Theory of nitride oxide adsorption on transition metal (111) surfaces: a first-principles investigation

In this work, we report a density functional theory study of nitric oxide (NO) adsorption on close-packed transition metal (TM) Rh(111), Ir(111), Pd(111) and Pt(111) surfaces in terms of adsorption sites, binding mechanism and charge transfer at a coverage of Theta(NO) = 0.25, 0.50, 0.75 monolayer (ML). Based on our study, an unified picture for the interaction between NO and TM(111) and site preference is established, and valuable insights are obtained. At low coverage (0.25 ML), we find that the interaction of NO/TM(111) is determined by an electron donation and back-donation process via the interplay between NO 5 sigma/2 pi* and TM d-bands. The extent of the donation and back-donation depends critically on the coordination number (adsorption sites) and TM d-band filling, and plays an essential role for NO adsorption on TM surfaces. DFT calculations shows that for TMs with high d-band filling such as Pd and Pt, hollow-site NO is energetically the most favorable, and top-site NO prefers to tilt away from the normal direction. While for TMs with low d-band filling (Rh and Ir), top-site NO perpendicular to the surfaces is energetically most favorable. Electronic structure analysis show that irrespective of the TM and adsorption site, there is a net charge transfer from the substrate to the adsorbate due to overwhelming back-donation from the TM substrate to the adsorbed NO molecules. The adsorption-induced change of the work function with respect to bare surfaces and dipole moment is however site dependent, and the work function increases for hollow-site NO, but decreases for top-site NO, because of differences in the charge redistribution. The interplay between the energetics, lateral interaction and charge transfer, which is element dependent, rationalizes the structural evolution of NO adsorption on TM(111) surfaces in the submonolayer regime.

Spatio-temporal patterns of throughfall and solute deposition in an open tropical rain forest

The brief interaction of precipitation with a forest canopy can create a high spatial variability of both throughfall and solute deposition. We hypothesized that (i) the variability in natural forest systems is high but depends on system-inherent stability, (ii) the spatial variability of solute deposition shows seasonal dynamics depending on the increase in rainfall frequency, and (iii) spatial patterns persist only in the short-term. The study area in the north-western Brazilian state of Rondonia is subject to a climate with a distinct wet and dry season. We collected rain and throughfall on an event basis during the early wet season (n = 14) and peak of the wet season (n = 14) and analyzed the samples for pH and concentrations of NH4+, Na+, K+, Ca2+ Mg2+,, Cl-, NO3-, SO42- and DOC. The coefficient 3 4 cient of variation for throughfall based on both sampling intervals was 29%, which is at the lower end of values reported from other tropical forest sites, but which is higher than in most temperate forests. Coefficients of variation of solute deposition ranged from 29% to 52%. This heterogeneity of solute deposition is neither particularly high nor particularly tow compared with a range of tropical and temperate forest ecosystems. We observed an increase in solute deposition variability with the progressing wet season, which was explained by a negative correlation between heterogeneity of solute deposition and antecedent dry period. The temporal stability of throughfall. patterns was Low during the early wet season, but gained in stability as the wet season progressed. We suggest that rapid plant growth at the beginning of the rainy season is responsible for the lower stability, whereas less vegetative activity during the later rainy season might favor the higher persistence of ""hot"" and ""cold"" spots of throughfall. quantities. The relatively high stability of throughfall patterns during later stages of the wet season may influence processes at the forest floor and in the soil. Solute deposition patterns showed less clear trends but all patterns displayed a short-term stability only. The weak stability of those patterns is apt to impede the formation of solute deposition -induced biochemical microhabitats in the soil. (C) 2008 Elsevier B.V. All rights reserved.

Elderly online: Effects of a digital inclusion program in cognitive performance

There is little empirical data about the impact of digital inclusion on cognition among older adults. This paper aimed at investigating the effects of a digital inclusion program in the cognitive performance of older individuals who participated in a computer learning workshop named ""Idosos On-Line`` (Elderly Online). Forty-two aged individuals participated in the research study: 22 completed the computer training workshop and 20 constituted the control group. All subjects answered a sociodemographic questionnaire and completed the Addenbrooke`s cognitive examination, revised (ACE-R), which examines five cognitive domains: orientation and attention, memory, verbal fluency, language, and visuo-spatial skills. It was noted that the experimental group`s cognitive performance significantly improved after the program, particularly in the language and memory domains, when compared to the control group. These findings suggest that the acquisition of new knowledge and the use of a new tool, that makes it possible to access the Internet, may bring gains to cognition. (C) 2010 Elsevier Ireland Ltd. All rights reserved.

