Transition-metal 13-atom clusters assessed with solid and surface-biased functionals

First-principles density-functional theory studies have reported open structures based on the formation of double simple-cubic (DSC) arrangements for Ru(13), Rh(13), Os(13), and Ir(13), which can be considered an unexpected result as those elements crystallize in compact bulk structures such as the face-centered cubic and hexagonal close-packed lattices. In this work, we investigated with the projected augmented wave method the dependence of the lowest-energy structure on the local and semilocal exchange-correlation (xc) energy functionals employed in density-functional theory. We found that the local-density approximation (LDA) and generalized-gradient formulations with different treatment of the electronic inhomogeneities (PBE, PBEsol, and AM05) confirm the DSC configuration as the lowest-energy structure for the studied TM(13) clusters. A good agreement in the relative total energies are obtained even for structures with small energy differences, e. g., 0.10 eV. The employed xc functionals yield the same total magnetic moment for a given structure, i.e., the differences in the bond lengths do not affect the moments, which can be attributed to the atomic character of those clusters. Thus, at least for those systems, the differences among the LDA, PBE, PBEsol, and AM05 functionals are not large enough to yield qualitatively different results. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3577999]

The role of electron localization in the atomic structure of transition-metal 13-atom clusters: the example of Co(13), Rh(13), and Hf(13)

The crystalline structure of transition-metals (TM) has been widely known for several decades, however, our knowledge on the atomic structure of TM clusters is still far from satisfactory, which compromises an atomistic understanding of the reactivity of TM clusters. For example, almost all density functional theory (DFT) calculations for TM clusters have been based on local (local density approximation-LDA) and semilocal (generalized gradient approximation-GGA) exchange-correlation functionals, however, it is well known that plain DFT fails to correct the self-interaction error, which affects the properties of several systems. To improve our basic understanding of the atomic and electronic properties of TM clusters, we report a DFT study within two nonlocal functionals, namely, the hybrid HSE (Heyd, Scuseria, and Ernzerhof) and GGA + U functionals, of the structural and electronic properties of the Co(13), Rh(13), and Hf(13) clusters. For Co(13) and Rh(13), we found that improved exchange-correlation functionals decrease the stability of open structures such as the hexagonal bilayer (HBL) and double simple-cubic (DSC) compared with the compact icosahedron (ICO) structure, however, DFT-GGA, DFT-GGA + U, and DFT-HSE yield very similar results for Hf(13). Thus, our results suggest that the DSC structure obtained by several plain DFT calculations for Rh(13) can be improved by the use of improved functionals. Using the sd hybridization analysis, we found that a strong hybridization favors compact structures, and hence, a correct description of the sd hybridization is crucial for the relative energy stability. For example, the sd hybridization decreases for HBL and DSC and increases for ICO in the case of Co(13) and Rh(13), while for Hf(13), the sd hybridization decreases for all configurations, and hence, it does not affect the relative stability among open and compact configurations.

Bulk structures of PtO and PtO(2) from density functional calculations

Platinum plays an important role in catalysis and electrochemistry, and it is known that the direct interaction of oxygen with Pt surfaces can lead to the formation of platinum oxides (PtO(x)), which can affect the reactivity. To contribute to the atomistic understanding of the atomic structure of PtO(x), we report a density functional theory study of the atomic structure of bulk PtO(x) (1 <= x <= 2). From our calculations, we identified a lowest-energy structure (GeS type, space group Pnma) for PtO, which is 0.181 eV lower in energy than the structure suggested by W. J. Moore and L. Pauling [J. Am. Chem. Soc. 63, 1392 (1941)] (PtS type). Furthermore, two atomic structures were identified for PtO(2), which are almost degenerate in energy with the lowest-energy structure reported so far for PtO(2) (CaCl(2) type). Based on our results and analysis, we suggest that Pt and O atoms tend to form octahedron motifs in PtO(x) even at lower O composition by the formation of Pt-Pt bonds.

