Mn, Cu, and Zn abundances in barium stars and their correlations with neutron capture elements

Barium stars are optimal sites for studying the correlations between the neutron-capture elements and other species that may be depleted or enhanced, because they act as neutron seeds or poisons during the operation of the s-process. These data are necessary to help constrain the modeling of the neutron-capture paths and explain the s-process abundance curve of the solar system. Chemical abundances for a large number of barium stars with different degrees of s-process excesses, masses, metallicities, and evolutionary states are a crucial step towards this goal. We present abundances of Mn, Cu, Zn, and various light and heavy elements for a sample of barium and normal giant stars, and present correlations between abundances contributed to different degrees by the weak-s, mains, and r-processes of neutron capture, between Fe-peak elements and heavy elements. Data from the literature are also considered in order to better study the abundance pattern of peculiar stars. The stellar spectra were observed with FEROS/ESO. The stellar atmospheric parameters of the eight barium giant stars and six normal giants that we analyzed lie in the range 4300 < T(eff)/K < 5300, -0.7 < [Fe/H] <= 0.12 and 1.5 <= log g < 2.9. Carbon and nitrogen abundances were derived by spectral synthesis of the molecular bands of C(2), CH, and CN. For all other elements we used the atomic lines to perform the spectral synthesis. A very large scatter was found mainly for the Mn abundances when data from the literature were considered. We found that [Zn/Fe] correlates well with the heavy element excesses, its abundance clearly increasing as the heavy element excesses increase, a trend not shown by the [Cu/Fe] and [Mn/Fe] ratios. Also, the ratios involving Mn, Cu, and Zn and heavy elements usually show an increasing trend toward higher metallicities. Our results suggest that a larger fraction of the Zn synthesis than of Cu is owed to massive stars, and that the contribution of the main-s process to the synthesis of both elements is small. We also conclude that Mn is mostly synthesized by SN Ia, and that a non-negligible fraction of the synthesis of Mn, Cu, and Zn is owed to the weak s-process.

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]

Isotopic view of vegetation and carbon and nitrogen cycles in a cerrado ecosystem, southeastern Brazil

Carbon and nitrogen biogeochemical cycles in savannas are strongly regulated by the seasonal distribution of precipitation and pulses of nutrients released during the wetting of the dry soil and are critical to the dynamics of microorganisms and vegetation. The objective of this study was to investigate the spatial and temporal variability of C and N isotope ratios as indicators of the cycling of these elements in a cerrado sensu stricto area, within a protected area in a State Park in the state of São Paulo, Brazil. The foliar δ13C and δ15N values varied from -33.6 to -24.4 ‰ and -2.5 to 4.5 ‰, respectively. The δ13C values showed a consistent relationship with canopy height, revealing the importance of structure of the canopy over the C isotopic signature of the vegetation. Carbon isotopic variations associated with the length of the dry season indicated the importance of recent fixed C to the integrated isotopic signature of the leaf organic C. The studied Cerrado species showed a depleted foliar δ15N, but a wide range of foliar Nitrogen with no difference among canopy heights. However, seasonal variability was observed, with foliar δ15N values being higher in the transition period between dry and rainy seasons. The variation of the foliar C and N isotope ratios presented here was consistent with highly diverse vegetation with high energy available but low availability of water and N.

Absorption of metals and characterization of chemical elements present in three species of Gracilaria (Gracilariaceae) Greville: a genus of economical importance

Gracilaria Greville is a genus of seaweed that is economically explored by the cosmetic, pharmaceutical and food industries. One of the biggest problems associated with growing Gracilaria is the discharge of heavy metals into the marine environment. The absorption of heavy metals was investigated with the macroalga Gracilaria tenuistipitata Zhang et Xia, cultivated in a medium containing copper (Cu) and cadmium (Cd). In biological samples, EC50 concentrations of 1 ppm for cadmium and 0.95 ppm for copper were used. These concentrations were based on seaweed growth curves obtained over a period of six days in previous studies. ICP-AES was used to determine the amount of metal that seaweeds absorbed during this period. G. tenuistipitata was able to bioaccumulate both metals, about 17% of copper and 9% of cadmium. Basal natural levels of Cu were found in control seaweeds and in G. tenuistipitata exposed to Cd. In addition, the repertoire of other important chemical elements, as well as their concentrations, was determined for G. tenuistipitata and two other important seaweeds, G. birdiae Plastino & Oliveira and G. domingensis (Kützing) Sonder ex Dickie, collected in natural environments on the Brazilian shore.