DFT and electrochemical studies on nortriptyline oxidation sites

A study on the possible sites of oxidation and epoxidation of nortriptyline was performed using electrochemical and quantum chemical methods; these sites are involved in the biological responses (for example, hepatotoxicity) of nortriptyline and other similar antidepressants. Quantum chemical studies and electrochemical experiments demonstrated that the oxidation and epoxidation sites are located on the apolar region of nortriptyline, which will useful for understanding the molecule`s activity. Also, for the determination of the compound in biological fluids or in pharmaceutical formulations, we propose a useful analytical methodology using a graphite-polyurethane composite electrode, which exhibited the best performance when compared with boron-doped diamond or glassy carbon surfaces.

EFFECTS OF 14-WEEK SWIMMING TRAINING PROGRAM ON THE PSYCHOLOGICAL, HORMONAL, AND PHYSIOLOGICAL PARAMETERS OF ELITE WOMEN ATHLETES

Santhiago, V, da Silva, ASR, Papoti, M, and Gobatto, CA. Effects of 14-week swimming training program on the psychological, hormonal, and physiological parameters of elite women athletes. J Strength Cond Res 25(3): 825-832, 2011-The purpose of the study was to investigate the influence of a 14-week swimming training program on psychological, hormonal, and performance parameters of elite women swimmers. Ten Olympic and international-level elite women swimmers were evaluated 4 times along the experiment (i.e., in T1, T2, T3, and T4). On the first day at 8: 00 AM, before the blood collecting at rest for the determination of hormonal parameters, the athletes had their psychological parameters assessed by the profile of mood-state questionnaire. At 3: 00 AM, the swimmers had their anaerobic threshold assessed. On the second day at 3: 00 AM, the athletes had their alactic anaerobic performance measured. Vigor score and testosterone levels were lower (p <= 0.05) in T4 compared with T3. In addition, the rate between the peak blood lactate concentration and the median velocity obtained in the alactic anaerobic performance test increased in T4 compared with T3 (p < 0.05). For practical applications, the swimming coaches should not use a tapering with the present characteristics to avoid unexpected results.

RESPONSES OF HEMATOLOGICAL PARAMETERS AND AEROBIC PERFORMANCE OF ELITE MEN AND WOMEN SWIMMERS DURING A 14-WEEK TRAINING PROGRAM

Santhiago, V, da Silva, ASR, Papoti, M, and Gobatto, CA. Responses of hematological parameters and aerobic performance of elite men and women swimmers during a 14-week training program. J Strength Cond Res 23(4): 1097-1105, 2009-The main purpose of the present investigation was to verify the responses of hematological parameters in men and women competitive swimmers during a 14-week training program. Twenty-three Olympic and international athletes were evaluated 4 times during the experiment: at the beginning of the endurance training phase (T1), at the end of the endurance training phase (T2), at the end of the quality phases (T3), and at the end of the taper period (T4). On the first day at 8:00 AM, each swimmer had a blood sample taken for the determination of hematological parameters. At 3:00 PM, the athletes had their aerobic performance measured by anaerobic threshold. On the second day at 8: 00 AM, the swimmers had their aerobic performance measured by critical velocity. Hematocrit and mean corpuscular volume diminished (p <= 0.05) from T1 to T2 (men: 5.8 and 7.2%; women: 11.6 and 6.8%), and increased (p <= 0.05) from T2 to T3 (men: 7.2 and 6.0%; women: 7.4 and 5.2%). These results were related to the plasma volume changes of the athletes. However, these alterations do not seem to affect the swimmers` aerobic performance. For practical applications, time-trial performance is better than aerobic performance (i.e., anaerobic threshold and critical velocity) for monitoring training adaptations.

Friere`s Dialogic Concept Enables Family Health Program Teams to Incorporate Health Promotion

Objective The study analyzes the possibility of incorporating health promotion measures into the work processes of Family Health Program teams at a primary health care clinic in Brazil. Design and Sample We used the participatory research concept developed in 1968 by Freire. The study sample comprised the end-users of the health care system, together with 3 multidisciplinary teams. A total of 77 health care users and 55 health professionals participated in the study. Measures Culture circles composed of health care professionals, and users from different areas investigated generative topics, encoded/decoded topics, and engaged in critical probing for clarification. Topics affecting quality of life and health were heuristically evaluated. Results Although most topics were related to changing the focus of health care facilities, some were related to subsidizing community-based interventions, improving environmental strategies, individual skills, and public policies. Incorporating the novel health promotion measures and creating an expanded full-treatment clinic are important steps toward that goal. Conclusions Topics that can stimulate dialogue among the members of the culture circles include creating an environment of closer cultural contact, with repercussions for work processes, family health models, and general health models, as well as the inclusion of social aspects in the decision-making processes related to health issues that affect the living conditions of the population.