The accuracy of the Clock Drawing Test compared to that of standard screening tests for Alzheimer`s disease: results from a study of Brazilian elderly with heterogeneous educational backgrounds

Background: Although the Clock Drawing Test (CDT) is the second most used test in the world for the screening of dementia, there is still debate over its sensitivity specificity, application and interpretation in dementia diagnosis. This study has three main aims: to evaluate the sensitivity and specificity of the CDT in a sample composed of older adults with Alzheimer`s disease (AD) and normal controls; to compare CDT accuracy to the that of the Mini-mental State Examination (MMSE) and the Cambridge Cognitive Examination (CAMCOG), and to test whether the association of the MMSE with the CDT leads to higher or comparable accuracy as that reported for the CAMCOG. Methods: Cross-sectional assessment was carried out for 121 AD and 99 elderly controls with heterogeneous educational levels from a geriatric outpatient clinic who completed the Cambridge Examination for Mental Disorder of the Elderly (CAMDEX). The CDT was evaluated according to the Shulman, Mendez and Sunderland scales. Results: The CDT showed high sensitivity and specificity. There were significant correlations between the CDT and the MMSE (0.700-0.730; p < 0.001) and between the CDT and the CAMCOG (0.753-0.779; p < 0.001). The combination of the CDT with the MMSE improved sensitivity and specificity (SE = 89.2-90%; SP = 71.7-79.8%). Subgroup analysis indicated that for elderly people with lower education, sensitivity and specificity were both adequate and high. Conclusions: The CDT is a robust screening test when compared with the MMSE or the CAMCOG, independent of the scale used for its interpretation. The combination with the MMSE improves its performance significantly, becoming equivalent to the CAMCOG.

Surveillance Programme for Healthcare Associated Infections in the State of Sao Paulo, Brazil. Implementation and the first three years` results

Governmental programmes should be developed to collect and analyse data on healthcare associated infections (HAIs). This study describes the healthcare setting and both the implementation and preliminary results of the Programme for Surveillance of Healthcare Associated Infections in the State of Sao Paulo (PSHAISP), Brazil, from 2004 to 2006. Characterisation of the healthcare settings was carried out using a national database. The PSHAISP was implemented using components for acute care hospitals (ACH) or long term care facilities (LTCF). The components for surveillance in ACHs were surgical unit, intensive care unit and high risk nursery. The infections included in the surveillance were surgical site infection in clean surgery, pneumonia, urinary tract infection and device-associated bloodstream infections. Regarding the LTCF component, pneumonia, scabies and gastroenteritis in all inpatients were reported. In the first year of the programme there were 457 participating healthcare settings, representing 51.1% of the hospitals registered in the national database. Data obtained in this study are the initial results and have already been used for education in both surveillance and the prevention of HAI. The results of the PSHAISP show that it is feasible to collect data from a large number of hospitals. This will assist the State of Sao Paulo in assessing the impact of interventions and in resource allocation. (C) 2010 The Hospital Infection Society. Published by Elsevier Ltd. All rights reserved.

Double disruption of alpha(2A)- and alpha(2C)-adrenoceptors results in sympathetic hyperactivity and high-bone-mass phenotype

Evidence demonstrates that sympathetic nervous system (SNS) activation causes osteopenia via beta(2)-adrenoceptor (beta(2)-AR) signaling. Here we show that female mice with chronic sympathetic hyperactivity owing to double knockout of adrenoceptors that negatively regulate norepinephrine release, alpha(2A)-AR and alpha(2C)-AR(alpha(2A)/alpha(2C)-ARKO), present an unexpected and generalized phenotype of high bone mass with decreased bone resorption and increased formation. In alpha(2A)/alpha(2C)-ARKO versus wild-type (WT) mice, micro-computed tomographic (mu CT) analysis showed increased, better connected, and more plate-shaped trabeculae in the femur and vertebra and increased cortical thickness in the vertebra, whereas biomechanical analysis showed increased tibial and femoral strength. Tibial mRNA expression of tartrate-resistant acid phosphatase (TRACP) and receptor activator of NF-kappa B (RANK), which are osteoclast-related factors, was lower in knockout (KO) mice. Plasma leptin and brain mRNA levels of cocaine amphetamine-regulated transcript (CART), which are factors that centrally affect bone turnover, and serum levels of estradiol were similar between mice strains. Tibial beta(2)-AR mRNA expression also was similar in KO and WT littermates, whereas alpha(2A)-, alpha(2B)- and alpha(2C)-AR mRNAs were detected in the tibia of WT mice and in osteoblast-like MC3T3-E1 cells. By immunohistochemistry, we detected alpha(2A)-, alpha(2B)-, alpha(2C)- and beta(2)-ARs in osteoblasts, osteoclasts, and chondrocytes of 18.5-day-old mouse fetuses and 35-day-old mice. Finally, we showed that isolated osteoclasts in culture are responsive to the selective alpha(2)-AR agonist clonidine and to the nonspecific alpha-AR antagonist phentolamine. These findings suggest that beta(2)-AR is not the single adrenoceptor involved in bone turnover regulation and show that alpha(2)-AR signaling also may mediate the SNS actions in the skeleton. (c) 2011 American Society for Bone and Mineral Research.

