Hybrid density functional study of small Rh-n (n=2-15) clusters

The physical properties of small rhodium clusters, Rh-n, have been in debate due to the shortcomings of density functional theory (DFT). To help in the solution of those problems, we obtained a set of putative lowest energy structures for small Rh-n (n = 2-15) clusters employing hybrid-DFT and the generalized gradient approximation (GGA). For n = 2-6, both hybrid and GGA functionals yield similar ground-state structures (compact), however, hybrid favors compact structures for n = 7-15, while GGA favors open structures based on simple cubic motifs. Thus, experimental results are crucial to indicate the correct ground-state structures, however, we found that a unique set of structures (compact or open) is unable to explain all available experimental data. For example, the GGA structures (open) yield total magnetic moments in excellent agreement with experimental data, while hybrid structures (compact) have larger magnetic moments compared with experiments due to the increased localization of the 4d states. Thus, we would conclude that GGA provides a better description of the Rh-n clusters, however, a recent experimental-theoretical study [ Harding et al., J. Chem. Phys. 133, 214304 (2010)] found that only compact structures are able to explain experimental vibrational data, while open structures cannot. Therefore, it indicates that the study of Rh-n clusters is a challenging problem and further experimental studies are required to help in the solution of this conundrum, as well as a better description of the exchange and correlation effects on the Rh n clusters using theoretical methods such as the quantum Monte Carlo method.

Encapsulation of small magnetic clusters in fullerene cages: A density functional theory investigation within van der Waals corrections

The encapsulation of magnetic transition-metal (TM) clusters inside carbon cages (fullerenes, nanotubes) has been of great interest due to the wide range of applications, which spread from medical sensors in magnetic resonance imaging to photonic crystals. Several theoretical studies have been reported; however, our atomistic understanding of the physical properties of encapsulated magnetic TM 3d clusters is far from satisfactory. In this work, we will report general trends, derived from density functional theory within the generalized gradient approximation proposed by Perdew, Burke, and Ernzerhof (PBE), for the encapsulation properties of the TMm@C-n (TM = Fe, Co, Ni; m = 2-6, n = 60,70,80,90) systems. Furthermore, to understand the role of the van der Waals corrections to the physical properties, we employed the empirical Grimme's correction (PBE + D2). We found that both PBE and PBE + D2 functionals yield almost the same geometric parameters, magnetic and electronic properties, however, PBE + D2 strongly enhances the encapsulation energy. We found that the center of mass of the TMm clusters is displaced towards the inside C-n surfaces, except for large TMm clusters (m = 5 and 6). For few cases, e. g., Co-4 and Fe-4, the encapsulation changes the putative lowest-energy structure compared to the isolated TMm clusters. We identified few physical parameters that play an important role in the sign and magnitude of the encapsulation energy, namely, cluster size, fullerene equatorial diameter, shape, curvature of the inside C-n surface, number of TM atoms that bind directly to the inside C-n surface, and the van der Waals correction. The total magnetic moment of encapsulated TMm clusters decreases compared with the isolated TMm clusters, which is expected due to the hybridization of the d-p states, and strongly depends on the size and shape of the fullerene cages.

The last mangroves of Marajo Island - Eastern Amazon: Impact of climate and/or relative sea-level changes