Essential regulatory elements for NHE3 gene transcription in renal proximal tubule cells

The objectives of the present study were to identify the cis-elements of the promoter absolutely required for the efficient rat NHE3 gene transcription and to locate positive and negative regulatory elements in the 5’-flanking sequence (5’FS), which might modulate the gene expression in proximal tubules, and to compare this result to those reported for intestinal cell lines. We analyzed the promoter activity of different 5’FS segments of the rat NHE3 gene, in the OKP renal proximal tubule cell line by measuring the activity of the reporter gene luciferase. Because the segment spanning the first 157 bp of 5’FS was the most active it was studied in more detail by sequential deletions, point mutations, and gel shift assays. The essential elements for gene transcription are in the region -85 to -33, where we can identify consensual binding sites for Sp1 and EGR-1, which are relevant to NHE3 gene basal transcription. Although a low level of transcription is still possible when the first 25 bp of the 5’FS are used as promoter, efficient transcription only occurs with 44 bp of 5’FS. There are negative regulatory elements in the segments spanning -1196 to -889 and -467 to -152, and positive enhancers between -889 and -479 bp of 5’FS. Transcription factors in the OKP cell nuclear extract efficiently bound to DNA elements of rat NHE3 promoter as demonstrated by gel shift assays, suggesting a high level of similarity between transcription factors of both species, including Sp1 and EGR-1.

Analyzing the n→π* Electronic Transition of Formaldehyde in Water. A Sequential Monte Carlo/Time-Dependent Density Functional Theory

The n→π* absorption transition of formaldehyde in water is analyzed using combined and sequential classical Monte Carlo (MC) simulations and quantum mechanics (QM) calculations. MC simulations generate the liquid solute-solvent structures for subsequent QM calculations. Using time-dependent density functional theory in a localized set of gaussian basis functions (TD-DFT/6-311++G(d,p)) calculations are made on statistically relevant configurations to obtain the average solvatochromic shift. All results presented here use the electrostatic embedding of the solvent. The statistically converged average result obtained of 2300 cm-1 is compared to previous theoretical results available. Analysis is made of the effective dipole moment of the hydrogen-bonded shell and how it could be held responsible for the polarization of the solvent molecules in the outer solvation shells.

Transition to complete synchronization in phase-coupled oscillators with nearest neighbor coupling

We investigate synchronization in a Kuramoto-like model with nearest neighbor coupling. Upon analyzing the behavior of individual oscillators at the onset of complete synchronization, we show that the time interval between bursts in the time dependence of the frequencies of the oscillators exhibits universal scaling and blows up at the critical coupling strength. We also bring out a key mechanism that leads to phase locking. Finally, we deduce forms for the phases and frequencies at the onset of complete synchronization.

Ventilation behavior in trained and untrained men during incremental test: evidence of one metabolic transition point

