927 resultados para Chitosan. Adsorption kinetics. Kinetic Model. Adsorption Isotherm.Tetracycline. Sodium Cromoglycate
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The effects of the nongray absorption (i.e., atmospheric opacity varying with wavelength) on the possible upper bound of the outgoing longwave radiation (OLR) emitted by a planetary atmosphere have been examined. This analysis is based on the semigray approach, which appears to be a reasonable compromise between the complexity of nongray models and the simplicity of the gray assumption (i.e., atmospheric absorption independent of wavelength). Atmospheric gases in semigray atmospheres make use of constant absorption coefficients in finite-width spectral bands. Here, such a semigray absorption is introduced in a one-dimensional (1D) radiative– convective model with a stratosphere in radiative equilibrium and a troposphere fully saturated with water vapor, which is the semigray gas. A single atmospheric window in the infrared spectrum has been assumed. In contrast to the single absolute limit of OLR found in gray atmospheres, semigray ones may also show a relative limit. This means that both finite and infinite runaway effects may arise in some semigray cases. Of particular importance is the finding of an entirely new branch of stable steady states that does not appear in gray atmospheres. This new multiple equilibrium is a consequence of the nongray absorption only. It is suspected that this new set of stable solutions has not been previously revealed in analyses of radiative–convective models since it does not appear for an atmosphere with nongray parameters similar to those for the earth’s current state
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AIMS: Experimental models have reported conflicting results regarding the role of dispersion of repolarization in promoting atrial fibrillation (AF). Repolarization alternans, a beat-to-beat alternation in action potential duration, enhances dispersion of repolarization when propagation velocity is involved. METHODS AND RESULTS: In this work, original electrophysiological parameters were analysed to study AF susceptibility in a chronic sheep model of pacing-induced AF. Two pacemakers were implanted, each with a single right atrial lead. Right atrial depolarization and repolarization waves were documented at 2-week intervals. A significant and gradual decrease in the propagation velocity at all pacing rates and in the right atrial effective refractory period (ERP) was observed during the weeks of burst pacing before sustained AF developed when compared with baseline conditions. Right atrial repolarization alternans was observed, but because of the development of 2/1 atrioventricular block with far-field ventricular interference, its threshold could not be precisely measured. Non-sustained AF was not observed at baseline, but appeared during the electrical remodelling in association with a decrease in both ERP and propagation velocity. CONCLUSION: We report here on the feasibility of measuring ERP, atrial repolarization alternans, and propagation velocity kinetics and their potential in predicting susceptibility to AF in a free-behaving model of pacing-induced AF using the standard pacemaker technology.
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Contact aureoles provide an excellent geologic environment to study the mechanisms of metamorphic reactions in a natural system. The Torres del Paine (TP) intrusion is one of the most spectacular natural laboratories because of its excellent outcrop conditions. It formed in a period from 12.59 to 12.43 Ma and consists of three large granite and four smaller mafic batches. The oldest granite is on top, the youngest at the bottom of the granitic complex, and the granites overly the mafic laccolith. The TP intruded at a depth of 2-3 km into regional metamorphic anchizone to greenschist facies pelites, sandstones, and conglomerates of the Cerro Toro and Punta Barrosa formations. It formed a thin contact aureole of 150-400 m width. This thesis focuses on the reaction kinetics of the mineral cordierite in the contact aureole using quantitative textural analysis methods. First cordierite was formed from chlorite break¬down (zone I, ca. 480 °C, 750 bar). The second cordierite forming reaction was the muscovite break-down, which is accompanied by a modal decrease in biotite and the appearance of k- feldspar (zone II, 540-550 °C, 750 bar). Crystal sizes of the roundish, poikiloblastic cordierites were determined from microscope thin section images by manually marking each crystal. Images were then automatically processed with Matlab. The correction for the intersection probability of each crystal radius yields the crystal size distribution