70 resultados para RESIDENCE TIME DISTRIBUTION


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We show that an electrostatic qubit located near a Bose-Einstein condensate trapped in a symmetric double-well potential can be used to measure the duration the qubit has spent in one of its quantum states. The strong, medium, and weak measurement regimes are analyzed. The analogy between the residence and the traversal (tunnelling) times is highlighted.

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Marine radiocarbon bomb-pulse time histories of annually resolved archives from temperate regions have been underexploited. We present here series of Delta C-14 excess from known-age annual increments of the long-lived bivalve mollusk Arctica islandica from 4 sites across the coastal North Atlantic (German Bight, North Sea; Tromso, north Norway; Siglufjordur, north Icelandic shelf; Grimsey, north Icelandic shelf) combined with published series from Georges Bank and Sable Bank (NW Atlantic) and the Oyster Ground (North Sea). The atmospheric bomb pulse is shown to be a step-function whose response in the marine environment is immediate but of smaller amplitude and which has a longer decay time as a result of the much larger marine carbon reservoir. Attenuation is determined by the regional hydrographic setting of the sites, vertical mixing, processes controlling the isotopic exchange of C-14 at the air-sea boundary, C-14 content of the freshwater flux, primary productivity, and the residence time of organic matter in the sediment mixed layer. The inventories form a sequence from high magnitude-early peak (German Bight) to low magnitude-late peak (Grimsey). All series show a rapid response to the increase in atmospheric Delta C-14 excess but a slow response to the subsequent decline resulting from the succession of rapid isotopic air-sea exchange followed by the more gradual isotopic equilibration in the mixed layer due to the variable marine carbon reservoir and incorporation of organic carbon from the sediment mixed layer. The data constitute calibration series for the use of the bomb pulse as a high-resolution dating tool in the marine environment and as a tracer of coastal ocean water masses.

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Dapivirine mucoadhesive gels and freeze-dried tablets were prepared using a 3 x 3 x 2 factorial design. An artificial neural network (ANN) with multi-layer perception was used to investigate the effect of hydroxypropyl-methylcellulose (HPMC): polyvinylpyrrolidone (PVP) ratio (XI), mucoadhesive concentration (X2) and delivery system (gel or freeze-dried mucoadhesive tablet, X3) on response variables; cumulative release of dapivirine at 24 h (Q(24)), mucoadhesive force (F-max) and zero-rate viscosity. Optimisation was performed by minimising the error between the experimental and predicted values of responses by ANN. The method was validated using check point analysis by preparing six formulations of gels and their corresponding freeze-dried tablets randomly selected from within the design space of contour plots. Experimental and predicted values of response variables were not significantly different (p > 0.05, two-sided paired t-test). For gels, Q(24) values were higher than their corresponding freeze-dried tablets. F-max values for freeze-dried tablets were significantly different (2-4 times greater, p > 0.05, two-sided paired t-test) compared to equivalent gets. Freeze-dried tablets having lower values for X1 and higher values for X2 components offered the best compromise between effective dapivirine release, mucoadhesion and viscosity such that increased vaginal residence time was likely to be achieved. (C) 2009 Elsevier B.V. All rights reserved.

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Precise control over the interfacial area of aqueous and organic slugs in segmented flow in a microchannel reactor provides an attractive means to optimize the yield and productivity of a phase-transfer-catalyzed reaction. Herein, we report the selective alkylation of phenylacetonitrile to the monoalkylated product in a microchannel of 250-mu m internal diameter operated in a continuous and solvent-free manner in the slug-flow regime. The conversion of phenylacetonitrile increased from 40% to 99% as a result of a 97% larger slug surface-to-volume ratio when the volumetric aqueous-to-organic phase flow ratio was raised from 1.0 to 6.1 at the same residence time. The larger surface-to-volume ratio significantly promoted catalyst phase transfer but decreased selectivity because of the simultaneous increase of the rate of the consecutive reaction to the dialkylated product. There exists all Optimum flow ratio with a maximum productivity. Conversion and selectivity in the microchannel reactor were both found to be significantly larger than in a stirred reactor.

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The kinetics of the liquid-phase hydrogenation of citral (3,7-dimethyl-2,6-octadienal) on Au/TiO2 and Pt-Sn/TiO2 thin films was studied in the temperature range 313-353 K and citral concentrations of 0.25-10.0 mol m(-3). The thin films were deposited onto the inner walls of silica capillaries with internal diameter of 250 mu m. First-order dependence on hydrogen pressure and near zero order dependence on citral concentration were observed for the initial rate of citral hydrogenation over the Pt-Sn/TiO2 and Au/TiO2 thin films. The Au/TiO2 catalyst prevents citronellal formation. The highest yield of unsaturated alcohols was obtained on the Pt-Sn/TiO2 film at a reaction temperature of 343 K, liquid residence time of 30 min and a citral conversion of 99%. (C) 2011 Elsevier B.V. All rights reserved.

