111 resultados para coordination sites


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Although sparsely populated today, the Llanos de Mojos, Bolivia, sustained large sedentary societies in the Late Holocene (ca. 500 to 1400 AD). In order to gain insight into the subsistence of these people, we undertook macrobotanical and phytolith analyses of sediment samples, and starch grain and phytolith analyses of artifact residues, from four large habitation sites within this region. Macrobotanical remains show the presence of maize (Zea mays), squash (Cucurbita sp.), peanut (Arachis hypogaea), cotton (Gossypium sp.), and palm fruits (Arecaceae). Microbotanical results confirm the widespread use of maize at all sites, along with manioc (Manihot esculenta), squash, and yam (Dioscorea sp.). These integrated results present the first comprehensive archaeobotanical evidence of the diversity of plants cultivated, processed, and consumed, by the pre-Hispanic inhabitants of the Amazonian lowlands of Bolivia.

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The electronic structure and oxidation state of atomic Au adsorbed on a perfect CeO2(111) surface have been investigated in detail by means of periodic density functional theory-based calculations, using the LDA+U and GGA+U potentials for a broad range of U values, complemented with calculations employing the HSE06 hybrid functional. In addition, the effects of the lattice parameter a0 and of the starting point for the geometry optimization have also been analyzed. From the present results we suggest that the oxidation state of single Au atoms on CeO2(111) predicted by LDA+U, GGA+U, and HSE06 density functional calculations is not conclusive and that the final picture strongly depends on the method chosen and on the construction of the surface model. In some cases we have been able to locate two well-defined states which are close in energy but with very different electronic structure and local geometries, one with Au fully oxidized and one with neutral Au. The energy difference between the two states is typically within the limits of the accuracy of the present exchange-correlation potentials, and therefore, a clear lowest-energy state cannot be identified. These results suggest the possibility of a dynamic distribution of Au0 and Au+ atomic species at the regular sites of the CeO2(111) surface.

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We report here a unique chiral hybrid gallium sulfide, [NC2H8]2[Ga10S16(N2C12H12)(NC2H7)2] 1, consisting of helical chains of organically-functionalised supertetrahedral clusters which form quadruple-stranded helical nanotubes of ca. 3 nm diameter. This material therefore consists of discrete metal-organic nanotubes which, to the best of our knowledge, are extremely rare. Whilst solvothermal reactions involving 1,2-di(4-pyridyl)ethylene (DPE) resulted in the formation of such single-walled chiral nanotubes, the use of longer 4,4’-trimethylenedipyridine (TMP) ligands resulted in the synthesis of a two-dimensional hybrid gallium sulfide, [C5H6N]3[Ga10S16(OH)(N2C13H14)] 2 in which, for the first time, inorganic and organic linkages between supertetrahedral clusters coexist.

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We use density functional theory calculations with Hubbard corrections (DFT+U) to investigate electronic aspects of the interaction between ceria surfaces and gold atoms. Our results show that Au adatoms at the (111) surface of ceria can adopt Au0, Au+ or Au� electronic configurations depending on the adsorption site. The strongest adsorption sites are on top of the surface oxygen and in a bridge position between two surface oxygen atoms, and in both cases charge transfer from the gold atom to one of the Ce cations at the surface is involved. Adsorption at other sites, including the hollow sites of the surface, and an O–Ce bridging site, is weaker and does not involve charge transfer. Adsorption at an oxygen vacancy site is very strong and involves the formation of an Au� anion. We argue that the ability of gold atoms to stabilise oxygen vacancies at the ceria surface by moving into the vacancy site and attracting the excess electrons of the defect could be responsible for the enhanced reducibility of ceria surfaces in the presence of gold. Finally, we rationalise the differences in charge transfer behaviour from site to site in terms of the electrostatic potential at the surface and the coordination of the species.

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Drawing upon a national database of unimplemented planning permissions and 18 in-depth case studies, this paper provides both a quantitative and qualitative analysis of the phenomenon of stalled sites in England. The practical and conceptual difficulties of classifying sites as stalled are critically reviewed. From the literature, it is suggested that planning permission may not be implemented due to lack of financial viability, strategic behaviour by landowners and house-builders and other problems associated with the development process. Consistent with poor viability, the analysis of the national database indicates that a substantial proportion of the stalled sites is high density apartment development and/or is located in low house value areas. The case studies suggest that a combination of interlinked issues may need to be resolved before a planning permission can be implemented. These include; the sale of the land to house-builders, re-negotiation of the planning permission and, most importantly, improvement in housing market conditions.