in the rock. Samples from zone I below the laccolith have the largest crystals (0.09 mm). Cordierites from zone II are smaller, with a maximum crystal radius of 0.057 mm. Rocks from zone II have a larger number of small cordierite crystals than rocks from zone I. A combination of these quantitative analysis with numerical modeling of nucleation and growth, is used to infer nucleation and growth parameters which are responsible for the observed mineral textures. For this, the temperature-time paths of the samples need to be known. The thermal history is complex because the main body of the intrusion was formed by several intrusive batches. The emplacement mechanism and duration of each batch can influence the thermal structure in the aureole. A possible subdivision of batches in smaller increments, so called pulses, will focus heat at the side of the intrusion. Focusing all pulses on one side increases the contact aureole size on that side, but decreases it on the other side. It forms a strongly asymmetric contact aureole. Detailed modeling shows that the relative thicknesses of the TP contact aureole above and below the intrusion (150 and 400 m) are best explained by a rapid emplacement of at least the oldest granite batch. Nevertheless, temperatures are significantly too low in all models, compared to observed mineral assemblages in the hornfelses. Hence, an other important thermal mechanisms needs to take place in the host rock. Clastic minerals in the immature sediments outside the contact aureole are hydrated due to small amounts of expelled fluids during contact metamorphism. This leads to a temperature increase of up to 50 °C. The origin of fluids can be traced by stable isotopes. Whole rock stable isotope data (6D and δ180) and chlorine concentrations in biotite document that the TP intrusion induced only very small amounts of fluid flow. Oxygen whole rock data show δ180 values between 9.0 and 10.0 %o within the first 5 m of the contact. Values increase to 13.0 - 15.0 %o further away from the intrusion. Whole rock 6D values display a more complex zoning. First, host rock values (-90 to -70 %o) smoothly decrease towards the contact by ca. 20 %o, up to a distance of ca. 150 m. This is followed by an increase of ca. 20 %o within the innermost 150 m of the aureole (-97.0 to -78 %o at the contact). The initial decrease in 6D values is interpreted to be due to Rayleigh fractionation accompanying the dehydration reactions forming cordierite, while the final increase reflects infiltration of water-rich fluids from the intrusion. An over-estimate on the quantity and the corresponding thermal effect yields a temperature increase of less than 30 °C. This suggests that fluid flow might have contributed only for a small amount to the thermal evolution of the system. A combination of the numerical growth model with the thermal model, including the hydration reaction enthalpies but neglecting fluid flow and incremental growth, can be used to numerically reproduce the observed cordierite textures in the contact aureole. This yields kinetic parameters which indicate fast cordierite crystallization before the thermal peak in the inner aureole, and continued reaction after the thermal peak in the outermost aureole. Only small temperature dependencies of the kinetic parameters seem to be needed to explain the obtained crystal size data. - Les auréoles de contact offrent un cadre géologique privilégié pour l'étude des mécanismes de réactions métamorphiques associés à la mise en place de magmas dans la croûte terrestre. Par ses conditions d'affleurements excellentes, l'intrusion de Torres del Paine représente un site exceptionnel pour améliorer nos connaissances de ces processus. La formation de cette intrusion composée de trois injections granitiques principales et de quatre injections mafiques de volume inférieur couvre une période allant de 12.50 à 12.43 Ma. Le plus vieux granite forme la partie sommitale de l'intrusion alors que l'injection la plus jeune s'observe à la base du complexe granitique; les granites recouvrent la partie mafique du laccolite. L'intrusion du Torres del Paine s'est mise en place a 2-3 km de profondeur dans un encaissant métamorphique. Cet encaissant est caractérisé par un métamorphisme régional de faciès anchizonal à schiste vert et est composé de pélites, de grès, et des conglomérats des formations du Cerro Toro et Punta Barrosa. La mise en place des différentes injections granitiques a généré une auréole de contact de 150-400 m d'épaisseur autour de l'intrusion. Cette thèse se concentre sur la cinétique de réaction associée à la formation de la cordiérite dans les auréoles de contact en utilisant des méthodes quantitatives d'analyses de texture. On observe plusieurs générations