52 resultados para 362.8392

em CentAUR: Central Archive University of Reading - UK


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The origins of farming is the defining event of human history-the one turning point that has resulted in modern humans having a quite different type of lifestyle and cognition to all other animals and past types of humans. With the economic basis provided by farming, human individuals and societies have developed types of material culture that greatly augment powers of memory and computation, extending the human mental capacity far beyond that which the brain alone can provide. Archaeologists have long debated and discussed why people began living in settled communities and became dependent on cultivated plants and animals, which soon evolved into domesticated forms. One of the most intriguing explanations was proposed more than 20 years ago not by an archaeologist but by a psychologist: Nicholas Humphrey suggested that farming arose from the 'misapplication of social intelligence'. I explore this idea in relation to recent discoveries and archaeological interpretations in the Near East, arguing that social intelligence has indeed played a key role in the origin of farming and hence the emergence of the modern world.

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In this paper we show stability and convergence for a novel Galerkin boundary element method approach to the impedance boundary value problem for the Helmholtz equation in a half-plane with piecewise constant boundary data. This problem models, for example, outdoor sound propagation over inhomogeneous flat terrain. To achieve a good approximation with a relatively low number of degrees of freedom we employ a graded mesh with smaller elements adjacent to discontinuities in impedance, and a special set of basis functions for the Galerkin method so that, on each element, the approximation space consists of polynomials (of degree $\nu$) multiplied by traces of plane waves on the boundary. In the case where the impedance is constant outside an interval $[a,b]$, which only requires the discretization of $[a,b]$, we show theoretically and experimentally that the $L_2$ error in computing the acoustic field on $[a,b]$ is ${\cal O}(\log^{\nu+3/2}|k(b-a)| M^{-(\nu+1)})$, where $M$ is the number of degrees of freedom and $k$ is the wavenumber. This indicates that the proposed method is especially commendable for large intervals or a high wavenumber. In a final section we sketch how the same methodology extends to more general scattering problems.

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The impacts of climate change on crop productivity are often assessed using simulations from a numerical climate model as an input to a crop simulation model. The precision of these predictions reflects the uncertainty in both models. We examined how uncertainty in a climate (HadAM3) and crop General Large-Area Model (GLAM) for annual crops model affects the mean and standard deviation of crop yield simulations in present and doubled carbon dioxide (CO2) climates by perturbation of parameters in each model. The climate sensitivity parameter (lambda, the equilibrium response of global mean surface temperature to doubled CO2) was used to define the control climate. Observed 1966-1989 mean yields of groundnut (Arachis hypogaea L.) in India were simulated well by the crop model using the control climate and climates with values of lambda near the control value. The simulations were used to measure the contribution to uncertainty of key crop and climate model parameters. The standard deviation of yield was more affected by perturbation of climate parameters than crop model parameters in both the present-day and doubled CO2 climates. Climate uncertainty was higher in the doubled CO2 climate than in the present-day climate. Crop transpiration efficiency was key to crop model uncertainty in both present-day and doubled CO2 climates. The response of crop development to mean temperature contributed little uncertainty in the present-day simulations but was among the largest contributors under doubled CO2. The ensemble methods used here to quantify physical and biological uncertainty offer a method to improve model estimates of the impacts of climate change.

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This paper critiques contemporary research and policy approaches taken toward the analysis and abatement of mercury pollution in the small-scale gold mining sector. Unmonitored releases of mercury from gold amalgamation have caused considerable environmental contamination and human health complications in rural reaches of sub-Saharan Africa, Latin America and Asia. Whilst these problems have caught the attention of the scientific community over the past 15-20 years, the research that has since been undertaken has failed to identify appropriate mitigation measures, and has done little to advance understanding of why contamination persists. Moreover, the strategies used to educate operators about the impacts of acute mercury exposure, and the technologies implemented to prevent farther pollution, have been marginally effective at best. The mercury pollution problem will not be resolved until governments and donor agencies commit to carrying out research aimed at improving understanding of the dynamics of small scale gold mining communities. Acquisition of this knowledge is the key to designing and implementing appropriate support and abatement measures. (c) 2005 Elsevier B.V. All rights reserved.

