Structure of disordered gold-polymer thin films using small angle x-ray scattering

We have investigated the structure of disordered gold-polymer thin films using small angle x-ray scattering and compared the results with the predictions of a theoretical model based on two approaches-a structure form factor approach and the generalized Porod law. The films are formed of polymer-embedded gold nanoclusters and were fabricated by very low energy gold ion implantation into polymethylmethacrylate (PMMA). The composite films span (with dose variation) the transition from electrically insulating to electrically conducting regimes, a range of interest fundamentally and technologically. We find excellent agreement with theory and show that the PMMA-Au films have monodispersive or polydispersive characteristics depending on the implanted ion dose. (C) 2010 American Institute of Physics. [doi:10.1063/1.3493241]

Structure of PbTe(SiO(2))/SiO(2) multilayers deposited on Si(111)

The structure of thin films composed of a multilayer of PbTe nanocrystals embedded in SiO(2), named as PbTe(SiO(2)), between homogeneous layers of amorphous SiO(2) deposited on a single-crystal Si( 111) substrate was studied by grazing-incidence small-angle X-ray scattering (GISAXS) as a function of PbTe content. PbTe(SiO(2))/SiO(2) multilayers were produced by alternately applying plasma-enhanced chemical vapour deposition and pulsed laser deposition techniques. From the analysis of the experimental GISAXS patterns, the average radius and radius dispersion of PbTe nanocrystals were determined. With increasing deposition dose the size of the PbTe nanocrystals progressively increases while their number density decreases. Analysis of the GISAXS intensity profiles along the normal to the sample surface allowed the determination of the period parameter of the layers and a structure parameter that characterizes the disorder in the distances between PbTe layers. (C) 2010 International Union of Crystallography Printed in Singapore - all rights reserved

Unraveling effects of disorder on the electronic structure of SiO(2) from first principles

We present a first-principles systematic study of the electronic structure of SiO(2) including the crystalline polymorphs alpha quartz and beta cristobalite, and different types of disorder leading to the amorphous phase. We start from calculations within density functional theory and proceed to more sophisticated quasiparticle calculations according to the GW scheme. Our results show that different origins of disorder have also different impact on atomic and electronic-density fluctuations, which affect the electronic structure and, in particular, the size of the mobility gap in each case.

Structure of (46)Ti at low excitation energy

The nucleus (46)Ti has been studied with the reaction (42)Ca((7)Li,p2n)(46)Ti at a bombarding energy of 31 MeV. Thin target foils backed with a thick Au layer were used. Five new levels of negative parity were observed. Several lifetimes have been determined with the Doppler shift attenuation method. Low-lying experimental negative-parity levels are assigned to three bands with K(pi) = 3, 0, and 4, which are interpreted in terms of the large-scale shell model, considering particle-hole excitations from d(3/2) and s(1/2) orbitals. Shell model calculations were performed using a few effective interactions. However, good agreement was not achieved in the description of either negative- or positive-parity low-lying levels.

Communication structure of cortical networks

Large-scale cortical networks exhibit characteristic topological properties that shape communication between brain regions and global cortical dynamics. Analysis of complex networks allows the description of connectedness, distance, clustering, and centrality that reveal different aspects of how the network's nodes communicate. Here, we focus on a novel analysis of complex walks in a series of mammalian cortical networks that model potential dynamics of information flow between individual brain regions. We introduce two new measures called absorption and driftness. Absorption is the average length of random walks between any two nodes, and takes into account all paths that may diffuse activity throughout the network. Driftness is the ratio between absorption and the corresponding shortest path length. For a given node of the network, we also define four related measurements, namely in-and out-absorption as well as in-and out-driftness, as the averages of the corresponding measures from all nodes to that node, and from that node to all nodes, respectively. We find that the cat thalamo-cortical system incorporates features of two classic network topologies, Erdos-Renyi graphs with respect to in-absorption and in-driftness, and configuration models with respect to out-absorption and out-driftness. Moreover, taken together these four measures separate the network nodes based on broad functional roles (visual, auditory, somatomotor, and frontolimbic).

Short-range structure of Pb(1-x)Ba(x)Zr(0.65)Ti(0.35)O(3) ceramic compounds probed by XAS and Raman scattering techniques

Ti K-edge x-ray absorption near-edge spectroscopy (XANES) and Raman scattering were used to study the solid solution effects on the structural and vibrational properties of Pb(1-x)Ba(x)Zr(0.65)Ti(0.35)O(3) with 0.0 < x < 0.40. Compared with x-ray diffraction techniques, which indicates that the average crystal symmetry changes with the substitution of Pb by Ba ions or with temperature variations for samples with x=0.00, 0.10, and 0.20, local structural probes such as XANES and Raman scattering results demonstrate that at local level, the symmetry changes are much less prominent. Theoretical XANES spectra calculation corroborate with the interpretation of the XANES experimental data.