This study aimed to describe and compare the ventilation behavior during an incremental test utilizing three mathematical models and to compare the feature of ventilation curve fitted by the best mathematical model between aerobically trained (TR) and untrained ( UT) men. Thirty five subjects underwent a treadmill test with 1 km.h(-1) increases every minute until exhaustion. Ventilation averages of 20 seconds were plotted against time and fitted by: bi-segmental regression model (2SRM); three-segmental regression model (3SRM); and growth exponential model (GEM). Residual sum of squares (RSS) and mean square error (MSE) were calculated for each model. The correlations between peak VO2 (VO2PEAK), peak speed (Speed(PEAK)), ventilatory threshold identified by the best model (VT2SRM) and the first derivative calculated for workloads below (moderate intensity) and above (heavy intensity) VT2SRM were calculated. The RSS and MSE for GEM were significantly higher (p < 0.01) than for 2SRM and 3SRM in pooled data and in UT, but no significant difference was observed among the mathematical models in TR. In the pooled data, the first derivative of moderate intensities showed significant negative correlations with VT2SRM (r = -0.58; p < 0.01) and Speed(PEAK) (r = -0.46; p < 0.05) while the first derivative of heavy intensities showed significant negative correlation with VT2SRM (r = -0.43; p < 0.05). In UT group the first derivative of moderate intensities showed significant negative correlations with VT2SRM (r = -0.65; p < 0.05) and Speed(PEAK) (r = -0.61; p < 0.05), while the first derivative of heavy intensities showed significant negative correlation with VT2SRM (r= -0.73; p < 0.01), Speed(PEAK) (r = -0.73; p < 0.01) and VO2PEAK (r = -0.61; p < 0.05) in TR group. The ventilation behavior during incremental treadmill test tends to show only one threshold. UT subjects showed a slower ventilation increase during moderate intensities while TR subjects showed a slower ventilation increase during heavy intensities.

Prediction of good glass formers in the Al-Ni-La and Al-Ni-Gd systems using topological instability and electronegativity

A new criterion has been recently proposed combining the topological instability (lambda criterion) and the average electronegativity difference (Delta e) among the elements of an alloy to predict and select new glass-forming compositions. In the present work, this criterion (lambda.Delta e) is applied to the Al-Ni-La and Al-Ni-Gd ternary systems and its predictability is validated using literature data for both systems and additionally, using own experimental data for the Al-La-Ni system. The compositions with a high lambda.Delta e value found in each ternary system exhibit a very good correlation with the glass-forming ability of different alloys as indicated by their supercooled liquid regions (Delta T(x)) and their critical casting thicknesses. In the case of the Al-La-Ni system, the alloy with the largest lambda.Delta e value, La(56)Al(26.5)Ni(17.5), exhibits the highest glass-forming ability verified for this system. Therefore, the combined lambda.Delta e criterion is a simple and efficient tool to select new glass-forming compositions in Al-Ni-RE systems. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3563099]

Effect of Alloying Elements on Thermal Diffusivity of Gray Cast Iron Used in Automotive Brake Disks

The purpose of this work was to experimentally investigate the thermal diffusivity of four different gray cast iron alloys, regularly used to produce brake disks for automotive vehicles. Thermal diffusivity measurements were performed at temperatures ranging from room temperature to 600 A degrees C. The influence of the thermal conductivity on the thermomechanical fatigue life is also briefly presented. The measurements were sensitive to the influence of the carbon equivalent and alloying elements, such as molybdenum, copper and chromium. Molybdenum, unlike copper, lowered the thermal diffusivity of the gray cast iron, and alloy E (without molybdenum), besides presenting a relatively low carbon equivalent content and an increase in the values of the thermal diffusivity, presented the best performance during the thermomechanical fatigue. The molybdenum present in alloys B and C did not fulfill the expectations of providing the best thermomechanical fatigue behavior. Consequently, its elimination in the gray cast iron alloy for this application will result in a significant economy.

Anomalous thermodynamic properties in ferropericlase throughout its spin crossover transition

The thermodynamics properties of ferropericlase (Mg(1-x)Fe(x)O where x=0.1875) (Fp) throughout its spin crossover were investigated by first principles. Fp was treated as an ideal solid solution of pure high-spin and low-spin states. The Gibbs free energies of the pure states were addressed using the LDA+U method. A vibrational virtual-crystal model was developed to address the vibrational properties of the pure spin cases and used in conjunction with quasiharmonic theory to compute their vibrational free energies. The thermodynamics properties of Fp display significant anomalies that should be typical of spin crossover systems in general. In Fp, in particular, they are fundamental for understanding the state of earth's interior, where the pressure and temperature conditions of the crossover are realized.