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The regulation of phosphoinositide (PI) 3-kinase activities has been linked to many normal and disease-related processes, including cell survival, cell growth and proliferation, cell differentiation, cell motility, and intracellular vesicle trafficking. However, as the family of enzymes has now grown to include eight true members, in three functional classes, plus several related protein kinases that are also inhibited by the widely used PI 3-kinase selective inhibitors, wortmannin and LY294002, extended methodologies are required to identify which type of kinase is involved in a particular cellular process, or protein complex, under study. A robust in vitro PI 3-kinase assay, suitable for use with immunoprecipitates, or purified proteins, is described here together with a series of modifications of substrate and assay conditions that will aid researchers in the identification of the particular class and isoform of PI 3-kinase that is involved in a signaling process under investigation.

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Two sets of ligands, set-1 and set-2, have been prepared by mixing 1,3-diaminopentane and carbonyl compounds (2-acetylpyridine or pyridine-2-carboxaldehyde) in 1:1 and 1:2 ratios, respectively, and employed for the synthesis of complexes with Ni(II) perchlorate, Ni(II) thiocyanate and Ni(II) chloride. Ni(II) perchlorate yields the complexes having general formula [NiL2](ClO4)(2)(L = L-1 [N-3-(1-pyridin-2-yl-ethylidene)-pentane-1,3-diamine] for complex 1 or L-2[N-3-pyridin-2-ylmethylene-pentane-1,3-diamine] for complex 2) in which the Schiff bases are monocondensed terdentate, whereas Ni(II) thiocyanate results in the formation of tetradentate Schiff base complexes, [NiL(SCN)(2)] (L = L-3[N,N'-bis-(1-pyridin-2- yl-ethylidine)-pentane-1,3-diamine] for complex 3 or L-4 [N,N'-bis(pyridin-2-ylmethyline)-pentane-1,3- diamine] for complex 4) irrespective of the sets of ligands used. Complexes 5 {[NiL3(N-3)(2)]} and 6 {[NiL4(N-3)(2)]} are prepared by adding sodium azide to the methanol solution of complexes 1 and 2. Addition of Ni(II) chloride to the set-1 or set-2 ligands produces [Ni(pn)(2)]Cl-2, 7, as the major product, where pn = 1,3-diaminopentane. Formation of the complexes has been explained by the activation of the imine bond by the counter anion and thereby favouring the hydrolysis of the Schiff base. All the complexes have been characterized by elemental analyses and spectral data. Single crystal X-ray diffraction studies con. firm the structures of three representative members, 1, 4 and 7; all of them have distorted octahedral geometry around Ni(II). The bis-complex of terdentate ligands, 1, is the mer isomer, and complexes 4 and 7 possess trans geometry. (C) 2008 Elsevier B. V. All rights reserved.

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Reaction of CuCl2 center dot 2H(2)O with the 1:1 condensate (L) of 2-(2-aminoethyl) pyridine and 1-methyl-2-imidazolecarboxaldehyde in methanol yields monomeric CuLCl2 center dot H2O (1). Recrystallisation of 1 from aqueous methanol medium containing excess of PF6- affords the 1D coordination polymer [CuLCl](n)(PF6)(n) (2). A chloride bridge results in the coordination polymer. A face-to-face interaction is observed between the imidazole rings in 2. The interaction influences the structure and magnetic properties of 2 markedly. The complex 2 is ferromagnetic with a J value of 1.79 +/- 0.01 cm (1). The imidazole fragments in 2 are coordinated to the metal. In mononuclear [HgL2 ''](ClO4)(2), where L '' is the 1:2 condensate of ethylenediamine and 1-methyl-2-imidazolecarboxaldehyde, the imidazolyl moieties are not under the direct influence of the metal. Here the imidazole-imidazole interaction is angular and more distant. (C) 2009 Elsevier B.V. All rights reserved.

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Condensations of 2-(2-aminoethyl)pyridine with 4-methylimidazole-5-carboxaldehyde and 1-methyl-2-imidazolecarboxaldehyde generate the tridentate N donor ligands L and L' respectively. Reactions of Cu(NCS)(2) with L and L' yield respectively CuL(SCN)(NCS) (1) containing a CuN4S core and CuL'(NCS)(2) (2) having a CuN5 core. Both the cores are square pyramidal with SCN bound in 1 at the axial position through the S end. This differential behaviour of SCN in the two complexes despite the ligands being very similar, is investigated by DFT calculations at the B3LYP/TZV level. It is found that DFT calculations predict isolation of the Cu(ligand)(NCS)(2) species for both the ligands L and L'. Presence of an offsetting intermolecular H-bonding between the N atom of the thiocyanate and the N-H proton of the ligand L of an adjacent molecule makes the binding of SCN via the S end feasible in 1 resulting in the H-bonded-dimer Cu2L2(SCN)(2)(NCS)(2). The strength of the H-bond is estimated as 27.1 kJ mol (1) from the DFT calculations. The question of such H-bonding does not arise with L' as it lacks in a similar H atom. Dimeric 1 represents a case of two non-interacting spins. (C) 2008 Elsevier B. V. All rights reserved.

