949 resultados para Materials and the technique
Resumo:
Although tactile representations of the two body sides are initially segregated into opposite hemispheres of the brain, behavioural interactions between body sides exist and can be revealed under conditions of tactile double simultaneous stimulation (DSS) at the hands. Here we examined to what extent vision can affect body side segregation in touch. To this aim, we changed hand-related visual input while participants performed a go/no-go task to detect a tactile stimulus delivered to one target finger (e.g., right index), stimulated alone or with a concurrent non-target finger either on the same hand (e.g., right middle finger) or on the other hand (e.g., left index finger = homologous; left middle finger = non-homologous). Across experiments, the two hands were visible or occluded from view (Experiment 1), images of the two hands were either merged using a morphing technique (Experiment 2), or were shown in a compatible vs incompatible position with respect to the actual posture (Experiment 3). Overall, the results showed reliable interference effects of DSS, as compared to target-only stimulation. This interference varied as a function of which non-target finger was stimulated, and emerged both within and between hands. These results imply that the competition between tactile events is not clearly segregated across body sides. Crucially, non-informative vision of the hand affected overall tactile performance only when a visual/proprioceptive conflict was present, while neither congruent nor morphed hand vision affected tactile DSS interference. This suggests that DSS operates at a tactile processing stage in which interactions between body sides can occur regardless of the available visual input from the body.
Resumo:
Although the ‘chronicle of chronicles’ compiled at Worcester c1095-c1140 is now firmly attributed to John of Worcester, rather than Florence, major questions remain. A central issue is that the semi-autograph manuscript of the chronicle (now Oxford, Corpus Christi College, Ms 157) underwent several alterations to its structure and contents, as codicological evidence demonstrates. These included the incorporation of important illuminations, which have been surprisingly little considered in their overall manuscript context. This article focuses on these illuminations, and will argue that their presence in this version of the chronicle makes it something even more distinctive than the learned, revisionist chronological work of Marianus Scotus upon which it was based. John of Worcester’s chosen images are linked not only to his political narrative but also to theological works and to cutting-edge science, newly translated from Arabic. The presence of such miniatures in a twelfth-century chronicle is unique, and they are central to the final form given to the Worcester chronicle by John of Worcester himself in this key manuscript. Their analysis thus brings into focus the impressive assembly of materials which the chronicle offered to readers, to shape their understanding of ongoing events.
Resumo:
Two members of the tetradentate N-donor ligand families 6,6′-bis(1,2,4-triazin-3-yl)-2,2′-bipyridine (BTBP) and 2,9-bis(1,2,4-triazin-3-yl)-1,10-phenanthroline (BTPhen) currently being developed for separating actinides from lanthanides have been studied. It has been confirmed that CyMe4-BTPhen 2 has faster complexation kinetics than CyMe4-BTBP 1. The values for the HOMO−LUMO gap of 2 are comparable with those of CyMe4-BTBP 1 for which the HOMO−LUMO gap was previously calculated to be 2.13 eV. The displacement of BTBP from its bis-lanthanum(III) complex by BTPhen was observed by NMR, and constitutes the only direct evidence for the greater thermodynamic stability of the complexes of BTPhen. NMR competition experiments suggest the following order of bis-complex stability: 1:2 bis-BTPhen complex ≥ heteroleptic BTBP/BTPhen 1:2 bis-complex > 1:2 bis-BTBP complex. Kinetics studies on some bis-triazine N-donor ligands using the stopped-flow technique showed a clear relationship between the rates of metal ion complexation and the degree to which the ligand is preorganized for metal binding. The BTBPs must overcome a significant (ca. 12 kcal mol−1) energy barrier to rotation about the central biaryl C−C axis in order to achieve the cis−cis conformation that is required to form a complex, whereas the cis−cis conformation is fixed in the BTPhens. Complexation thermodynamics and kinetics studies in acetonitrile show subtle differences between the thermodynamic stabilities of the complexes formed, with similar stability constants being found for both ligands. The first crystal structure of a 1:1 complex of CyMe4-BTPhen 2 with Y(NO3)3 is also reported. The metal ion is 10- coordinate being bonded to the tetradentate ligand 2 and three bidentate nitrate ions. The tetradentate ligand is nearly planar with angles between consecutive rings of 16.4(2)°, 6.4(2)°, 9.7(2)°, respectively.