The dynamics, over the last 7500 years, of a mangrove at Marajo Island in northern Brazil were studied by pollen and sedimentary facies analyses using sediment cores. This island, located at the mouth of the Amazon River. is influenced by riverine inflow combined with tidal fluctuations of the equatorial Atlantic Ocean. Herbaceous vegetation intermingled with rainforest dominates the central area of the island, while varzea is the main vegetation type along the littoral. In particular, the modem northeastern coastal zone is covered by a mosaic of dense rainforest, herbaceous vegetation, mangroves, varzea, and restinga. The integration of pollen data and fades descriptions indicates a tidal mud flat colonized by mangroves in the interior of Marajo Island between similar to 7500 cal yr BP and similar to 3200 cal yr BP. During the late Holocene, mangroves retracted to a small area (100-700 m in width) along the northeastern coastal plain. Mangrove expansion during the early and mid Holocene was likely caused by the post-glacial sea-level rise which, combined with tectonic subsidence, led to a rise in tidal water salinity. Salinity must have further increased due to low river discharge resulting from increased aridity during the early and mid Holocene. The shrinking of the area covered by mangrove vegetation during the late Holocene was likely caused by the increase in river discharge during the late Holocene, which has maintained relatively low tidal water salinity in Marajo Island. Tidal water salinity is relatively higher in the northeastern part of the island than in others, due to the southeast-northwest trending current along the littoral. The mixing of marine and riverine freshwater inflows has provided a refuge for mangroves in this area. The increase in flow energy during the last century is related to landward sand migration, which explains the current retraction of mangroves. These changes may indicate an increased exposure to tidal influence driven by the relative sea-level rise, either associated with global fluctuations or tectonic subsidence, and/or by an increase in river water discharge. (C) 2012 Elsevier B.V. All rights reserved.

A model of road effect using line integrals and a test of the performance of two new road indices using the distribution of small mammals in an Atlantic Forest landscape

Effects of roads on wildlife and its habitat have been measured using metrics, such as the nearest road distance, road density, and effective mesh size. In this work we introduce two new indices: (1) Integral Road Effect (IRE), which measured the sum effects of points in a road at a fixed point in the forest; and (2) Average Value of the Infinitesimal Road Effect (AVIRE), which measured the average of the effects of roads at this point. IRE is formally defined as the line integral of a special function (the infinitesimal road effect) along the curves that model the roads, whereas AVIRE is the quotient of IRE by the length of the roads. Combining tools of ArcGIS software with a numerical algorithm, we calculated these and other road and habitat cover indices in a sample of points in a human-modified landscape in the Brazilian Atlantic Forest, where data on the abundance of two groups of small mammals (forest specialists and habitat generalists) were collected in the field. We then compared through the Akaike Information Criterion (AIC) a set of candidate regression models to explain the variation in small mammal abundance, including models with our two new road indices (AVIRE and IRE) or models with other road effect indices (nearest road distance, mesh size, and road density), and reference models (containing only habitat indices, or only the intercept without the effect of any variable). Compared to other road effect indices, AVIRE showed the best performance to explain abundance of forest specialist species, whereas the nearest road distance obtained the best performance to generalist species. AVIRE and habitat together were included in the best model for both small mammal groups, that is, higher abundance of specialist and generalist small mammals occurred where there is lower average road effect (less AVIRE) and more habitat. Moreover, AVIRE was not significantly correlated with habitat cover of specialists and generalists differing from the other road effect indices, except mesh size, which allows for separating the effect of roads from the effect of habitat on small mammal communities. We suggest that the proposed indices and GIS procedures could also be useful to describe other spatial ecological phenomena, such as edge effect in habitat fragments. (C) 2012 Elsevier B.V. All rights reserved.

Quantum Monte Carlo study of small aluminum clusters Al-n (n=2-13)

Using fixed node diffusion quantum Monte Carlo (FN-DMC) simulations and density functional theory (DFT) within the generalized gradient approximations, we calculate the total energies of the relaxed and unrelaxed neutral, cationic, and anionic aluminum clusters, Al-n (n = 1-13). From the obtained total energies, we extract the ionization potential and electron detachment energy and compare with previous theoretical and experimental results. Our results for the electronic properties from both the FN-DMC and DFT calculations are in reasonably good agreement with the available experimental data. A comparison between the FN-DMC and DFT results reveals that their differences are a few tenths of electron volt for both the ionization potential and the electron detachment energy. We also observe two distinct behaviors in the electron correlation contribution to the total energies from smaller to larger clusters, which could be assigned to the structural transition of the clusters from planar to three-dimensional occurring at n = 4 to 5.