Learning benefits of self-controlled knowledge of results in 10-year-old children

PIBIC-CNPq-Conselho Nacional de Desenvolvimento Cientifico e Technologico

An external focus of attention results in greater swimming speed

We examined effects of attentional focus on swimming speed. Participants` task was to swim one length of a pool (16 m) using the front crawl stroke. In Experiment 1, intermediate swimmers were given attentional focus instructions related to the crawl arm stroke or the leg kick, respectively. Participants were instructed to focus on ""pulling your hands back"" or ""pushing the instep down"" (internal focus), or on ""pushing the water back/down"" (external focus), respectively. Swim times were significantly shorter with an external focus. In Experiment 2, a control condition was included. Times were significantly faster in the external focus compared with both the internal focus and control conditions. These findings have implications for enhancing performance in swimming.

Relative frequency of knowledge of results and task complexity in the motor skill acqusition

The aim of this study was to investigate the effects of knowledge of results (KR) frequency and task complexity on motor skill acquisition. The task consisted of throwing a bocha ball to place it as close as possible to the target ball. 120 students ages 11 to 73 years were assigned to one of eight experimental groups according to knowledge of results frequency (25, 50, 75, and 100%) and task complexity (simple and complex). Subjects performed 90 trials in the acquisition phase and 10 trials in the transfer test. The results showed that knowledge of results given at a frequency of 25% resulted in an inferior absolute error than 50% and inferior variable error than 50, 75, and 100 I frequencies, but no effect of task complexity was found.

Effect of bandwidth knowledge of results on the learning of a grip force control task

An experiment was conducted to investigate the persistence of the effect of ""bandwidth knowledge of results (KR)"" manipulated during the learning phase of performing a manual force-control task. The experiment consisted of two phases, an acquisition phase with the goal of maintaining 60% maximum force in 30 trials, and a second phase with the objective of maintaining 40% of maximum force in 20 further trials. There were four bandwidths of KR: when performance error exceeded 5, 10, or 15% of the target, and a control group (0% bandwidth). Analysis showed that 5, 10, and 15% bandwidth led to better performance than 0% bandwidth KR at the beginning of the second phase and persisted during the extended trials.

Experimental results on the nonlinear H(infinity) control via quasi-LPV representation and game theory for wheeled mobile robots

In this paper, nonlinear dynamic equations of a wheeled mobile robot are described in the state-space form where the parameters are part of the state (angular velocities of the wheels). This representation, known as quasi-linear parameter varying, is useful for control designs based on nonlinear H(infinity) approaches. Two nonlinear H(infinity) controllers that guarantee induced L(2)-norm, between input (disturbances) and output signals, bounded by an attenuation level gamma, are used to control a wheeled mobile robot. These controllers are solved via linear matrix inequalities and algebraic Riccati equation. Experimental results are presented, with a comparative study among these robust control strategies and the standard computed torque, plus proportional-derivative, controller.

Cluster identification and characterization in the riser of a circulating fluidized bed from numerical simulation results

A methodology of identification and characterization of coherent structures mostly known as clusters is applied to hydrodynamic results of numerical simulation generated for the riser of a circulating fluidized bed. The numerical simulation is performed using the MICEFLOW code, which includes the two-fluids IIT`s hydrodynamic model B. The methodology for cluster characterization that is used is based in the determination of four characteristics, related to average life time, average volumetric fraction of solid, existing time fraction and frequency of occurrence. The identification of clusters is performed by applying a criterion related to the time average value of the volumetric solid fraction. A qualitative rather than quantitative analysis is performed mainly owing to the unavailability of operational data used in the considered experiments. Concerning qualitative analysis, the simulation results are in good agreement with literature. Some quantitative comparisons between predictions and experiment were also presented to emphasize the capability of the modeling procedure regarding the analysis of macroscopic scale coherent structures. (c) 2007 Elsevier Inc. All rights reserved.

Design of concrete-filled steel tubular columns under axial loading according to NBR 8800:2008 and Eurocode 4:2004: tests results and comparisons

In this paper results of tests on 32 concrete-filled steel tubular columns under axial load are reported. The test parameters were the concrete compressive strength, the column slenderness (L/D) and the wall thickness (t). The test results were compared with predictions from the codes NBR 8800:2008 and EN 1994-1-1:2004 (EC4). The columns were 3, 5, 7 and 10 length to diameter ratios (L/D) and were tested with 30MPa, 60MPa, 80MPa and 100MPa concrete compressive strengths. The results of ultimate strength predicted by codes showed good agreement with experimental results. The results of NBR 8800 code were the most conservative and the EC4 showed the best results, in mean, but it was not conservative for usual concrete-filled short columns.

