911 resultados para Preferential hydration
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We present an analysis of the oceanic heat advection and its variability in the upper 500 m in the southeastern tropical Pacific (100W–75W, 25S–10S) as simulated by the global coupled model HiGEM, which has one of the highest resolutions currently used in long-term integrations. The simulated climatology represents a temperature advection field arising from transient small-scale (<450 km) features, with structures and transport that appear consistent with estimates based on available observational data for the mooring at 20S, 85W. The transient structures are very persistent (>4 months), and in specific locations they generate an important contribution to the local upper-ocean heat budget, characterised by scales of a few hundred kilometres, and periods of over a year. The contribution from such structures to the local, long-term oceanic heat budget however can be of either sign, or vanishing, depending on the location; and, although there appears some organisation in preferential areas of activity, the average over the entire region is small. While several different mechanisms may be responsible for the temperature advection by transients, we find that a significant, and possibly dominant, component is associated with vortices embedded in the large-scale, climatological salinity gradient associated with the fresh intrusion of mid-latitude intermediate water which penetrates north-westward beneath the tropical thermocline
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The electrospinning of urethane based low molecular weight polymers differing only in the nature of the hydrogen bonding end-groups has been investigated. For the end-groups with the lowest binding constants at maximum solubility only droplets, are produced at the electrode; in contrast, increasing the binding constant of the end-group results in electrospun fibres being produced. The properties of the fibres produced are subject to changes in solvent, concentration and temperature. Typical diameters for these fibres were found to be some 10 s of μm, rather than the sub-micron dimensions often produced in electrospinning systems. Such diameters are related to the high initial concentrations required; this also may influence the rate of solvent removal and preferential surface solidification which feature in these examples. A simple theoretical model is used to relate the association constant to the molecular weight required for fibre formation; significantly lower levels of association are required for higher molecular weight macromonomers compared to smaller molecular systems.
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This article discusses the sources of competitive advantage in the interwar British radio industry. Specifically, it examines why sections of the industry that reaped substantial monopoly rents from the downstream value chain failed to dominate the industry. During the 1920s Marconi (which controlled the fundamental UK patents) had a key cost advantage, as had other members of the ‘Big Six’ electrical engineering firms which formed the BBC and were granted preferential royalties. Meanwhile the valve manufacturers' cartel was also able to extract high rents from set manufacturers. The vertical integration literature suggests that input monopolists have incentives to control downstream production. Yet—in contrast to the gramophone industry, which became concentrated into two huge companies following market saturation in the 1930s—radio retained a much more competitive structure. The Big Six failed to capitalize fully on their initial cost advantages owing to logistical weaknesses in supplying markets subject to rapid technical and design obsolescence. Subsequently, during the 1930s, marketing innovations are shown to have played a key role in allowing several independents to establish successful brands. This gave them sufficient scale to provide strong bargaining positions with input suppliers, negating most of their initial cost disadvantage.
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By using simulation methods, we studied the adsorption of binary CO2-CH4 mixtures on various CH4 preadsorbed carbonaceous materials (e.g., triply periodic carbon minimal surfaces, slit-shaped carbon micropores, and Harris's virtual porous carbons) at 293 K. Regardless of the different micropore geometry, two-stage mechanism of CH4 displacement from carbon nanospaces by coadsorbed CO2 has been proposed. In the first stage, the coadsorbed CO2 molecules induced the enhancement of CH4 adsorbed amount. In the second stage, the stronger affinity of CO2 to flat/curved graphitic surfaces as well as CO2-CO2 interactions cause the displacement of CH4 molecules from carbonaceous materials. The operating conditions of CO2-induced cleaning of the adsorbed phase from CH4 mixture component strongly depend on the size of the carbon micropores, but, in general, the enhanced adsorption field in narrow carbon ultramicropores facilitates the nonreactive displacement of CH4 by coadsorbed CO2. This is because in narrow carbon ultramicropores the equilibrium CO2/CH4 selectivity (i.e., preferential adsorption toward CO2) increased significantly. The adsorption field in wider micropores (i.e., the overall surface energy) for both CO2 and CH4 is very similar, which decreases the preferential CO2 adsorption. This suppresses the displacement of CH4 by coadsorbed CO2 and assists further adsorption of CH4 from the bulk mixture (i.e., CO2/CH4 mixing in adsorbed phase).