de cordiérite dans l'auréole de contact. La première cordiérite est formée par la décomposition de la chlorite (zone I, environ 480 °C, 750 bar), alors qu'une seconde génération de cordiérite est associée à la décomposition de la muscovite, laquelle est accompagnée par une diminution modale de la teneur en biotite et l'apparition de feldspath potassique (zone II, 540-550 °C, 750 bar). Les tailles des cristaux de cordiérites arrondies et blastic ont été déterminées en utilisant des images digitalisées des lames minces et en marquant individuellement chaque cristal. Les images sont ensuite traitées automatiquement à l'aide du programme Matlab. La correction de la probabilité d'intersection en fonction du rayon des cristaux permet de déterminer la distribution de la taille des cristaux dans la roche. Les échantillons de la zone I, en dessous du lacolite, sont caractérisés par de relativement grands cristaux (0.09 mm). Les cristaux de cordiérite de la zone II sont plus petits, avec un rayon maximal de 0.057 mm. Les roches de la zone II présentent un plus grand nombre de petits cristaux de cordiérite que les roches de la zone I. Une combinaison de ces analyses quantitatives avec un modèle numérique de nucléation et croissance a été utilisée pour déduire les paramètres de nucléation et croissance contrôlant les différentes textures minérales observées. Pour développer le modèle de nucléation et de croissance, il est nécessaire de connaître le chemin température - temps des échantillons. L'histoire thermique est complexe parce que l'intrusion est produite par plusieurs injections successives. En effet, le mécanisme d'emplace¬ment et la durée de chaque injection peuvent influencer la structure thermique dans l'auréole. Une subdivision des injections en plus petits incréments, appelés puises, permet de concentrer la chaleur dans les bords de l'intrusion. Une mise en place préférentielle de ces puises sur un côté de l'intrusion modifie l'apport thermique et influence la taille de l'auréole de contact produite, auréole qui devient asymétrique. Dans le cas de la première injection de granite, une modélisation détaillée montre que l'épaisseur relative de l'auréole de contact de Torres del Paine au-dessus et en dessous de l'intrusion (150 et 400 m) est mieux expliquée par un emplacement rapide du granite. Néanmoins, les températures calculées dans l'auréole de con¬tact sont trop basses pour que les modèles thermiques soient cohérants par rapport à la taille de cette auréole. Ainsi, un autre mecanisme exothermique est nécessaire pour permettre à la roche encais¬sante de produire les assemblages observés. L'observation des roches encaissantes entourant les granites montre que les minéraux clastiques dans les sédiments immatures au-dehors de l'auréole sont hydratés suite à la petite quantité de fluide expulsée durant le métamorphisme de contact et/ou la mise en place des granites. Les réactions d'hydratation peuvent permettre une augmentation de la température jusqu'à 50 °C. Afin de déterminer l'origine des fluides, une étude isotopique de roches de l'auréole de contact a été entreprise. Les isotopes stables d'oxygène et d'hydrogène sur la roche totale ainsi que la concentration en chlore dans la biotite indiquent que la mise en place des granites du Torres del Paine n'induit qu'une circulation de fluide limitée. Les données d'oxygène sur roche totale montrent des valeurs δ180 entre 9.0 et 10.0%o au sein des cinq premiers mètres du contact. Les valeurs augmentent jusqu'à 13.0 - 15.0 plus on s'éloigne de l'intrusion. Les valeurs 5D sur roche totale montrent une zonation plus complexe. Les valeurs de la roche encaissante (-90 à -70%o) diminuent progressivement d'environ 20%o depuis l'extérieur de l'auréole jusqu'à une distance d'environ 150 m du granite. Cette diminution est suivie par une augmentation d'environ 20%o au sein des 150 mètres les plus proches du contact (-97.0 à -78%o au contact). La diminution initiale des valeurs de 6D est interprétée comme la conséquence du fractionnement de Rayleigh qui accompagne les réactions de déshydratation formant la cordiérite, alors que l'augmentation finale reflète l'infiltration de fluide riche en eau venant de l'intrusion. A partir de ces résultats, le volume du fluide issu du granite ainsi que son effet thermique a pu être estimé. Ces résultats montrent que l'augmentation de température associée à ces fluides est limitée à un maximum de 30 °C. La contribution de ces fluides dans le bilan thermique est donc faible. Ces différents résultats nous ont permis de créer un modèle thermique associé à la for¬mation de l'auréole de contact qui intègre la mise en place rapide du granite et les réactions d'hydratation lors du métamorphisme. L'intégration de ce modèle thermique