Defining Nutrient and Biochemical Oxygen Demand Baselines for Tropical Rivers and Streams in So Paulo State (Brazil): A Comparison Between Reference and Impacted Sites

Determining reference concentrations in rivers and streams is an important tool for environmental management. Reference conditions for eutrophication-related water variables are unavailable for Brazilian freshwaters. We aimed to establish reference baselines for So Paulo State tropical rivers and streams for total phosphorus (TP) and nitrogen (TN), nitrogen-ammonia (NH(4) (+)) and Biochemical Oxygen Demand (BOD) through the best professional judgment and the trisection methods. Data from 319 sites monitored by the So Paulo State Environmental Company (2005 to 2009) and from the 22 Water Resources Management Units in So Paulo State were assessed (N = 27,131). We verified that data from different management units dominated by similar land cover could be analyzed together (Analysis of Variance, P = 0.504). Cumulative frequency diagrams showed that industrialized management units were characterized by the worst water quality (e.g. average TP of 0.51 mg/L), followed by agricultural watersheds. TN and NH(4) (+) were associated with urban percentages and population density (Spearman Rank Correlation Test, P < 0.05). Best professional judgment and trisection (median of lower third of all sites) methods for determining reference concentrations showed agreement: 0.03 & 0.04 mg/L (TP), 0.31 & 0.34 mg/L (TN), 0.06 & 0.10 mg-N/L (NH(4) (+)) and 2 & 2 mg/L (BOD), respectively. Our reference concentrations were similar to TP and TN reference values proposed for temperate water bodies. These baselines can help with water management in So Paulo State, as well as providing some of the first such information for tropical ecosystems.

Spectral characteristics of atrial electrograms in sinus rhythm correlates with sites of ganglionated plexuses in patients with paroxysmal atrial fibrillation

Aims To verify whether spectral components of atrial electrograms (AE) during sinus rhythm (SR) correlate with cardiac ganglionated plexus (GP) sites. Methods and results Thirteen patients undergoing atrial fibrillation (AF) ablation were prospectively enrolled. Prior to radio frequency application, endocardial AE were recorded with a sequential point-by-point approach. Electrical stimuli were delivered at 20 Hz, amplitude 100 V, and pulse width of 4 ms. A vagal response was defined as a high-frequency stimulation (HFS) evoked atrioventricular block or a prolongation of RR interval. Spectral analysis was performed on single AE during SR, sampling rate of 1000 Hz, Hanning window. Overall, 1488 SR electrograms were analysed from 186 different left atrium sites, 129 of them corresponding to negative vagal response sites, and 57 to positive response sites. The electrogram duration and the number of deflections were similar in positive and negative response sites. Spectral power density of sites with vagal response was lower between 26 and 83 Hz and higher between 107 and 200 Hz compared with negative response sites. The area between 120 and 170 Hz normalized to the total spectrum area was tested as a diagnostic parameter. Receiver operating characteristic curve analysis demonstrated that an area120-170/area(total) value >0.14 identified vagal sites with 70.9% sensitivity and 72.1% specificity. Conclusion Spectral analysis of AE during SR in sites that correspond to the anatomical location of the GP is feasible and may be a simpler method of mapping the cardiac autonomic nervous system, compared with the HFS technique.

Using a New Criterion to Identify Sites for Mean Soil Water Storage Evaluation

Establishing a few sites in which measurements of soil water storage (SWS) are time stable significantly reduces the efforts involved in determining average values of SWS. This study aimed to apply a new criterion the mean absolute bias error (MABE)-to identify temporally stable sites for mean SWS evaluation. The performance of MABE was compared with that of the commonly used criterion, the standard deviation of relative difference (SDRD). From October 2004 to October 2008, SWS of four soil layers (0-1.0, 1.0-2.0,2.0-3.0, and 3.0-4.0 m) was measured, using a neutron probe, at 28 sites on a hillslope of the Loess Plateau, China. A total of 37 SWS data sets taken over time were divided into two subsets, the first consisting of 22 dates collected during the calibration period from October 2004 to September 2006, and the second with 15 dates collected during the validation period from October 2006 to October 2008. The results showed that if a critical value of 5% for MABE was defined, more than half the sites were temporally stable for both periods, and the number of temporally stable sires generally increased with soil depth. Compared with SDRD, MABE was more suitable for the identification of time-stable sites for mean SS prediction. Since the absolute prediction error of drier sites is more sensitive to changes in relative difference in terms of mean SWS prediction, the sites of wet sectors should be preferable for mean SWS prediction for the same changes in relative difference.