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The importance of the second messengers calcium (Ca(2+)) and diacylglycerol (DAG) in platelet signal transduction was established more than 30 years ago. Whereas protein kinase C (PKC) family members were discovered as the targets of DAG, little is known about the molecular identity of the main Ca(2+) sensor(s). We here identify Ca(2+) and DAG-regulated guanine nucleotide exchange factor I (CalDAG-GEFI) as a critical molecule in Ca(2+)-dependent platelet activation. CalDAG-GEFI, through activation of the small GTPase Rap1, directly triggers integrin activation and extracellular signal-regulated kinase-dependent thromboxane A(2) (TxA(2)) release. CalDAG-GEFI-dependent TxA(2) generation provides crucial feedback for PKC activation and granule release, particularly at threshold agonist concentrations. PKC/P2Y12 signaling in turn mediates a second wave of Rap1 activation, necessary for sustained platelet activation and thrombus stabilization. Our results lead to a revised model for platelet activation that establishes one molecule, CalDAG-GEFI, at the nexus of Ca(2+)-induced integrin activation, TxA(2) generation, and granule release. The preferential activation of CalDAG-GEFI over PKC downstream of phospholipase C activation, and the different kinetics of CalDAG-GEFI- and PKC/P2Y12-mediated Rap1 activation demonstrate an unexpected complexity to the platelet activation process, and they challenge the current model that DAG/PKC-dependent signaling events are crucial for the initiation of platelet adhesion.
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A rheological model of sea ice is presented that incorporates the orientational distribution of ice thickness in leads embedded in isotropic floe ice. Sea ice internal stress is determined by coulombic, ridging and tensile failure at orientations where corresponding failure criteria are satisfied at minimum stresses. Because sea ice traction increases in thinner leads and cohesion is finite, such failure line angles are determined by the orientational distribution of sea ice thickness relative to the imposed stresses. In contrast to the isotropic case, sea ice thickness anisotropy results in these failure lines becoming dependent on the stress magnitude. Although generally a given failure criteria type can be satisfied at many directions, only two at most are considered. The strain rate is determined by shearing along slip lines accompanied by dilatancy and closing or opening across orientations affected by ridging or tensile failure. The rheology is illustrated by a yield curve determined by combining coulombic and ridging failure for the case of two pairs of isotropically formed leads of different thicknesses rotated with regard to each other, which models two events of coulombic failure followed by dilatancy and refreezing. The yield curve consists of linear segments describing coulombic and ridging yield as failure switches from one lead to another as the stress grows. Because sliding along slip lines is accompanied by dilatancy, at typical Arctic sea ice deformation rates a one-day-long deformation event produces enough open water that these freshly formed slip lines are preferential places of ridging failure.
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A discrete-element model of sea ice is used to study how a 90° change in wind direction alters the pattern of faults generated through mechanical failure of the ice. The sea-ice domain is 400km in size and consists of polygonal floes obtained through a Voronoi tessellation. Initially the floes are frozen together through viscous–elastic joints that can break under sufficient compressive, tensile and shear deformation. A constant wind-stress gradient is applied until the initially frozen ice pack is broken into roughly diamond-shaped aggregates, with crack angles determined by wing-crack formation. Then partial refreezing of the cracks delineating the aggregates is modelled through reduction of their length by a particular fraction, the ice pack deformation is neglected and the wind stress is rotated by 90°. New cracks form, delineating aggregates with a different orientation. Our results show the new crack orientation depends on the refrozen fraction of the initial faults: as this fraction increases, the new cracks gradually rotate to the new wind direction, reaching 90° for fully refrozen faults. Such reorientation is determined by a competition between new cracks forming at a preferential angle determined by the wing-crack theory and at old cracks oriented at a less favourable angle but having higher stresses due to shorter contacts across the joints
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Terahertz power transmission spectroscopy (TPTS) measurements have been carried out to detect a difference between the hydration shells of G-quadruplex forming DNA sequences in strand and quadruplex configuration. Evidence of a change in hydration shell was observed.