dans le modèle numérique de croissance minérale nous permet de calculer les textures des cordiérites. Cepen¬dant, ce modèle est dépendant de la vitesse de croissance et de nucléation de ces cordiérites. Nous avons obtenu ces paramètres en comparant les textures prédites par le modèle et les textures observées dans les roches de l'auréole de contact du Torres del Paine. Les paramètres cinétiques extraits du modèle optimisé indiquent une cristallisation rapide de la cordiérite avant le pic thermique dans la partie interne de l'auréole, et une réaction continue après le pic thermique dans la partie la plus externe de l'auréole. Seules de petites dépendances de température des paramètres de cinétique semblent être nécessaires pour expliquer les don¬nées obtenues sur la distribution des tailles de cristaux. Ces résultats apportent un éclairage nouveau sur la cinétique qui contrôle les réactions métamorphiques.
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Mathematical methods combined with measurements of single-cell dynamics provide a means to reconstruct intracellular processes that are only partly or indirectly accessible experimentally. To obtain reliable reconstructions, the pooling of measurements from several cells of a clonal population is mandatory. However, cell-to-cell variability originating from diverse sources poses computational challenges for such process reconstruction. We introduce a scalable Bayesian inference framework that properly accounts for population heterogeneity. The method allows inference of inaccessible molecular states and kinetic parameters; computation of Bayes factors for model selection; and dissection of intrinsic, extrinsic and technical noise. We show how additional single-cell readouts such as morphological features can be included in the analysis. We use the method to reconstruct the expression dynamics of a gene under an inducible promoter in yeast from time-lapse microscopy data.
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The adsorption of As(V) onto alpha -Al2O3 was investigated at 25, 50 and 70 degreesC using batch adsorption experiments. Results indicate that As is strongly adsorbed at low pH and gets progressively released to the fluid with increasing pH above 7. At any pH, increasing temperature favors aqueous species of As over surface species. Surface complexation constants were determined at the experimental temperatures by fitting the adsorption data. Adsorption reactions were then converted to semi-isocolumbic reactions, i.e, reactions with balanced like-charged aqueous species. Intrinsic adsorption constants of semi-isocolumbic reactions change linearly when plotted against inverse temperature, suggesting that the heat capacity of these reactions remains constant over the temperature range considered. This permitted thermodynamic parameters of intrinsic surface complexation constants to be determined. Changes in surface complexation constants result in a change in the surface speciation with increasing temperature. This change is similar to the one observed for aqueous species, i.e. increasing temperature favors less negatively charged species below a pH of 9 and more negatively charged species above a pH of 10. Comparison with the stability of As surface complexes with Fe suggests that surface complexes with Al are more stable. (C) 2001 Elsevier Science Ltd. All rights reserved.
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Kinetic studies on soil potassium release can contribute to a better understanding of K availability to plants. This study was conducted to evaluate K release rates from the whole soil, clay, silt, and sand fractions of B-horizon samples of a basalt-derived Oxisol and a sienite-derived Ultisol, both representative soils from coffee regions of Minas Gerais State, Brazil. Potassium was extracted from each fraction after eight different shaking time periods (0-665 h) with either 0.001 mol L-1 citrate or oxalate at a 1:10 solid:solution ratio. First-order, Elovich, zero-order, and parabolic diffusion equations were used to parameterize the time dependence of K release. For the Oxisol, the first-order equation fitted best to the experimental data of K release, with similar rates for all fractions and independent of the presence of citrate or oxalate in the extractant solution. For all studied Ultisol fractions, in which K release rates increased when extractions were performed with citrate solution, the Elovich model described K release kinetics most adequately. The highest potassium release rate of the Ultisol silt fraction was probably due to the transference of "non-exchangeable" K to the extractant solution, whereas in the Oxisol exchangeable potassium represented the main K source in all studied fractions.