Evidence of the participation of electronic excited states in the mechanism of positronium formation in substitutional Tb1-xEux(dpm)(3) solid solutions studied by optical and positron annihilation spectroscopies

Positronium formation in the bimary molecular solid solutions Tb1-xEux (dpm)(3) (dpm = dipivaloylmethanate) has been investigated. A strong linear correlation between the D-5(4) Tb(III) energy level excited state lifetime and the positronium formation probability has been observed. This correlation indicates that the ligand-to-metal charge transfer LMCT states act in both luminescence quenching and positronium formation inhibition, as previously proposed. A kinetic mechanism is proposed to explain this correlation and shows that excited electronic states have a very important role in the positronium formation mechanism.

Magneto-optical probe of quantum Hall states in a wide parabolic well modulated by random potential

Polarized photoluminescence from weakly coupled random multiple well quasi-three-dimensional electron system is studied in the regime of the integer quantum Hall effect. Two quantum Hall ferromagnetic ground states assigned to the uncorrelated miniband quantum Hall state and to the spontaneous interwell phase coherent dimer quantum Hall state are observed. Photoluminescence associated with these states exhibits features caused by finite-size skyrmions: dramatic reduction of the electron spin polarization when the magnetic field is increased past the filling factor nu = 1. The effective skyrmion size is larger than in two-dimensional electron systems.

Condom use at last sexual relationship among adolescents of Santiago Island, Cape Verde, - West Africa

Objective: To estimate factors associated with condom use at last sexual intercourse among adolescents. Methods: Cross-sectional study of a representative sample of 368 sexually active adolescents aged 13-17 years from eight public high schools on Santiago Island, Cape Verde, 2007. The level of significance was 5.0% obtained from logistic regression, considering the association between condom use and socio-demographic, sexual and reproductive variables. Results: The prevalence of condom use at last sexual intercourse was 94.9%. Factors associated with condom use at last sexual relationship were: non-Catholic religion (OR=0.68, 95%CI: 0.52; 0.88) and affective-sexual partnership before the interview (OR=5.15, 95%CI: 1.79; 14.80). Conclusions: There was a high prevalence of condom use at last sexual intercourse of adolescents.

Influence of small-scale inhomogeneities on the cosmological consistency tests

The current cosmological dark sector (dark matter plus dark energy) is challenging our comprehension about the physical processes taking place in the Universe. Recently, some authors tried to falsify the basic underlying assumptions of such dark matterdark energy paradigm. In this Letter, we show that oversimplifications of the measurement process may produce false positives to any consistency test based on the globally homogeneous and isotropic ? cold dark matter (?CDM) model and its expansion history based on distance measurements. In particular, when local inhomogeneity effects due to clumped matter or voids are taken into account, an apparent violation of the basic assumptions (Copernican Principle) seems to be present. Conversely, the amplitude of the deviations also probes the degree of reliability underlying the phenomenological DyerRoeder procedure by confronting its predictions with the accuracy of the weak lensing approach. Finally, a new method is devised to reconstruct the effects of the inhomogeneities in a ?CDM model, and some suggestions of how to distinguish between clumpiness (or void) effects from different cosmologies are discussed.

The distribution and abundance of small mammals in agroecosystems of southeastern Brazil

The conservation of biodiversity in agricultural landscapes depends on information about the ways in which species are affected by the conversion of native habitats into novel anthropogenic environments and the strategies that the species use to persist in these altered ecosystems. Here, we investigate how small mammals occupy the different agroecosystems of an agricultural landscape in the state of Sao Paulo, Brazil. From August 2003 through January 2005, we surveyed small mammals using Sherman traps at 16 sampling sites in each of the four predominant environments of the local agricultural landscape: remnant fragments of semideciduous forest, Eucalyptus plantations, sugarcane plantations, and pastures. With a total effort of 23,040 trap-nights and a capture success of 0.8%, we captured 177 rodents and marsupials belonging to eight species. The assemblage represented by these mammals is essentially composed of generalist species, which are common in degraded areas. Sugarcane plantations had the highest abundance, whereas pastures had the lowest species richness. Our results suggest that the loss of forest species can be related to the loss of native forest. The results also indicate that to improve the conservation value of agricultural landscapes, native forest fragments should be conserved, extensive monocultures should be avoided and agricultural impacts should be mitigated.