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The adsorption and co-adsorption of lithium and oxygen at the surface of rutile-like manganese dioxide(b-MnO2), which are important in the context of Li–air batteries, are investigated using density functional theory. In the absence of lithium, the most stable surface of b-MnO2, the (110), adsorbs oxygen in the form of peroxo groups bridging between two manganese cations. Conversely, in the absence of excess oxygen, lithium atoms adsorb on the (110) surface at two different sites, which are both tricoordinated to surface oxygen anions, and the adsorption always involves the transfer of one electron from the adatom to one of the five-coordinated manganese cations at the surface, creating (formally) Li+ and Mn3+ species. The co-adsorption of lithium and oxygen leads to the formation of a surface oxide, involving the dissociation of the O2 molecule, where the O adatoms saturate the coordination of surface Mn cations and also bind to the Li adatoms. This process is energetically more favourable than the formation of gas-phase lithium peroxide (Li2O2) monomers, but less favourable than the formation of Li2O2 bulk. These results suggest that the presence of b-MnO2 in the cathode of a nonaqueous Li–O2 battery lowers the energy for the initial reduction of oxygen during cell discharge.

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Samples containing red pigment have been collected from two different archaeological sites dating to the Neolithic (Çatalhöyük in Turkey and Sheikh-e Abad in Iran) and have been analysed by a range of techniques. Sub-samples were examined by IR spectroscopy and X-ray diffraction, whilst thin sections were studied using optical polarising microscopy, synchrotron based IR microscopy and environmental scanning electron microscopy with energy dispersive X-ray analysis. Thin layers of red paint in a wall painting from Çatalhöyük were found to contain ochre (hematite and clay) as well as an unexpected component, grains of red and colourless obsidian, which have not been identified in any previous studies of the wall paintings at Çatalhöyük. These small grains of obsidian may have improved the reflective properties of the paint and made the artwork more vivid in the darkness of the buildings. Analysis of a roughly shaped ball of red sediment found on a possible working surface at Sheikh-e Abad revealed that the cause of the red colouring was the mineral hematite, which was probably from a source of terra rossa sediment in the local area. The results of this work suggest it is unlikely that this had been altered by the Neolithic people through mixing with other minerals.

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The current state of the art in the planning and coordination of autonomous vehicles is based upon the presence of speed lanes. In a traffic scenario where there is a large diversity between vehicles the removal of speed lanes can generate a significantly higher traffic bandwidth. Vehicle navigation in such unorganized traffic is considered. An evolutionary based trajectory planning technique has the advantages of making driving efficient and safe, however it also has to surpass the hurdle of computational cost. In this paper, we propose a real time genetic algorithm with Bezier curves for trajectory planning. The main contribution is the integration of vehicle following and overtaking behaviour for general traffic as heuristics for the coordination between vehicles. The resultant coordination strategy is fast and near-optimal. As the vehicles move, uncertainties may arise which are constantly adapted to, and may even lead to either the cancellation of an overtaking procedure or the initiation of one. Higher level planning is performed by Dijkstra's algorithm which indicates the route to be followed by the vehicle in a road network. Re-planning is carried out when a road blockage or obstacle is detected. Experimental results confirm the success of the algorithm subject to optimal high and low-level planning, re-planning and overtaking.

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The use of social network sites (SNS) has become very valuable to educational institutions. Some universities have formally integrated these social media in their educational systems and are using them to improve their service delivery. The main aim of this study was to establish whether African universities have embraced this emerging technology by having official presence on SNS. A purposive sampling method was used to study 24 universities from which data were obtained by visiting their official websites and following the official links to the most common SNS.

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The decomposition of soil organic matter (SOM) is temperature dependent, but its response to a future warmer climate remains equivocal. Enhanced rates of decomposition of SOM under increased global temperatures might cause higher CO2 emissions to the atmosphere, and could therefore constitute a strong positive feedback. The magnitude of this feedback however remains poorly understood, primarily because of the difficulty in quantifying the temperature sensitivity of stored, recalcitrant carbon that comprises the bulk (>90%) of SOM in most soils. In this study we investigated the effects of climatic conditions on soil carbon dynamics using the attenuation of the 14C ‘bomb’ pulse as recorded in selected modern European speleothems. These new data were combined with published results to further examine soil carbon dynamics, and to explore the sensitivity of labile and recalcitrant organic matter decomposition to different climatic conditions. Temporal changes in 14C activity inferred from each speleothem was modelled using a three pool soil carbon inverse model (applying a Monte Carlo method) to constrain soil carbon turnover rates at each site. Speleothems from sites that are characterised by semi-arid conditions, sparse vegetation, thin soil cover and high mean annual air temperatures (MAATs), exhibit weak attenuation of atmospheric 14C ‘bomb’ peak (a low damping effect, D in the range: 55–77%) and low modelled mean respired carbon ages (MRCA), indicating that decomposition is dominated by young, recently fixed soil carbon. By contrast, humid and high MAAT sites that are characterised by a thick soil cover and dense, well developed vegetation, display the highest damping effect (D = c. 90%), and the highest MRCA values (in the range from 350 ± 126 years to 571 ± 128 years). This suggests that carbon incorporated into these stalagmites originates predominantly from decomposition of old, recalcitrant organic matter. SOM turnover rates cannot be ascribed to a single climate variable, e.g. (MAAT) but instead reflect a complex interplay of climate (e.g. MAAT and moisture budget) and vegetation development.