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In situ generation of HCl or HBr in alcohol leads to O-protonation of the amide group of carbamazepine. Six salt phases have been produced using this method and their crystal structures determined by single crystal diffraction. A new polymorph of carbamazepine hydrochloride is described as are two polymorphs of carbamazepine hydrobromide. All are protonated at the amide O atom to give RC(OH)NH2 cations. Prolonged exposure to air results in addition of water to the solid salt forms. Such hydration of carbamazepine hydrobromide simply gives a monohydrated phase, but similar treatment of the equivalent hydrochloride results in partial loss of HCl and the transfer of the remaining proton from the amide group to water to give [carbamazepine][H3O]0.5[Cl]0.5·H2O. A similar hydronium chloride species is the only product isolated after reaction of the carbamazepine analogue cytenamide with HCl generated in methanol.
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Seed dormancy induction and alleviation in the winter-flowering moist temperate woodland species Galanthus nivalis and Narcissus pseudonarcissus are complex and poorly understood. Temperature, light and desiccation were investigated to elucidate their role in the germination ecophysiology of these species. Outdoor and laboratory experiments simulating different seasonal temperatures, seasonal durations, and temperature fluctuations; the presence of light during different seasons; and intermittent drying (during the summer period) over several ‘years’ investigated the importance of these factors in germination. Warm summer-like temperatures (20°C) were necessary for germination at subsequent cooler autumn-like temperatures (greatest at 15°C in G. nivalis and 10°C in N. pseudonarcissus). As the warm temperature duration increased so did germination at subsequent cooler temperatures; further germination occurred in subsequent ‘years’ at cooler temperatures following a second, and also third, warm period. Germination was significantly greater in darkness, particularly in G. nivalis. Dormancy increased with seed maturation period in G. nivalis, because seeds extracted from green capsules germinated more readily than those from yellow. Desiccation increased dormancy in an increasing proportion of N. pseudonarcissus seeds the later they were dried in ‘summer’. Seed viability was only slightly reduced by desiccation in N. pseudonarcissus but was poor and variable in G. nivalis. Shoot formation occurred both at the temperature at which germination was greatest and also if 5°C cooler. In summary, continuous hydration of seeds of both species during warm summer-like temperatures results in the gradual release of seed dormancy; thereafter, darkness and cooler temperatures promote germination. Cold temperatures, increased seed maturity (G. nivalis), and desiccation (N. pseudonarcissus) increase dormancy while light inhibits germination.
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Among the range of materials used in bioengineering, parylene-C has been used in combination with silicon oxide and in presence of the serum proteins, in cell patterning. However, the structural properties of adsorbed serum proteins on these substrates still remain elusive. In this study, we use an optical biosensing technique to decipher the properties of fibronectin (Fn) and serum albumin adsorbed on parylene-C and silicon oxide substrates. Our results show the formation of layers with distinct structural and adhesive properties. Thin, dense layers are formed on parylene-C, whereas thicker, more diffuse layers are formed on silicon oxide. These results suggest that Fn acquires a compact structure on parylene-C and a more extended structure on silicon oxide. Nonetheless, parylene-C and silicon oxide substrates coated with Fn host cell populations that exhibit focal adhesion complexes and good cell attachment. Albumin adopts a deformed structure on parylene-C and a globular structure on silicon oxide, and does not support significant cell attachment on either surface. Interestingly, the co-incubation of Fn and albumin at the ratio found in serum, results in the preferential adsorption of albumin on parylene-C and Fn on silicon oxide. This finding is supported by the exclusive formation of focal adhesion complexes in differentiated mouse embryonic stem cells (CGR8), cultured on Fn/albumin coated silicon oxide, but not on parylene-C. The detailed information provided in this study on the distinct properties of layers of serum proteins on substrates such as parylene-C and silicon oxide is highly significant in developing methods for cell patterning.