Lifecycle assessment of fuel ethanol from sugarcane in Brazil

This paper presents the lifecycle assessment (LCA) of fuel ethanol, as 100% of the vehicle fuel, from sugarcane in Brazil. The functional unit is 10,000 km run in an urban area by a car with a 1,600-cm(3) engine running on fuel hydrated ethanol, and the resulting reference flow is 1,000 kg of ethanol. The product system includes agricultural and industrial activities, distribution, cogeneration of electricity and steam, ethanol use during car driving, and industrial by-products recycling to irrigate sugarcane fields. The use of sugarcane by the ethanol agribusiness is one of the foremost financial resources for the economy of the Brazilian rural area, which occupies extensive areas and provides far-reaching potentials for renewable fuel production. But, there are environmental impacts during the fuel ethanol lifecycle, which this paper intents to analyze, including addressing the main activities responsible for such impacts and indicating some suggestions to minimize the impacts. This study is classified as an applied quantitative research, and the technical procedure to achieve the exploratory goal is based on bibliographic revision, documental research, primary data collection, and study cases at sugarcane farms and fuel ethanol industries in the northeast of SA o pound Paulo State, Brazil. The methodological structure for this LCA study is in agreement with the International Standardization Organization, and the method used is the Environmental Design of Industrial Products. The lifecycle impact assessment (LCIA) covers the following emission-related impact categories: global warming, ozone formation, acidification, nutrient enrichment, ecotoxicity, and human toxicity. The results of the fuel ethanol LCI demonstrate that even though alcohol is considered a renewable fuel because it comes from biomass (sugarcane), it uses a high quantity and diversity of nonrenewable resources over its lifecycle. The input of renewable resources is also high mainly because of the water consumption in the industrial phases, due to the sugarcane washing process. During the lifecycle of alcohol, there is a surplus of electric energy due to the cogeneration activity. Another focus point is the quantity of emissions to the atmosphere and the diversity of the substances emitted. Harvesting is the unit process that contributes most to global warming. For photochemical ozone formation, harvesting is also the activity with the strongest contributions due to the burning in harvesting and the emissions from using diesel fuel. The acidification impact potential is mostly due to the NOx emitted by the combustion of ethanol during use, on account of the sulfuric acid use in the industrial process and because of the NOx emitted by the burning in harvesting. The main consequence of the intensive use of fertilizers to the field is the high nutrient enrichment impact potential associated with this activity. The main contributions to the ecotoxicity impact potential come from chemical applications during crop growth. The activity that presents the highest impact potential for human toxicity (HT) via air and via soil is harvesting. Via water, HT potential is high in harvesting due to lubricant use on the machines. The normalization results indicate that nutrient enrichment, acidification, and human toxicity via air and via water are the most significant impact potentials for the lifecycle of fuel ethanol. The fuel ethanol lifecycle contributes negatively to all the impact potentials analyzed: global warming, ozone formation, acidification, nutrient enrichment, ecotoxicity, and human toxicity. Concerning energy consumption, it consumes less energy than its own production largely because of the electricity cogeneration system, but this process is highly dependent on water. The main causes for the biggest impact potential indicated by the normalization is the nutrient application, the burning in harvesting and the use of diesel fuel. The recommendations for the ethanol lifecycle are: harvesting the sugarcane without burning; more environmentally benign agricultural practices; renewable fuel rather than diesel; not washing sugarcane and implementing water recycling systems during the industrial processing; and improving the system of gases emissions control during the use of ethanol in cars, mainly for NOx. Other studies on the fuel ethanol from sugarcane may analyze in more details the social aspects, the biodiversity, and the land use impact.

Methane generation in tropical landfills: Simplified methods and field results

This paper deals with the use of simplified methods to predict methane generation in tropical landfills. Methane recovery data obtained on site as part of a research program being carried Out at the Metropolitan Landfill, Salvador, Brazil, is analyzed and used to obtain field methane generation over time. Laboratory data from MSW samples of different ages are presented and discussed: and simplified procedures to estimate the methane generation potential, L(o), and the constant related to the biodegradation rate, k are applied. The first order decay method is used to fit field and laboratory results. It is demonstrated that despite the assumptions and the simplicity of the adopted laboratory procedures, the values L(o) and k obtained are very close to those measured in the field, thus making this kind of analysis very attractive for first approach purposes. (C) 2008 Elsevier Ltd. All rights reserved.