Resumo:
Much has been written about where the boundaries of the firm are drawn, but little about what occurs at the boundaries themselves. When a firm subcontracts, does it inform its suppliers fully of what it requires, or is it willing to accept what they have available? In practice firms often engage in a dialogue, or conversation, with their suppliers, in which at first they set out their general requirements, and only when the supplier reports back on how these can be met are their more specific requirements set out. This paper models such conversations as a rational response to communication costs. The model is used to examine the impact of new information technology, such as CAD/CAM, on the conduct of subcontracting. It can also be used to examine its impact on the marketing activities of firms. The technique of analysis, which is based on the economic theory of teams, has more general applications too. It can be used to model all the forms of dialogue involved in the processes of coordination both within and between firms.
Resumo:
This paper takes the form of a dialogue between an archaeologist and a sociologist. In recent years, interdisciplinary working has become increasingly fashionable within academia. The aim of our exchange was to establish exactly what implications this way of working has for understandings of material culture. Our methodology was simple, involving the ‘archaeological’ and ‘sociological’ analysis of two different objects. In undertaking this work, we hoped to bring about new or different understandings of the objects under scrutiny. The process was indeed successful, but not necessarily in the ways we had expected. Ultimately, it revealed a complex set of questions about how the materials of culture are conceptualized and understood, and led us to a renewed appreciation of the theoretical and methodological qualities of what we do within our respective disciplines
Resumo:
The weekly dependence of pollutant aerosols in the urban environment of Lisbon (Portugal) is inferred from the records of atmospheric electric field at Portela meteorological station (38°47′N,9°08′W). Measurements were made with a Bendorf electrograph. The data set exists from 1955 to 1990, but due to the contaminating effect of the radioactive fallout during 1960 and 1970s, only the period between 1980 and 1990 is considered here. Using a relative difference method a weekly dependence of the atmospheric electric field is found in these records, which shows an increasing trend between 1980 and 1990. This is consistent with a growth of population in the Lisbon metropolitan area and consequently urban activity, mainly traffic. Complementarily, using a Lomb–Scargle periodogram technique the presence of a daily and weekly cycle is also found. Moreover, to follow the evolution of theses cycles, in the period considered, a simple representation in a colour surface plot representation of the annual periodograms is presented. Further, a noise analysis of the periodograms is made, which validates the results found. Two datasets were considered: all days in the period, and fair-weather days only.
Resumo:
Recent studies of the variation of geomagnetic activity over the past 140 years have quantified the "coronal source" magnetic flux F-s that leaves the solar atmosphere and enters the heliosphere and have shown that it has risen, on average, by an estimated 34% since 1963 and by 140% since 1900. This variation of open solar flux has been reproduced by Solanki et al. [2000] using a model which demonstrates how the open flux accumulates and decays, depending on the rate of flux emergence in active regions and on the length of the solar cycle. We here use a new technique to evaluate solar cycle length and find that it does vary in association with the rate of change of F-s in the way predicted. The long-term variation of the rate of flux emergence is found to be very similar in form to that in F-s, which may offer a potential explanation of why F-s appears to be a useful proxy for extrapolating solar total irradiance back in time. We also find that most of the variation of cosmic ray fluxes incident on Earth is explained by the strength of the heliospheric field (quantified by F-s) and use observations of the abundance of the isotope Be-10 (produced by cosmic rays and deposited in ice sheets) to study the decrease in F-s during the Maunder minimum. The interior motions at the base of the convection zone, where the solar dynamo is probably located, have recently been revealed using the helioseismology technique and found to exhibit a 1.3-year oscillation. This periodicity is here reported in observations of the interplanetary magnetic field and geomagnetic activity but is only present after 1940, When present, it shows a strong 22-year variation, peaking near the maximum of even-numbered sunspot cycles and showing minima at the peaks of odd-numbered cycles. We discuss the implications of these long-term solar and heliospheric variations for Earth's environment.
Resumo:
An equation of Monge-Ampère type has, for the first time, been solved numerically on the surface of the sphere in order to generate optimally transported (OT) meshes, equidistributed with respect to a monitor function. Optimal transport generates meshes that keep the same connectivity as the original mesh, making them suitable for r-adaptive simulations, in which the equations of motion can be solved in a moving frame of reference in order to avoid mapping the solution between old and new meshes and to avoid load balancing problems on parallel computers. The semi-implicit solution of the Monge-Ampère type equation involves a new linearisation of the Hessian term, and exponential maps are used to map from old to new meshes on the sphere. The determinant of the Hessian is evaluated as the change in volume between old and new mesh cells, rather than using numerical approximations to the gradients. OT meshes are generated to compare with centroidal Voronoi tesselations on the sphere and are found to have advantages and disadvantages; OT equidistribution is more accurate, the number of iterations to convergence is independent of the mesh size, face skewness is reduced and the connectivity does not change. However anisotropy is higher and the OT meshes are non-orthogonal. It is shown that optimal transport on the sphere leads to meshes that do not tangle. However, tangling can be introduced by numerical errors in calculating the gradient of the mesh potential. Methods for alleviating this problem are explored. Finally, OT meshes are generated using observed precipitation as a monitor function, in order to demonstrate the potential power of the technique.