Homeotropic surface anchoring and the layer-thinning transition in free-standing films

In this work, we investigate the interplay between surface anchoring and finite-size effects on the smectic-isotropic transition in free-standing smectic films. Using an extended McMillan model, we study how a homeotropic anchoring stabilizes the smectic order above the bulk transition temperature. In particular, we determine how the transition temperature depends on the surface ordering and film thickness. We identify a characteristic anchoring for which the transition temperature does not depend on the film thickness. For strong surface ordering, we found that the thickness dependence of the transition temperature can be well represented by a power-law relation. The power-law exponent exhibits a weak dependence on the range of film thicknesses, as well as on the molecular alkyl tail length. Our results reproduce the main experimental findings concerning the layer-thinning transitions in free-standing smectic films.

Sao Paulo: globalisation and metropolitan transition

The recent transformations taking place in the city of Sao Paulo show how the global urban dimension goes hand in hand with local deprivation and segregation. Both globalisation trends and segregation dynamics orientate a social and spatial process of change which has as the main result the dissolution of the urban condition in Sao Paulo. The metropolisation dynamics currently at work in South American cities can be understood, taking into consideration evidences and facts coming from the analysis of Sao Paulo, as a transition resulting from the globalisation process which takes place in contemporary cities.

Report of a chimeric origin of transposable elements in a bovine-coding gene

Despite the wide distribution of transposable elements (TEs) in mammalian genomes, part of their evolutionary significance remains to be discovered. Today there is a substantial amount of evidence showing that TEs are involved in the generation of new exons in different species. In the present study, we searched 22,805 genes and reported the occurrence of TE-cassettes in coding sequences of 542 cow genes using the RepeatMasker program. Despite the significant number (542) of genes with TE insertions in exons only 14 (2.6%) of them were translated into protein, which we characterized as chimeric genes. From these chimeric genes, only the FAST kinase domains 3 (FASTKD3) gene, present on chromosome BTA 20, is a functional gene and showed evidence of the exaptation event. The genome sequence analysis showed that the last exon coding sequence of bovine FASTKD3 is similar to 85% similar to the ART2A retrotransposon sequence. In addition, comparison among FASTKD3 proteins shows that the last exon is very divergent from those of Homo sapiens, Pan troglodytes and Canis familiares. We suggest that the gene structure of bovine FASTKD3 gene could have originated by several ectopic recombinations between TE copies. Additionally, the absence of TE sequences in all other species analyzed suggests that the TE insertion is clade-specific, mainly in the ruminant lineage.

Toxic and essential elements in blood from delivering women in selected areas of Sao Paulo State, Brazil

This study was designed to evaluate the degree of environmental contamination and possible exposure of pregnant women to toxic elements in seven selected areas of Sao Paulo State, Brazil. The overall median concentration of Mo in maternal blood was 0.53 mu g L(-1), highly significant differences found between sites (p < 0.0001). Cd was found to be low overall - 0.09 mu g L(-1) (0.01-0.58 mu g L(-1)) - with mothers from the Coastal and Rural 1 sites having the highest levels (p < 0.016). Median Hg concentration was 0.60 mu g L (1) (0.06 mu g L (1)-4.35 mu g L (1)); median Pb level was 16.2 mu g L (1) (3.5-57.7 mu g L(-1)) and no differences between sites were observed for both metals. Median Mn level was 16.7 mu g L(-1) (7.0-39.7 mu g L(-1)), being highest in Urban 2 site (p < 0.016). Concentrations of maternal Co were found to range between 0.06 mu g L(-1) and 1.1 mu g L(-1) (median 0.25 mu g L(-1)) and As level was 0.60 mu g L(-1) (0.10-3.8 mu g L(-1)) overall, with no statistical significance between sites for Co and As. Median Se concentrations were found to be 64 mg L(-1) (36-233 mu g L(-1)), with the highest median levels found in Urban 3 site; site differences were statistically significant (p < 0.0001). Correlation for each element (between paired maternal and cord blood) was measured only in Rural site 1; significant correlation was shown for Hg, Pb, Mn and Co (p < 0.05). These findings may be interpreted as indicating low environmental contamination in Sao Paulo State, Brazil. These findings could also indicate that pregnant women have little or no contact with pollutants, possibly due to awareness campaigns carried out by public health practitioners.