from the rural outskirts to the town centre and has a source area of around 5-10 km2. These large-scale heat fluxes are compared with local-scale eddy covariance measurements. Clear seasonal trends are revealed by the long duration of this dataset and variability in monthly QH is related to the meteorological conditions. At shorter time scales the response of QH to solar radiation often gives rise to close agreement between the measurements, but during times of rapidly changing cloud cover spatial differences in the net radiation (Q*) coincide with greater differences between heat fluxes. For clear days QH lags Q*, thus the ratio of QH to Q* increases throughout the day. In summer the observed energy partitioning is related to the vegetation fraction through use of a footprint model. The results demonstrate the value of scintillometry for integrating surface heterogeneity and offer improved understanding of the influence of anthropogenic materials on surface-atmosphere interactions.

CO2 emission estimation in the urban environment: measurement of the CO2 storage term

Eddy covariance has been used in urban areas to evaluate the net exchange of CO2 between the surface and the atmosphere. Typically, only the vertical flux is measured at a height 2–3 times that of the local roughness elements; however, under conditions of relatively low instability, CO2 may accumulate in the airspace below the measurement height. This can result in inaccurate emissions estimates if the accumulated CO2 drains away or is flushed upwards during thermal expansion of the boundary layer. Some studies apply a single height storage correction; however, this requires the assumption that the response of the CO2 concentration profile to forcing is constant with height. Here a full seasonal cycle (7th June 2012 to 3rd June 2013) of single height CO2 storage data calculated from concentrations measured at 10 Hz by open path gas analyser are compared to a data set calculated from a concurrent switched vertical profile measured (2 Hz, closed path gas analyser) at 10 heights within and above a street canyon in central London. The assumption required for the former storage determination is shown to be invalid. For approximately regular street canyons at least one other measurement is required. Continuous measurements at fewer locations are shown to be preferable to a spatially dense, switched profile, as temporal interpolation is ineffective. The majority of the spectral energy of the CO2 storage time series was found to be between 0.001 and 0.2 Hz (500 and 5 s respectively); however, sampling frequencies of 2 Hz and below still result in significantly lower CO2 storage values. An empirical method of correcting CO2 storage values from under-sampled time series is proposed.

Reactive nitrogen intermediate susceptibility of Mycobacterium tuberculosis genotypes in an urban setting

BACKGROUND: Mycobacterium tuberculosis genotypes resistant to reactive nitrogen intermediates (RNI) predominate in certain urban communities, suggesting that this phenotype influences disease transmission. OBJECTIVE: To compare different M. tuberculosis genotypes for resistance to RNI generated in vitro. DESIGN: We genotyped 420 M. tuberculosis isolates from a neighborhood in Sao Paulo, Brazil, and analyzed them for susceptibility to RNI generated in acidified sodium nitrite (ASN) solution. RESULTS: Seventy-one (43%) of 167 recent-infection strains and 68 (43%) of 158 endogenous infection strains showed moderate- to high-level ASN resistance. CONCLUSION: ASN resistance of M. tuberculosis is not necessarily a determining factor for enhanced transmission.

People, places and public health : evaluating the benefits of civic environmentalism in an urban local government context

Recent political, economic and social trends pose threats to the sustainability both of ecosystems and of human health. Australia’s environmental management record is poor, and while by international standards Australians enjoy good health, this is variable (AIHW, 2000). Within developed nations, heart disease, depression, alcohol dependence and stroke are major health issues (Mathers et al. 2002). In Australia, mental disorder is the number one contributor to the disease burden (Vos & Mathers 2000). Recent research has highlighted the role of social capital as a key determinant of health (Kawachi et al., 1997). Despite this, Putnam (1995) observes that social connectedness and civic engagement are in decline. People have less time for leisure and for volunteering, as many juggle paid work and caring for children. Anecdotal evidence suggests that engagement in civic environmentalism has human health benefits, relating to a combination of exposure to natural environments and increased social capital (Maller, Brown, Townsend & St. Leger, 2002). This link is supported by Furnass (1996) who defines well-being as including: satisfactory human relationships, meaningful occupation, opportunities for contact with nature, creative expression, and making a positive contribution to human society. Research conducted by Deakin University confirms the efficacy of linking people and places through civic environmentalism for addressing both ecosystem sustainability and human health and wellbeing. The research has included a pilot study to explore the human health benefits of membership of a local parkland ‘Friends’ group, and a more detailed follow-up study. The aims of the pilot study included:- To identify the range of motivations for joining the Friends group;- To document members’ perceptions of the benefits gained from membership of the group;- To assess the potential for Friends groups to be used as an ‘upstream’ health promotion measure.Face-to-face interviews were conducted with eleven members of a ‘Friends’ group in the eastern suburbs of Melbourne. Data was analysed thematically and key findings included:- Motivations: environmental; social; and pragmatic.- General benefits: community belonging; personal satisfaction; learning opportunities; physical activity; and better environment.- Health benefits: physical health; mental health; and social support. There was unanimous support for the use of ‘Friends’ groups as a tool for health promotion.The follow-up study, in the western suburbs of Melbourne, expanded on the pilot study by measuring the group’s social capital and by collecting self-report data on levels of health service usage. Data was collected through face-to-face interviews and a questionnaire. The findings were similar to the pilot study in relation to the motivations, benefits and the health promotion potential of such groups. However, health service usage data highlighted an apparent anomaly: while respondents perceived significant health benefits, some were nevertheless utilising health services at a relatively high level. This poses some questions requiring further exploration: Is this due to the poorer baseline health of the high health service usage members compared with their fellow members? Does involvement in the group offer health benefits that enable people who would otherwise be too unhealthy to participate in community groups to continue such involvement?If this is the case, then we may do well to look to locally-based mechanisms for promoting ecological sustainability as a tool also for promoting human health. Instead of prescribing a pill, connecting people and places through engagement with a local friends group may address our health problems at the same time as addressing local environmental problems.