Resumo:
The [Ru(phen)2(dppz)]2+ complex (1) is non-emissive in water but is highly luminescent in organic solvents or when bound to DNA, making it a useful probe for DNA binding. To date, a complete mechanistic explanation for this “light-switch” effect is still lacking. With this in mind we have undertaken an ultrafast time resolved infrared (TRIR) study of 1 and directly observe marker bands between 1280–1450 cm-1, which characterise both the emissive “bright” and the non-emissive “dark” excited states of the complex, in CD3CN and D2O respectively. These characteristic spectral features are present in the [Ru(dppz)3]2+ solvent light-switch complex but absent in [Ru(phen)3]2+, which is luminescent in both solvents. DFT calculations show that the vibrational modes responsible for these characteristic bands are predominantly localised on the dppz ligand. Moreover, they reveal that certain vibrational modes of the “dark” excited state couple with vibrational modes of two coordinating water molecules, and through these to the bulk solvent, thus providing a new insight into the mechanism of the light-switch effect. We also demonstrate that the marker bands for the “bright” state are observed for both L- and D enantiomers of 1 when bound to DNA and that photo-excitation of the complex induces perturbation of the guanine and cytosine carbonyl bands. This perturbation is shown to be stronger for the L enantiomer, demonstrating the different binding site properties of the two enantiomers and the ability of this technique to determine the identity and nature of the binding site of such intercalators.
Resumo:
The human body occupies a central place in Rukeyser’s poetry. Her characters’ physical experiences inspire their search for an artistic form and a holistic vision that reconciles the corporeal and conceptual aspects of their life. My thesis deals with Rukeyser’s reconciliation of disparate aspects of existence through the image of the human body and the practical experiences she underwent in her personal life and incorporated in her poetry. I discuss her poetry of the 1940s, where a tension is observed between the artist’s personal life and her art, which she attempts to resolve by adopting an artistic form that accommodates her quotidian experiences. I study, mainly through her poetry of the 1950s, Rukeyser’s poetic technique in the light of her organicist poetics and the combination of tendencies to coercion and suggestiveness distinguishing her style. I examine her portrayal of the suffering body in her poetry of the 1960s and 1970s. By means of their physical experiences, the ill, her despised and the imprisoned protagonists undergo a process of development whereby they perceive the different aspects of their identity and attempt to broaden perspectives on their situation by reconciling them. I argue that Rukeyser’s engagement with physical encounters and with the poem as an inclusive, organic body enables her to reconcile disparate elements in her poetry, such as her personal life and her art, her individual existence and the public world, as well as the distinct aspects of her characters’ identity. Her vatic outlook, which integrates distinct aspects of experience, is consistent with Merleau-Ponty’s idea of human perception as characterised by the two interdependent positions of immanence and transcendence. Rukeyser’s poetry depicts her physical engagement with quotidian events of her life as a factor of artistic inspiration. These situations constitute shared human experiences that enable her to imagine the links binding her to other people and the world at large. The poet’s personal experiences inspire her search for an artistic form that accommodates them. Her perception of the concrete aspect of her individual existence gains significance when it is linked to social and political issues. Both the private and public are thus seen as interconnected, and they affect the existence of each other while retaining their distinctness.