Do Terrestrial Tank Bromeliads in Brazil Create Safe Sites for Palm Establishment or Act as Natural Traps for Its Dispersed Seeds ?

This study shows for the first time that terrestrial tank bromeliads from Brazilian restinga can act as natural traps for dispersed palm Euterpe edulis seeds. Such bromeliads, which are shade intolerant, gain benefits by limiting palm recruitment since they hinder canopy formation and, consequently, increase luminosity over its aggregates.

Sites of Defoliation by Atta sexdens rubropilosa (Hymenoptera, Formicidae) in Artificial Plants

This study aimed to achieve a better understanding about the foraging behavior of leaf-cutter ant (Atta sexdens rubropilosa Forel) workers with respect to defoliation sites in plants. To accomplish that, artificial plants 70 cm in height were prepared and divided into four levels (heights), having natural plant leaves attached to them. Evaluations during the bioassays included the number of leaves dropped by the ants, as well as the percentage of plant mass removed. In all replicates, it became evident that the most exploited plant site is the apical region, which significantly differed from other plant levels.

Cyclophosphamide levels in sites of preparation and administration of antineoplastic drugs

The extensive use of antineoplastic agents in chemotherapy may be at risk to health care workers involved in the preparation and administration of these drugs. In this study cyclophosphamide, a drug classified as a human carcinogen, was quantified by adapting a previous analytical method using gas chromatography coupled to mass spectrometry (GC-MS) after solid phase extraction with diatomaceous earth. The drug was measured by analysis in surfaces (wipe samples) and gloves, collected from four different hospitals, before and after the practice of cleaning procedures, and the use of a closed-system device for the preparation and administration. Validation results were satisfactory and cyclophosphamide levels ranging from below the quantification limit to 141000 ng. Our findings demonstrated that surfaces and materials contamination was found in all hospitals during the traditional open technique for preparation and administration of cyclophosphamide and a significant reduction in contamination when a closed-system device was used. However, some values were considered unexpected, especially those obtained from samples collected after the cleaning surfaces.

The introduction of the Salmonella/microsome mutagenicity assay in a groundwater monitoring program

The objective of this study was to verify the possible inclusion of the Salmonella/microsome mutagenicity assay in a groundwater monitoring program as a complementary assay to assess water quality. Groundwater samples belonging to seven wells from different types of aquifers were analyzed. Three different methods for sample preparation were used: membrane filtration; liquid-liquid and XAD-4 extraction. The filtered samples were tested using TA98, TA100, YG1041 and YG1042 and the water extracts only with TA98 and TA100. No mutagenic activity was observed in any of the 16 filtered samples tested. Out of the 10 samples analyzed using XAD-4 extraction, five showed mutagenic activity with potency ranging from 130 to 1500 revertants/L. Concerning the liquid-liquid extraction, from the 11 samples analyzed, 3 showed mutagenicity. The XAD-4 extraction was the most suitable sample preparation. TA98 without S9 was found to be the most sensitive testing condition. The wells presenting water samples with mutagenic activity belonged to unconfined aquifers, which are more vulnerable to contamination. The data suggest that Salmonella/microsome assay can be used as an efficient screening tool to monitor groundwater for mutagenic activity. (C) 2009 Elsevier B.V. All rights reserved.

Generation and Analysis of Interaction Energy Maps of p-Substituted Benzoic Acid [(5-Nitro-thiophen-2-yl)-methylene]-Hydrazides Active against MRSA

In this preliminary study eighteen p-substituted benzoic acid [(5-nitro-thiophen-2-yl)-methylene]-hydrazides with antimicrobial activity were evaluated against multidrug-resistant Staphylococcus aureus, correlating the three-dimensional characteristics of the ligands with their respective bioactivities. The computer programs Sybyl and CORINA were used, respectively, for the design and three-dimensional conversion of the ligands. Molecular interaction fields were calculated using GRID program. Calculations using Volsurf resulted in a statistically consistent model with 48 structural descriptors showing that hydrophobicity is a fundamental property in the analyzed biological response.