Social support and infant malnutrition: a case-control study in an urban area of Southeastern Brazil

The relationship between malnutrition and social support was first suggested in the mid-1990s. Despite its plausibility, no empirical studies aimed at obtaining evidence of this association could be located. The goal of the present study was to investigate such evidence. A case-control study was carried out including 101 malnourished children (weight-for-age National Center for Health Statistics/WHO 5th percentile) aged 12-23 months, who were compared with 200 well-nourished children with regard to exposure to a series of factors related to their social support system. Univariate and multiple logistic regressions were carried out, odds ratios being adjusted for per capita family income, mother's schooling, and number of children. The presence of an interaction between income and social support variables was also tested. Absence of a partner living with the mother increased risk of malnutrition (odds ratio 2.4 (95 % CI 1.19, 4.89)), even after adjustment for per capita family income, mother's schooling, and number of children. The lack of economic support during adverse situations accounted for a very high risk of malnutrition (odds ratio 10.1 (95 % CI 3.48, 29.13)) among low-income children, but had no effect on children of higher-income families. Results indicate that receiving economic support is an efficient risk modulator for malnutrition among low-income children. In addition, it was shown that the absence of a partner living with the mother is an important risk factor for malnutrition, with an effect independent from per capita family income, mother's schooling, and number of children.

Phytoplankton primary productivity in an urban eutrophic reservoir (São Paulo, Brazil)

The aim of this study was to analyze temporal ..d vertical variation of the biomass and of phytoplankton primary productivity in an urban eutrophic reservoir, in relation to the physical and chemical characteristics of the water. The physical and chemical variables of the water were defined in the limnetic region of the reservoir, at depths of 0.0; 0.5; 1.0; 2.0; 3.0 and 4.0 meters. Three samples were taken to define both the physical and chemical variables, concomitantly with the biomass (chlorophyll-a and phaeophytin) and phytoplankton primary productivity (C-14 method). Based on data obtained on differences in depth of the mixture zone and the euphotic zone, it is hypothesised that, depending on the time of the year, phytoplankton is conditioned by differences in the light and nutrient regimes, which change according to the constant loads of nutrients thrown into the system. The highest concentration of chlorophyll-a in the photic zone of the limnetic region was observed in November 2000 (1,197.3 mg Chl L -1) and the lowest in November 1999 (94.0 mg ChI L -1), whereas the profiles of primary activity of phytoplankton presented the highest rates on the surface of the water column, with values varying from 84.7 (May 2000) to 1,376.7mg C m -3 h -1 (December 2000). Annual primary productivity was calculated at 1,567.0gC m -2y -1, considered euproductive. The primary productivity profiles reported in this study are typical of aquatic eutrophic systems, rich in plankton and with low light penetration. It can be stated that Garças Lake is a system that suffers from anthropogenic impact, through receiving large loads of organic pollution, reflecting on the physical and chemical characteristics of the water and on the high values of biomass and primary phytoplankton activity. © National Institute of Ecology, New Delhi.