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A new layered indium selenide, [C7H10N][In3Se5], was prepared under solvothermal conditions using 3,5-dimethylpyridine as a structure-directing agent. The crystal structure contains anionic layers of stoichiometry [In3Se5]− in which indium atoms with octahedral and tetrahedral coordination coexist. This material represents the first occurrence of octahedrally coordinated indium in a solvothermally-prepared indium selenide.

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A new iron(II) coordination polymer, [FeCl2(NC7H9)2(N2C12H12)], has been synthesized under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction. This material crystallizes in the monoclinic space group C2/c, with a = 11.2850(6), b = 13.8925(7), c = 17.0988(9) Å and β = 94.300(3)º (Z = 4). The crystal structure consists of neutral zig-zag chains, in which the iron(II) ions are octahedrally coordinated. The infinite polymer chains are packed into a three-dimensional structure through C–H···Cl interactions. Magnetic susceptibility measurements reveal the existence of weak antiferromagnetic interactions between the iron(II) ions. The effective magnetic moment, μ eff = 5.33 μ B , is consistent with a high-spin iron(II) configuration.

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Recent evidence indicates that each eye does not always fixate the same letter during reading and there has been some suggestion that processing difficulty may influence binocular coordination. We recorded binocular eye movements from children and adults reading sentences containing a word frequency manipulation. We found disparities of significant magnitude between the two eyes for all participants, with greater disparity magnitudes in children than adults. All participants made fewer crossed than uncrossed fixations. However, children made a higher proportion of crossed fixations than adults. We found no influence of word frequency on children’s fixations and on binocular coordination in adults.

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Trace element measurements in PM10–2.5, PM2.5–1.0 and PM1.0–0.3 aerosol were performed with 2 h time resolution at kerbside, urban background and rural sites during the ClearfLo winter 2012 campaign in London. The environment-dependent variability of emissions was characterized using the Multilinear Engine implementation of the positive matrix factorization model, conducted on data sets comprising all three sites but segregated by size. Combining the sites enabled separation of sources with high temporal covariance but significant spatial variability. Separation of sizes improved source resolution by preventing sources occurring in only a single size fraction from having too small a contribution for the model to resolve. Anchor profiles were retrieved internally by analysing data subsets, and these profiles were used in the analyses of the complete data sets of all sites for enhanced source apportionment. A total of nine different factors were resolved (notable elements in brackets): in PM10–2.5, brake wear (Cu, Zr, Sb, Ba), other traffic-related (Fe), resuspended dust (Si, Ca), sea/road salt (Cl), aged sea salt (Na, Mg) and industrial (Cr, Ni); in PM2.5–1.0, brake wear, other traffic-related, resuspended dust, sea/road salt, aged sea salt and S-rich (S); and in PM1.0–0.3, traffic-related (Fe, Cu, Zr, Sb, Ba), resuspended dust, sea/road salt, aged sea salt, reacted Cl (Cl), S-rich and solid fuel (K, Pb). Human activities enhance the kerb-to-rural concentration gradients of coarse aged sea salt, typically considered to have a natural source, by 1.7–2.2. These site-dependent concentration differences reflect the effect of local resuspension processes in London. The anthropogenically influenced factors traffic (brake wear and other traffic-related processes), dust and sea/road salt provide further kerb-to-rural concentration enhancements by direct source emissions by a factor of 3.5–12.7. The traffic and dust factors are mainly emitted in PM10–2.5 and show strong diurnal variations with concentrations up to 4 times higher during rush hour than during night-time. Regionally influenced S-rich and solid fuel factors, occurring primarily in PM1.0–0.3, have negligible resuspension influences, and concentrations are similar throughout the day and across the regions.