Exposure of small mammals to ticks and rickettsiae in Atlantic Forest patches in the metropolitan area of Recife, North-eastern Brazil

Between December 2007 and March 2009, small mammals were captured in 6 Atlantic Forest patches in Brazil. We assessed tick-host associations and whether they differ among forest strata, sites, seasons, and host age classes or between sexes. Moreover, we assessed the exposure of animals to Rickettsia spp. In total, 432 animals were captured and 808 ticks were found on 32-9% of them. Significant differences were found among host species, collection sites, and forest strata; microhabitat preference was a strong risk factor for tick infestation. The highest tick density rates were recorded in forest fragments settled in rural areas; 91.3% of the ticks were collected from animals trapped in these forest fragments. A high prevalence (68.8%) of antibodies to Rickettsia spp. was detected among animals. This study suggests that disturbed Atlantic Forest fragments provide an environment for ticks and small mammals, which are highly exposed to rickettsiae. It also indicates that forest patches settled in rural areas are usually associated with higher small mammal diversity as well as with higher tick density rates.

Drell-Yan as a probe of small x partons at the LHC

The predictions of Drell-Yan production of low-mass lepton pairs, at high rapidity at the LHC, are known to depend sensitively on the choice of factorization and renormalization scales. We show how this sensitivity can be greatly reduced by fixing the factorization scale of the LO contribution based on the known NLO matrix element, so that observations of this process at the LHC can make direct measurements of parton distribution functions in the low x domain; x less than or similar to 10(-4).

High-throughput sequencing of small RNA transcriptomes reveals critical biological features targeted by microRNAs in cell models used for squamous cell cancer research

Abstract Background The implication of post-transcriptional regulation by microRNAs in molecular mechanisms underlying cancer disease is well documented. However, their interference at the cellular level is not fully explored. Functional in vitro studies are fundamental for the comprehension of their role; nevertheless results are highly dependable on the adopted cellular model. Next generation small RNA transcriptomic sequencing data of a tumor cell line and keratinocytes derived from primary culture was generated in order to characterize the microRNA content of these systems, thus helping in their understanding. Both constitute cell models for functional studies of microRNAs in head and neck squamous cell carcinoma (HNSCC), a smoking-related cancer. Known microRNAs were quantified and analyzed in the context of gene regulation. New microRNAs were investigated using similarity and structural search, ab initio classification, and prediction of the location of mature microRNAs within would-be precursor sequences. Results were compared with small RNA transcriptomic sequences from HNSCC samples in order to access the applicability of these cell models for cancer phenotype comprehension and for novel molecule discovery. Results Ten miRNAs represented over 70% of the mature molecules present in each of the cell types. The most expressed molecules were miR-21, miR-24 and miR-205, Accordingly; miR-21 and miR-205 have been previously shown to play a role in epithelial cell biology. Although miR-21 has been implicated in cancer development, and evaluated as a biomarker in HNSCC progression, no significant expression differences were seen between cell types. We demonstrate that differentially expressed mature miRNAs target cell differentiation and apoptosis related biological processes, indicating that they might represent, with acceptable accuracy, the genetic context from which they derive. Most miRNAs identified in the cancer cell line and in keratinocytes were present in tumor samples and cancer-free samples, respectively, with miR-21, miR-24 and miR-205 still among the most prevalent molecules at all instances. Thirteen miRNA-like structures, containing reads identified by the deep sequencing, were predicted from putative miRNA precursor sequences. Strong evidences suggest that one of them could be a new miRNA. This molecule was mostly expressed in the tumor cell line and HNSCC samples indicating a possible biological function in cancer. Conclusions Critical biological features of cells must be fully understood before they can be chosen as models for functional studies. Expression levels of miRNAs relate to cell type and tissue context. This study provides insights on miRNA content of two cell models used for cancer research. Pathways commonly deregulated in HNSCC might be targeted by most expressed and also by differentially expressed miRNAs. Results indicate that the use of cell models for cancer research demands careful assessment of underlying molecular characteristics for proper data interpretation. Additionally, one new miRNA-like molecule with a potential role in cancer was identified in the cell lines and clinical samples.