Diversity of the KIR gene cluster in an urban Brazilian population

The activity of natural killer cells depends on the balance between activating and inhibitory signals coming from their receptors. Among these are the killer cell immunoglobulin-like receptors (KIR) that recognize specific HLA class I allotypes. Here we characterized KIR genetic diversity and their HLA ligands in the population of Curitiba, Parana State (n = 164), and compared it with other worldwide populations. The distribution of 2DL4 alleles was also analyzed. The Curitiba population did not differ significantly from European and Euro-descendant populations, but as an admixed population showed higher genetic diversity. We found 27 KIR profiles, many of them uncommon in European populations, in agreement with the elevated historically recent gene flow in the study population. The frequencies of KIR genes and their respective HLA ligands were distributed independently and none of the analyzed individuals lacked functional KIR-HLA ligand combinations. KIR gene frequencies of 33 worldwide populations were consistent with geographic and ethnic distribution, in agreement with demography being the major factor shaping the observed gene content diversity of the KIR locus.

Comparing remote sensing and ground-based methods of quantifying cover type and carbon storage in an urban forest

Understanding the canopy cover of an urban environment leads to better estimates of carbon storage and more informed management decisions by urban foresters. The most commonly used method for assessing urban forest cover type extent is ground surveys, which can be both timeconsuming and expensive. The analysis of aerial photos is an alternative method that is faster, cheaper, and can cover a larger number of sites, but may be less accurate. The objectives of this paper were (1) to compare three methods of cover type assessment for Los Angeles, CA: handdelineation of aerial photos in ArcMap, supervised classification of aerial photos in ERDAS Imagine, and ground-collected data using the Urban Forest Effects (UFORE) model protocol; (2) to determine how well remote sensing methods estimate carbon storage as predicted by the UFORE model; and (3) to explore the influence of tree diameter and tree density on carbon storage estimates. Four major cover types (bare ground, fine vegetation, coarse vegetation, and impervious surfaces) were determined from 348 plots (0.039 ha each) randomly stratified according to land-use. Hand-delineation was better than supervised classification at predicting ground-based measurements of cover type and UFORE model-predicted carbon storage. Most error in supervised classification resulted from shadow, which was interpreted as unknown cover type. Neither tree diameter or tree density per plot significantly affected the relationship between carbon storage and canopy cover. The efficiency of remote sensing rather than in situ data collection allows urban forest managers the ability to quickly assess a city and plan accordingly while also preserving their often-limited budget.

Patient satisfaction and nursing staff work satisfaction in an urban public teaching hospital

This study examined the level of patient satisfaction and nursing staff work satisfaction at an urban public hospital in the Southwestern United States. The primary objectives of this study were to determine: (1) the level of overall patient satisfaction and satisfaction with specific dimensions of hospital care; (2) the differences in patient satisfaction according to demographic characteristics (age, gender, ethnicity, and education completed) and predispositional factors (perceived health status, perceived level of pain, prior contact with the hospital, and hospital image) and the relative importance of each variable on patient satisfaction; (3) the level of overall work satisfaction and satisfaction with specific dimensions of work experienced by the medical/surgical nursing staff; (4) the differences in work satisfaction experienced by the nursing staff based on demographic variables (age, gender, ethnicity, and marital status) and professional factors (education completed, staff position, the number of years employed with the hospital, and number of years employed in nursing) and the relative importance of each variable on work satisfaction; and (5) to determine the effect of the nursing work milieu on patient and staff satisfaction.^ The study findings showed that patients experienced a moderate to low level of satisfaction with the dimensions of hospital care (admission process, daily care, information, nursing care, physician care, other hospital staff, living arrangements, and overall care). Of the eight dimensions of care, patients reported a relatively positive level of satisfaction (75 percent or better) with only one dimension: physician care. Ethnicity, perceived health status, and hospital image were significantly related to patient satisfaction. Hispanic patients, those who were in good health, and those who felt the hospital had a good image in their community were most satisfied with hospital care. Patients also reported areas of hospital care that needed the most improvement. Responses included: rude staff, better nursing care, and better communication.^ Findings from the nursing satisfaction survey indicated a low level of satisfaction with the dimensions of work (autonomy, pay, professional status, interaction, task requirements, and organizational policies). Only one dimension of work, professional status, received a mean satisfaction score in the positive range. Additionally, staff members were unanimously dissatisfied with their salaries. Frequently mentioned work-related problems reported by the staff included: staffing shortages, heavy patient loads. and excessive paperwork.^ The nursing milieu appeared to have had a significant effect on the satisfaction levels of patients nursing staff employees. The nursing staff were often short staffed, which increased the patient-to-nurse ratio. Consequently, patients did not receive the amount of attention and care they expected from the nursing staff. Crowded patient rooms allowed for little personal space and privacy. Dissatisfaction with living conditions served to influence patients' attitudes and satisfaction levels. These frustrations were often directed toward their primary caregivers, the nursing staff. Consequently, the nursing milieu appeared to directly affect and influence the satisfaction levels of both patients and staff. (Abstract shortened by UMI). ^

Pediatric asthma incidence in Texas and associations with ambient ozone levels in an urban area an analysis using Medicaid claims data