Resumo:
The objective of this work was to study the color, opacity, crystallinity, and the thermal and mechanical properties of films based on blends of gelatin and five different types of PVA [poly(vinyl alcohol)], with and without a plasticizer. The effect of the degree of hydrolysis of the PVA and the glycerol concentration on these properties was studied using colorimetry, differential scanning calorimetry (DSC), X-ray diffraction (XRD) and tensile mechanical tests. All films were essentially colorless (Delta E* < 5) and with low opacity ( Y <= 2.1). The DSC results were typical of partially crystalline materials, showing some phase separation characterized by a glass transition (T(g) = 40-55 degrees C), related to the amorphous part of the material, followed by two endothermic peaks related to the melting (T(m) = 100-160 and 170-210 degrees C) of the crystallites. The XRD results confirmed the crystallinity of the films. The film produced with PVA Celvol((R)) 418 (DH = 91.8%) showed the highest tensile resistance (tensile strength = 38 MPa), for films without plasticizer. However, with glycerol, the above-mentioned PVA and the PVA Celvol((R)) 504 produced the least resistant films of all the PVA types. But, although the mechanical properties of the blended films depended on the type of PVA used, there was no direct relationship between these properties and the degree of hydrolysis of the PVA. The properties studied were more closely dependent on the glycerol concentration. Finally, the mechanical resistance of the films presented a linear relationship with the glass transition temperature of the films. (c) 2007 Elsevier Ltd. All rights reserved.
Resumo:
A systematic and comprehensive study of the interaction of citrate-stabilized gold nanoparticles with triruthenium cluster complexes of general formula [Ru(3)(CH(3)COO)(6)(L)](+) [L = 4-cyanopyridine (4-CNpy), 4,4`-bipyridine (4,4`-bpy) or 4,4`-bis(pyridyl)ethylene (bpe)] has been carried out. The cluster-nanoparticle interaction in solution and the construction of thin films of the hybrid materials were investigated in detail by electronic and surface plasmon resonance (SPR) spectroscopy, Raman scattering spectroscopy and scanning electron microscopy (SEM). Citrate-stabilized gold nanoparticles readily interacted with [Ru(3)O(CH(3)COO)(6)(L)(3)](+) complexes to generate functionalized nanoparticles that tend to aggregate according to rates and extents that depend on the bond strength defined by the characteristics of the cluster L ligands following the sequence bpe > 4,4`-bpy >> 4-CNpy. The formation of compact thin films of hybrid AuNP/[Ru(3)O(CH(3)COO)(6)(L)(3)](+) derivatives with L = bpe and 4,4`-bpy indicated that the stability/lability of AuNP-cluster bonds as well as their solubility are important parameters that influence the film contruction process. Fluorine-doped tin oxide electrodes modified with thin films of these nanomaterials exhibited similar electrocatalytic activity but much higher sensitivity than a conventional gold electrode in the oxidation of nitrite ion to nitrate depending on the bridging cluster complex, demonstrating the high potential for the development of amperometric sensors.
Resumo:
The question posed in the title has been addressed by studying the swelling of celluloses at 20 C by twenty protic solvents, including water; linear- and branched-chain aliphatic alcohols; unsaturated aliphatic alcohols, and alkoxyalcohols. The biopolymers investigated included microcrystalline cellulose, MC, native and never-dried mercerized cotton cellulose, cotton and M-cotton, and native and never-dried mercerized eucalyptus cellulose, eucalyptus and M-eucalyptus, respectively. In most cases, better correlations with the physico-chemical properties of the solvents were obtained when the swelling was expressed as number of moles of solvent/anhydroglucose unit, nSw, rather than as % increase in sample weight. The descriptors employed in these correlations included, where available, Hildebrand`s solubility parameters, Gutmann`s acceptor and donor numbers, solvent molar volume, V(S), as well as solvatochromic parameters. The latter, employed for the first time for correlating the swelling of biopolymers, included empirical solvent polarity, E(T)(30), solvent ""acidity"", alpha(S), ""basicity"", beta(S), and dipolarity/polarizability, pi(S)*, respectively. Small regression coefficients and large sums of the squares of the residues were obtained when values of nSw were correlated with two solvent parameters. Much better correlations were obtained with three solvent parameters. The most statistically significant descriptor in the correlation equation depends on the cellulose, being pi(S)* for MC, cotton, and eucalyptus, and V(S) for M-cotton and M-eucalyptus. The best correlations were obtained with the same set of four parameters for all celluloses, namely, solvent pKa (or alpha(S)) beta(S), pi(S)*, and V(S), respectively. These results indicate that the supra-molecular structure of the biopolymer, in particular the average sizes of crystallites and micro-pores, and the presence of its chains in parallel (cellulose I) or anti-parallel (cellulose II) arrangements control its swelling. At least for the present biopolymer/solvent systems, use of solvatochromic parameters is a superior alternative to Hildebrand`s solubility parameters and/or Gutmann`s acceptor and donor numbers. The relevance of these results to the accessibility of the hydroxyl groups of cellulose, hence to its reactivity, is briefly discussed.