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Threat-relevant stimuli such as fear faces are prioritized by the human visual system. Recent research suggests that this prioritization begins during unconscious processing: A specialized (possibly subcortical) pathway evaluates the threat relevance of visual input, resulting in preferential access to awareness for threat stimuli. Our data challenge this claim. We used a continuous flash suppression (CFS) paradigm to present emotional face stimuli outside of awareness. It has been shown using CFS that salient (e.g., high contrast) and recognizable stimuli (faces, words) become visible more quickly than less salient or less recognizable stimuli. We found that although fearful faces emerge from suppression faster than other faces, this was wholly explained by their low-level visual properties, rather than their emotional content. We conclude that, in the competition for visual awareness, the visual system prefers and promotes unconscious stimuli that are more “face-like,” but the emotional content of a face has no effect on stimulus salience.
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Hydration-dependent DNA deformation has been known since Rosalind Franklin recognised that the relative humidity of the sample had to be maintained to observe a single conformation in DNA fibre diffraction. We now report for the first time the crystal structure, at the atomic level, of a dehydrated form of a DNA duplex and demonstrate the reversible interconversion to the hydrated form at room temperature. This system, containing d(TCGGCGCCGA) in the presence of Λ-[Ru(TAP)2(dppz)]2+ (TAP = 1,4,5,8-tetraazaphenanthrene, dppz = dipyridophenazine), undergoes a partial transition from an A/B hybrid to the A-DNA conformation, at 84-79% relative humidity. This is accompanied by an increase in kink at the central step from 22° to 51°, with a large movement of the terminal bases forming the intercalation site. This transition is reversible on rehydration. Seven datasets, collected from one crystal at room temperature, show the consequences of dehydration at near-atomic resolution. This result highlights that crystals, traditionally thought of as static systems, are still dynamic and therefore can be the subject of further experimentation.
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The aim of this study was to evaluate the effects of inulin as fat replacer on short dough biscuits and their corresponding doughs. A control formulation, with no replacement, and four formulations in which 10, 20, 30, and 40 % of shortening was replaced by inulin were studied. In the dough, shortening was observed surrounding flour components. At higher fat replacement levels, flour was more available for hydration leading to significant (P<0.05) harder doughs: from 2.76 (0.12)N in 10 % fat-replaced biscuits to 5.81 (1.56)N in 30 % fat-replaced ones. Biscuit structure was more continuous than dough structure. A continuous fat layer coated the matrix surface, where starch granules were embedded. In general, weight loss during baking and water activity decreased significantly (P<0.05) as fat replacement increased. Biscuit dimensions and aeration decreased when fat replacement increased, e.g., width gain was +1.20 mm in 10 fat-replaced biscuits and only +0.32 mm in 40 % fat-replaced ones. Panelist found biscuits with 20 % of fat replacement slightly harder than control biscuits. It can be concluded that shortening may be partially replaced, up to 20 %, with inulin. These low fat biscuits are similar than the control biscuits, and they can have additional health benefits derived from inulin presence.
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Background Children with callous-unemotional (CU) traits, a proposed precursor to adult psychopathy, are characterized by impaired emotion recognition, reduced responsiveness to others’ distress, and a lack of guilt or empathy. Reduced attention to faces, and more specifically to the eye region, has been proposed to underlie these difficulties, although this has never been tested longitudinally from infancy. Attention to faces occurs within the context of dyadic caregiver interactions, and early environment including parenting characteristics has been associated with CU traits. The present study tested whether infants’ preferential tracking of a face with direct gaze and levels of maternal sensitivity predict later CU traits. Methods Data were analyzed from a stratified random sample of 213 participants drawn from a population-based sample of 1233 first-time mothers. Infants’ preferential face tracking at 5 weeks and maternal sensitivity at 29 weeks were entered into a weighted linear regression as predictors of CU traits at 2.5 years. Results Controlling for a range of confounders (e.g., deprivation), lower preferential face tracking predicted higher CU traits (p = .001). Higher maternal sensitivity predicted lower CU traits in girls (p = .009), but not boys. No significant interaction between face tracking and maternal sensitivity was found. Conclusions This is the first study to show that attention to social features during infancy as well as early sensitive parenting predict the subsequent development of CU traits. Identifying such early atypicalities offers the potential for developing parent-mediated interventions in children at risk for developing CU traits.