Few recent estimates of childhood asthma incidence exist in the literature, although the importance of incidence surveillance for understanding asthma risk factors has been recognized. Asthma prevalence, morbidity and mortality reports have repeatedly shown that low-income children are disproportionately impacted by the disease. The aim of this study was to demonstrate the utility of Medicaid claims data for providing statewide estimates of asthma incidence. Medicaid Analytic Extract (MAX) data for Texas children ages 0-17 enrolled in Medicaid between 2004 and 2007 were used to estimate incidence overall and by age group, gender, race and county of residence. A 13+ month period of continuous enrollment was required in order to distinguish incident from prevalent cases identified in the claims data. Age-adjusted incidence of asthma was 4.26/100 person-years during 2005-2007, higher than reported in other populations. Incidence rates decreased with age, were higher for males than females, differed by race, and tended to be higher in rural than urban areas. With this study, we were able to demonstrate the utility of MAX data for estimating asthma incidence, and create a dataset of incident cases to use in further analysis. ^ In subsequent analyses, we investigated a possible association between ambient air pollutants and incident asthma among Medicaid-enrolled children in Harris County Texas between 2005 and 2007. This population is at high risk for asthma, and living in an area with historically poor air quality. We used a time-stratified case-crossover design and conditional logistic regression to calculate odds ratios, adjusted for weather variables and aeroallergens, to assess the effect of increases in ozone, NO2 and PM2.5 concentrations on risk of developing asthma. Our results show that a 10 ppb increase in ozone was significantly associated with asthma during the warm season (May-October), with the strongest effect seen when a 6-day cumulative lag period was used to compute the exposure metric (OR=1.05, 95% CI, 1.02–1.08). Similar results were seen for NO2 and PM 2.5 (OR=1.07, 95% CI, 1.03–1.11 and OR=1.12, 95% CI, 1.03–1.22, respectively). PM2.5 also had significant effects in the cold season (November-April), 5-day cumulative lag: OR=1.11, 95% CI, 1.00–1.22. When compared with children in the lowest quartile of O3 exposure, the risk for children in the highest quartile was 20% higher. This study indicates that these pollutants are associated with newly-diagnosed childhood asthma in this low-income urban population, particularly during the summer months. ^

Teaching safety at a summer camp: Evaluation of a children's fire safety curriculum in an urban community setting

Objectives: The purpose of this study was to evaluate the effectiveness of the Danger Rangers Fire Safety Curriculum in increasing the fire safety knowledge of low-income, minority children in pre-kindergarten to third grade in Austin, TX during a summer day camp in 2007.^ Methods: Data was collected from child participants via teacher and researcher administered tests at pretest, posttest (immediately after the completion of the fire safety module), and at a 3 week follow-up to asses retention. In addition, a self-administered questionnaire was collected from parents pre- and post-intervention to assess home-related fire/burn risk factors. Paired t-tests were conducted using STATA 12.0 to evaluate pretest, posttest, and retention test mean scores as well as mean fire safety rules listed by grade group. McNemar's test was used to determine if there was a difference in fire-related risk factors as reported by the parents of the participants before and after the intervention. Only those who had paired data for the tests/surveys being compared were included in the analysis.^ Results: The first/second grade group and the third grade group scored significantly higher on fire safety knowledge on the posttest compared to the pretest (p<0.0001 for both groups). However, there was no significant change in knowledge scores for the pre-kindergarten to kindergarten group (p=0.14). Among the first/second grade group, knowledge levels did not significantly decline between the posttest and retention test (p=0.25). However, the third grade group had significantly lower fire safety knowledge scores on the retention test compared to the posttest (p<0.001). A similar increase was seen in the amount of fire safety rules listed after the intervention (p<0.0001 between pre and posttest for both the first/second grade and third grade groups), with no decline from the posttest to the retention test (p=0.50) for the first/second grade group, but a significant decline in the third grade group (p=0.001). McNemar's chi-square test showed a significant increase in the percentage of participants' parents reporting smoke detector testing on a regular basis and having a fire escape plan for their family after the intervention (p=0.01 and p<0.0001, respectively). However, there was no significant change in the frequency of reports of the child playing in the kitchen while the parent cooks or the house/apartment having a working smoke detector.^ Conclusion: We found that general fire safety knowledge improved and the number of specific fire safety rules increased among the first to third grade children who participated in the Danger Rangers fire safety program. However, it did not significantly increase general fire safety knowledge among the pre-k/k group. This study also showed that a program targeted towards children has the potential to influence familial risk factors by proxy. The Danger Rangers Fire Safety Curriculum should be further evaluated by conducting a randomized controlled trial, using valid measures that assess fire safety attitudes, beliefs, behaviors, as well as fire/burn related outcomes.^