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Reactions of the 1: 2 condensate (L) of benzil dihydrazone and 2-acetylpyridine with Hg(ClO4)(2) center dot xH(2)O and HgI2 yield yellow [HgL2](ClO4)(2) (1) and HgLI2 (2), respectively. Homoleptic 1 is a 8-coordinate double helical complex with a Hg(II)N-8 core crystallising in the space group Pbca with cell dimensions: a = 16.2250(3), b = 20.9563(7), c = 31.9886(11) angstrom. Complex 2 is a 4-coordinate single helical complex having a Hg(II)N2I2 core crystallising in the space group P2(1)/n with cell dimensions a = 9.8011(3), b = 17.6736(6), c = 16.7123(6) angstrom and b = 95.760(3). In complex 1, the N-donor ligand L uses all of its binding sites to act as tetradentate. On the other hand, it acts as a bidentate N-donor ligand in 2 giving rise to a dangling part. From variable temperature H-1 NMR studies both the complexes are found to be stereochemically non-rigid in solution. In the case of 2, the solution process involves wrapping up of the dangling part of L around the metal. (C) 2008 Elsevier B.V. All rights reserved.

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X-ray crystallography shows that [Ag2L2(H2O)(2)](BF4)(2) where L is a 1:1 condensate of 1,2-diphenylethane-1,2-dione and 2-(2-aminoethyl pyridine), contains an Ag(I)-Ag(I) bond of length 2.979(2) angstrom and an angular, intraligand interaction of the keto O with the pi cloud of the pyridine moiety (O-pyridine centroid = 3.12 angstrom). Model MP2/6-311++G(d,p) calculations indicate that the observed lone pair-pi type interaction is stabilising and not merely a tolerated short contact. (C) 2008 Elsevier B.V. All rights reserved.

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Using bis(3,5-dimethylpyrazol-1-yl)methane as an N-N donor ligand, a trans-[Ru-III(N-N)(2)Cl-2](+) core has been isolated from the direct reaction of the ligand with RuCl3 center dot xH(2)O and characterized structurally for the. first time. The core displays a rhombic EPR spectrum and a quasireversible Ru(II/III) couple with an E-1/2 of -0.34 V versus NHE. (C) 2008 Elsevier B.V. All rights reserved.

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Using bis(3,5-dimethylpyrazol-1-yl) methane as the bidentate N donor ligand L, the yellow compound trans-[(RuL2)-L-III(OMe)(2)]ClO4 center dot CH2Cl2 is synthesized. It is a rare example of a mononuclear dialkoxo complex of Ru(III). It shows a quasireversible Ru(II/III) couple at -0.65 V versus NHE in acetonitrile at a Pt electrode. Its magnetic moment at room temperature corresponds to one unpaired electron. It displays a rhombic EPR spectrum in acetone at 77 K with g = 2.219, 2.062 and 1.855. (C) 2009 Elsevier B. V. All rights reserved.

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Starting from previously reported cis-Ru(MeL)(2)Cl-2, where MeL is 4,4,4',4'-tetramethyl-2,2'-bisoxazoline, cis-Ru(MeL)(2)Br-2 (1), cis-Ru( MeL)(2)I-2 (2), cis-Ru(MeL)(2)(NCS)(2) center dot H2O (3), cis-Ru(MeL)(2)(N-3)(2) (4) and cis-[Ru(MeL)(2)(MeCN)(2)](PF6)(2) center dot (CH3)(2)CO (5) are synthesised. The X-ray crystal structures of complexes 1, 2, 3 and 5 have been determined. All the five new complexes have been characterized by FTIR, ESIMS and H-1 NMR. In cyclic voltammetry in acetonitrile at a glassy carbon electrode, the complexes display a quasireversible Ru(II/III) couple in the range 0.32-1.71 V versus NHE. The Ru(II/III) potentials yield a satisfactorily linear correlation with Chatt's ligand constants P-L for the monodantate ligands. From the intercept and by comparing the known situation in Ru(2,2'-bipyridine)(2)L-2, it is concluded that MeL, a non-aromatic diimine, is significantly more pi-acidic than 2,2'-bipyridine. (c) 2008 Elsevier B.V. All rights reserved.