Structure of an Odorant-Binding Protein from the Mosquito Aedes aegypti Suggests a Binding Pocket Covered by a pH-Sensitive ""Lid""

Background: The yellow fever mosquito, Aedes aegypti, is the primary vector for the viruses that cause yellow fever, mostly in tropical regions of Africa and in parts of South America, and human dengue, which infects 100 million people yearly in the tropics and subtropics. A better understanding of the structural biology of olfactory proteins may pave the way for the development of environmentally-friendly mosquito attractants and repellents, which may ultimately contribute to reduction of mosquito biting and disease transmission. Methodology: Previously, we isolated and cloned a major, female-enriched odorant-binding protein (OBP) from the yellow fever mosquito, AaegOBP1, which was later inadvertently renamed AaegOBP39. We prepared recombinant samples of AaegOBP1 by using an expression system that allows proper formation of disulfide bridges and generates functional OBPs, which are indistinguishable from native OBPs. We crystallized AaegOBP1 and determined its three-dimensional structure at 1.85 angstrom resolution by molecular replacement based on the structure of the malaria mosquito OBP, AgamOBP1, the only mosquito OBP structure known to date. Conclusion: The structure of AaegOBP1 (= AaegOBP39) shares the common fold of insect OBPs with six alpha-helices knitted by three disulfide bonds. A long molecule of polyethylene glycol (PEG) was built into the electron-density maps identified in a long tunnel formed by a crystallographic dimer of AaegOBP1. Circular dichroism analysis indicated that delipidated AaegOBP1 undergoes a pH-dependent conformational change, which may lead to release of odorant at low pH (as in the environment in the vicinity of odorant receptors). A C-terminal loop covers the binding cavity and this ""lid"" may be opened by disruption of an array of acid-labile hydrogen bonds thus explaining reduced or no binding affinity at low pH.

Partial magnetic ordering and crystal structure of the ludwigites Co(2)FeO(2)BO(3) and Ni(2)FeO(2)BO(3)

We present an extensive study of the structural, magnetic, and thermodynamic properties of the two heterometallic oxyborates: Co(2)FeO(2)BO(3) and Ni(2)FeO(2)BO(3). This has been carried out through x-ray diffraction at room temperature (RT) and 150 K, dc and ac magnetic susceptibilities, and specific-heat experiments in single crystals above 2 K. The magnetic properties of these iron ludwigites are discussed in comparison with those of the other two known homometallic ludwigites: Fe(3)O(2)BO(3) and Co(3)O(2)BO(3). In both ludwigites now studied we have found that the magnetic ordering of the Fe(3+) ions occurs at temperatures very near to which they order in Fe(3)O(2)BO(3). A freezing of the divalent ions (Co and Ni) is observed at lower temperatures. Our x-ray diffraction study of both ludwigites at RT and 150 K showed very small ionic disorder in apparent contrast with the freezing of the divalent ion spins. The structural transition that occurs in homometallic Fe(3)O(2)BO(3) has not been found in the present mixed ludwigites in the temperature range investigated.

Electronic structure of In(2)O(3) and Sn-doped In(2)O(3) by hard x-ray photoemission spectroscopy

The valence and core levels of In(2)O(3) and Sn-doped In(2)O(3) have been studied by hard x-ray photoemission spectroscopy (hv = 6000 eV) and by conventional Al K alpha (hv = 1486.6 eV) x-ray photoemission spectroscopy. The experimental spectra are compared with density-functional theory calculations. It is shown that structure deriving from electronic levels with significant In or Sn 5s character is selectively enhanced under 6000 eV excitation. This allows us to infer that conduction band states in Sn-doped samples and states at the bottom of the valence band both contain a pronounced In 5s contribution. The In 3d core line measured at hv = 1486.6 eV for both undoped and Sn-doped In(2)O(3) display an asymmetric lineshape, and may be fitted with two components associated with screened and unscreened final states. The In 3d core line spectra excited at hv = 6000 eV for the Sn-doped samples display pronounced shoulders and demand a fit with two components. The In 3d core line spectrum for the undoped sample can also be fitted with two components, although the relative intensity of the component associated with the screened final state is low, compared to excitation at 1486.6 eV. These results are consistent with a high concentration of carriers confined close to the surface of nominally undoped In(2)O(3). This conclusion is in accord with the fact that a conduction band feature observed for undoped In(2)O(3) in Al K alpha x-ray photoemission is much weaker than expected in hard x-ray photoemission.

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.