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Supported ionic liquid membranes (SILMs) has the potential to be a new technological platform for gas/organic vapour separation because of the unique non-volatile nature and discriminating gas dissolution properties of room temperature ionic liquids (ILs). This work starts with an examination of gas dissolution and transport properties in bulk imidazulium cation based ionic liquids [Cnmim][NTf2] (n = 2.4, 6, 8.10) from simple gas H2, N2, to polar CO2, and C2H6, leading to a further analysis of how gas dissolution and diffusion are influenced by molecular specific gas-SILMs interactions, reflected by differences in gas dissolution enthalpy and entropy. These effects were elucidated again during gas permeation studies by examining how changes in these properties and molecular specific interactions work together to cause deviations from conventional solution–diffusion theory and their impact on some remarkably contrasting gas perm-selectivity performance. The experimental perm-selectivity for all tested gases showed varied and contrasting deviation from the solution–diffusion, depending on specific gas-IL combinations. It transpires permeation for simpler non-polar gases (H2, N2) is diffusion controlled, but strong molecular specific gas-ILs interactions led to a different permeation and selectivity performance for C2H6 and CO2. With exothermic dissolution enthalpy and large order disruptive entropy, C2H6 displayed the fastest permeation rate at increased gas phase pressure in spite of its smallest diffusivity among the tested gases. The C2H6 gas molecules “peg” on the side alkyl chain on the imidazulium cation at low concentration, and are well dispersed in the ionic liquids phase at high concentration. On the other hand strong CO2-ILs affinity resulted in a more prolonged “residence time” for the gas molecule, typified by reversed CO2/N2 selectivity and slowest CO2 transport despite CO2 possess the highest solubility and comparable diffusivity in the ionic liquids. The unique transport and dissolution behaviour of CO2 are further exploited by examining the residing state of CO2 molecules in the ionic liquid phase, which leads to a hypothesis of a condensing and holding capacity of ILs towards CO2, which provide an explanation to slower CO2 transport through the SILMs. The pressure related exponential increase in permeations rate is also analysed which suggests a typical concentration dependent diffusion rate at high gas concentration under increased gas feed pressure. Finally the strong influence of discriminating and molecular specific gas-ILs interactions on gas perm-selectivity performance points to future specific design of ionic liquids for targeted gas separations.

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A one-dimensional model of a rice pile is numerically studied for different driving mechanisms and different levels of medium disorder. The universality of the scaling exponents for the transit time distribution and avalanche size distribution is discussed. (C) 1997 Published by Elsevier Science B.V.

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Decreasing the constriction size and residence time in hydrodynamic cavitation is predicted to give increased hot spot temperatures at bubble collapse and increased radical formation rate. Cavitation in a 100 x 100 mu m(2) rectangular micro channel and in a circular 750 mu m diameter milli channel has been investigated with computational fluid dynamics software and with imaging and radical production experiments. No radical production has been measured in the micro channel. This is probably because there is no spherically symmetrical collapse of the gas pockets in the channel which yield high hot spot temperatures. The potassium iodide oxidation yield in the presence of chlorohydrocarbons in the milli channel of up to 60 nM min(-1) is comparable to values reported on hydrodynamic cavitation in literature, but lower than values for ultrasonic cavitation. These small constrictions can create high apparent cavitation collapse frequencies.

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The importance of accurately measuring gas diffusivity in porous materials has led to a number of methods being developed. In this study the Temporal Analysis of Products (TAP) reactor and Flux Response Technology (FRT) have been used to examine the diffusivity in the washcoat supported on cordierite monoliths. Herein, the molecular diffusion of propane within four monoliths with differently prepared alumina/CeZrOx washcoats was investigated as a function of temperature. Moment-based analysis of the observed TAP responses led to the calculation of the apparent intermediate gas constant, Kp, that characterises adsorption into the mesoporous network and apparent time delay, tapp, that characterises residence time in the mesoporous network. Additionally, FRT has been successfully adapted as an extensive in situ perturbation technique in measuring intraphase diffusion coefficients in the washcoats of the same four monolith samples. The diffusion coefficients obtained by moment-based analysis of TAP responses are larger than the coefficients determined by zero length column (ZLC) analysis of flux response profiles with measured values of the same monolith samples between 20 and 100 °C ranging from 2–5×10-9 m2 s-1 to 4–8×10-10 m2 s-1, respectively. The TAP and FRT data, therefore, provide a range of the lower and upper limits of diffusivity, respectively. The reported activation energies and diffusivities clearly correlate with the difference in the washcoat structure of different monolith samples.

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The ionic liquid, tributylmethylammonium methylcarbonate, has been employed as a catalytic base for clean N-methylation of indole with dimethylcarbonate. The reaction conditions were optimised under microwave heating to give 100% conversion and 100% selectivity to N-methylindole, and subsequently transferred to a high temperature/high pressure (285 degrees C/150 bar) continuous flow process using a short (3 min) residence time and 2 mol% of the catalyst to efficiently methylate a variety of different amines, phenols, thiophenols and carboxylic acid substrates. The extremely short residence times, versatility, and high selectivity have significant implications for the synthesis of a wide range of pharmaceutical intermediates, as high product throughputs can be obtained via this scalable continuous flow protocol. It has also been shown that the ionic liquid can be generated in situ from tributylamine, which has the net effect of transforming an ineffective stoichiometric base into a highly efficient catalyst for this broad class of reactions.