Solution structure of the human signaling protein RACK1

Background: The adaptor protein RACK1 (receptor of activated kinase 1) was originally identified as an anchoring protein for protein kinase C. RACK1 is a 36 kDa protein, and is composed of seven WD repeats which mediate its protein-protein interactions. RACK1 is ubiquitously expressed and has been implicated in diverse cellular processes involving: protein translation regulation, neuropathological processes, cellular stress, and tissue development. Results: In this study we performed a biophysical analysis of human RACK1 with the aim of obtaining low resolution structural information. Small angle X-ray scattering (SAXS) experiments demonstrated that human RACK1 is globular and monomeric in solution and its low resolution structure is strikingly similar to that of an homology model previously calculated by us and to the crystallographic structure of RACK1 isoform A from Arabidopsis thaliana. Both sedimentation velocity and sedimentation equilibrium analytical ultracentrifugation techniques showed that RACK1 is predominantly a monomer of around 37 kDa in solution, but also presents small amounts of oligomeric species. Moreover, hydrodynamic data suggested that RACK1 has a slightly asymmetric shape. The interaction of RACK1 and Ki1/57 was tested by sedimentation equilibrium. The results suggested that the association between RACK1 and Ki-1/57(122-413) follows a stoichiometry of 1:1. The binding constant (KB) observed for RACK1-Ki-1/57(122-413) interaction was of around (1.5 +/- 0.2) x 10(6) M(-1) and resulted in a dissociation constant (KD) of (0.7 +/- 0.1) x 10(-6) M. Moreover, the fluorescence data also suggests that the interaction may occur in a cooperative fashion. Conclusion: Our SAXS and analytical ultracentrifugation experiments indicated that RACK1 is predominantly a monomer in solution. RACK1 and Ki-1/57(122-413) interact strongly under the tested conditions.

Foraging by the omnivorous crab Pachygrapsus transversus affects the structure of assemblages on sub-tropical rocky shores

The roles of herbivory and predation in determining the structure and diversity of communities have been tested across most intertidal systems. In contrast, the importance of omnivorous consumers remains untested in many rocky shore communities. We tested the role of a small omnivorous crab in an intertidal food web on rocky shores of the sub-tropical southwest Atlantic. Exclusion of the grapsid crab Pachygrapsus transversus in the field resulted in significant changes in the abundance of functional groups in the sublittoral fringe of sheltered shores, where the dominant cover changed from a suite of macroalgae to an assemblage of filter-feeding animals (ascidians, sponges, mussels). In contrast, limpets, whelks, large crabs and fish did not significantly affect community composition of the assemblage. To examine the omnivorous feeding pattern of P. transversus, we did laboratory experiments to test its foraging behaviour among animal and algal groups. The crab showed selective behaviour, preferring invertebrate groups to macroalgae, and opportunistic behaviour among types of prey within those major groups. According to our results, the role of slow-moving and large fast-moving consumers is apparently negligible compared to the effect of an omnivorous consumer. P. transversus plays an important role in determining the intertidal community composition on these subtropical rocky shores, causing changes in the balance of functional groups and controlling invasive species.

The Influence of Different Land Uses on the Structure of Archaeal Communities in Amazonian Anthrosols Based on 16S rRNA and amoA Genes

Soil from the Amazonian region is usually regarded as unsuitable for agriculture because of its low organic matter content and low pH; however, this region also contains extremely rich soil, the Terra Preta Anthrosol. A diverse archaeal community usually inhabits acidic soils, such as those found in the Amazon. Therefore, we hypothesized that this community should be sensitive to changes in the environment. Here, the archaeal community composition of Terra Preta and adjacent soil was examined in four different sites in the Brazilian Amazon under different anthropic activities. The canonical correspondence analysis of terminal restriction fragment length polymorphisms has shown that the archaeal community structure was mostly influenced by soil attributes that differentiate the Terra Preta from the adjacent soil (i.e., pH, sulfur, and organic matter). Archaeal 16S rRNA gene clone libraries indicated that the two most abundant genera in both soils were Candidatus nitrosphaera and Canditatus nitrosocaldus. An ammonia monoxygenase gene (amoA) clone library analysis indicated that, within each site, there was no significant difference between the clone libraries of Terra Preta and adjacent soils. However, these clone libraries indicated there were significant differences between sites. Quantitative PCR has shown that Terra Preta soils subjected to agriculture displayed a higher number of amoA gene copy numbers than in adjacent soils. On the other hand, soils that were not subjected to agriculture did not display significant differences on amoA gene copy numbers between Terra Preta and adjacent soils. Taken together, our findings indicate that the overall archaeal community structure in these Amazonian soils is determined by the soil type and the current land use.

Inter-individual variability in temporal structure of the basketball shoot

This study analyzed inter-individual variability of the temporal structure applied in basketball throwing. Ten experienced male athletes in basketball throwing were filmed and a number of kinematic movement parameters analyzed. A biomechanical model provided the relative timing of the shoulder, elbow and wrist joint movements. Inter-individual variability was analyzed using sequencing and relative timing of tem phases of the throw. To compare the variability of the movement phases between subjects a discriminant analysis and an ANOVA were applied. The Tukey test was applied to determine where differences occurred. The significance level was p = 0.05. Inter-individual variability was explained by three concomitant factors: (a) a precision control strategy, (b) a velocity control strategy and (c) intrinsic characteristics of the subjects. Therefore, despite the fact that some actions are common to the basketball throwing pattern each performed demonstrated particular and individual characteristics.