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Activation of methane with a halogen followed by the metathesis of methyl halide is a novel route from methane to higher hydrocarbons or oxygenates. Thermodynamic analysis revealed that bromine is the most suitable halogen for this goal. Analysis of the published data on the reaction kinetics in a CSTR enabled us to judge on the effects of temperature, reactor residence time and the feed concentrations of bromine and methane to the conversion of methane and the selectivity towards mono or dibromomethane. The analysis indicated that high dibromomethane selectivity is attainable (over 90%) accompanied by high methane conversions. The metathesis of dibromomethane can provide an alternative route to the conversion of methane (natural gas) economically with smaller installations than the current syn-gas route. (c) 2005 Elsevier B.V. All rights reserved.

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The extraction of uranium(VI) from aqueous nitric acid solutions by tributylphosphate {TBP; 30%(v/v)} dissolved in the ionic liquid 1-butyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amide was investigated. The experiments were performed in a Teflon microchannel of 0.5 mm internal diameter, while the dioxouranium(VI) concentrations in the aqueous and the ionic liquid phases were determined by UV-Vis spectroscopy. The effects of initial nitric acid concentration (0.01-3 M), residence time, and phase flow rate ratio were studied. It was found that, with increasing nitric acid concentration, the percentage of dioxouranium(VI) extracted decreased and then increased again, while the extraction efficiency followed a slightly different trend. Overall mass transfer coefficients varied between 0.049 s and 0.312 s . © 2012 Elsevier B.V. All rights reserved.

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We present theoretical delay times and rates of thermonuclear explosions that are thought to produce Type Ia supernovae (SNe Ia), including the double-detonation sub-Chandrasekhar mass model, using the population synthesis binary evolution code startrack. If detonations of sub-Chandrasekhar mass carbon-oxygen white dwarfs following a detonation in an accumulated layer of helium on the white dwarf's surface ('double-detonation' models) are able to produce thermonuclear explosions which are characteristically similar to those of SNe Ia, then these sub-Chandrasekhar mass explosions may account for at least some substantial fraction of the observed SN Ia rate. Regardless of whether all double-detonations look like 'normal' SNe Ia, in any case the explosions are expected to be bright and thus potentially detectable. Additionally, we find that the delay time distribution of double-detonation sub-Chandrasekhar mass SNe Ia can be divided into two distinct formation channels: the 'prompt' helium-star channel with delay times

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Collagen molecules in articular cartilage have an exceptionally long lifetime, which makes them susceptible to the accumulation of advanced glycation end products (AGEs). In fact, in comparison to other collagen-rich tissues, articular cartilage contains relatively high amounts of the AGE pentosidine. To test the hypothesis that this higher AGE accumulation is primarily the result of the slow turnover of cartilage collagen, AGE levels in cartilage and skin collagen were compared with the degree of racemization of aspartic acid (% d-Asp, a measure of the residence time of a protein). AGE (N(epsilon)-(carboxymethyl)lysine, N(epsilon)-(carboxyethyl)lysine, and pentosidine) and % d-Asp concentrations increased linearly with age in both cartilage and skin collagen (p <0.0001). The rate of increase in AGEs was greater in cartilage collagen than in skin collagen (p <0.0001). % d-Asp was also higher in cartilage collagen than in skin collagen (p <0.0001), indicating that cartilage collagen has a longer residence time in the tissue, and thus a slower turnover, than skin collagen. In both types of collagen, AGE concentrations increased linearly with % d-Asp (p <0.0005). Interestingly, the slopes of the curves of AGEs versus % d-Asp, i.e. the rates of accumulation of AGEs corrected for turnover, were identical for cartilage and skin collagen. The present study thus provides the first experimental evidence that protein turnover is a major determinant in AGE accumulation in different collagen types. From the age-related increases in % d-Asp the half-life of cartilage collagen was calculated to be 117 years and that of skin collagen 15 years, thereby providing the first reasonable estimates of the half-lives of these collagens.

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This paper investigates a queuing system for QoS optimization of multimedia traffic consisting of aggregated streams with diverse QoS requirements transmitted to a mobile terminal over a common downlink shared channel. The queuing system, proposed for buffer management of aggregated single-user traffic in the base station of High-Speed Downlink Packet Access (HSDPA), allows for optimum loss/delay/jitter performance for end-user multimedia traffic with delay-tolerant non-real-time streams and partially loss tolerant real-time streams. In the queuing system, the real-time stream has non-preemptive priority in service but the number of the packets in the system is restricted by a constant. The non-real-time stream has no service priority but is allowed unlimited access to the system. Both types of packets arrive in the stationary Poisson flow. Service times follow general distribution depending on the packet type. Stability condition for the model is derived. Queue length distribution for both types of customers is calculated at arbitrary epochs and service completion epochs. Loss probability for priority packets is computed. Waiting time distribution in terms of Laplace-Stieltjes transform is obtained for both types of packets. Mean waiting time and jitter are computed. Numerical examples presented demonstrate the effectiveness of the queuing system for QoS optimization of buffered end-user multimedia traffic with aggregated real-time and non-real-time streams.