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In a recent paper [Phys. Rev. B 50, 3477 (1994)], P. Fratzl and O. Penrose present the results of the Monte Carlo simulation of the spinodal decomposition problem (phase separation) using the vacancy dynamics mechanism. They observe that the t1/3 growth regime is reached faster than when using the standard Kawasaki dynamics. In this Comment we provide a simple explanation for the phenomenon based on the role of interface diffusion, which they claim is irrelevant for the observed behavior.
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We present a method to compute, assuming a continuous distribution of sources, the elementary potential created by a differential element of volume of matter, whose integral generates a known adsorption field V(z) for a planar surface. We show that this elementary potential is univocally determined by the original field and can be used to generate adsorption potentials for other nontrivial geometries. We illustrate the method for the Chizmeshya-Cole-Zaremba physisorption potential and discuss several examples and applications.
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Using the experimental values of the chemical potentials of liquid 4He and of a 3He impurity in liquid 4He, we derive a model-independent lower (upper) bound to the kinetic (potential) energy per particle at zero temperature. The values of the bounds at the experimental saturation density are 13.42 K for the kinetic energy and -20.59 K for the potential energy. All the theoretical calculations based on the Lennard-Jones potential violate the upper-bound condition for the potential energy.
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Organic acids play an important role in the nutritional conditions of plants. Their relevance is related to their formation dynamics, mineralization rate and adsorption by soil colloids. This study was carried out to evaluate the dynamics of mineralization and adsorption of organic acid (acetic acid - AA, citric acid - CA and humic acid - HA) applied to the soil. Samples of two Oxisols were used: Rhodic Haplustox (LV) and Typic Haplustox (LVA). The mineralization experiment was arranged in a 2 x 3 x 5 factorial design, based on the factors: two soils (LV and LVA) x three organic acid (OA) types (AA, CA and HA) x five OA rates (0, 1, 2, 4, and 8 mmol dm-3). Organic carbon mineralization in samples was measured by the C-CO2 efflux, produced by the microbial activity, in a 30-day (measurements after 4, 8, 12, 21, and 30 days) and in a 4-day experiment (measured after 24, 48, 72 and 96 h). Organic acid adsorption was tested in a 2 x 2 x 5 x 4 factorial design, with the factors and levels: two Oxisols; two organic acids (AA and CA); five OA rates (0, 1, 2, 4, and 8 mmol dm-3) and four adsorption periods (6, 24, 48, and 72 h). The C-CO2 production of soil treated with CA was highest. In the adsorption experiment, the affinity of CA to soil adsorption sites was greatest. The adsorption of organic acids to soils may be an important mechanism by which bioavailability and thus mineralization capacity by microbial activity are reduced.
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ABSTRACT Intrinsic equilibrium constants for 22 representative Brazilian Oxisols were estimated from a cadmium adsorption experiment. Equilibrium constants were fitted to two surface complexation models: diffuse layer and constant capacitance. Intrinsic equilibrium constants were optimized by FITEQL and by hand calculation using Visual MINTEQ in sweep mode, and Excel spreadsheets. Data from both models were incorporated into Visual MINTEQ. Constants estimated by FITEQL and incorporated in Visual MINTEQ software failed to predict observed data accurately. However, FITEQL raw output data rendered good results when predicted values were directly compared with observed values, instead of incorporating the estimated constants into Visual MINTEQ. Intrinsic equilibrium constants optimized by hand calculation and incorporated in Visual MINTEQ reliably predicted Cd adsorption reactions on soil surfaces under changing environmental conditions.
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It is now well accepted that cellular responses to materials in a biological medium reflect greatly the adsorbed biomolecular layer, rather than the material itself. Here, we study by molecular dynamics simulations the competitive protein adsorption on a surface (Vroman effect), i.e. the non-monotonic behavior of the amount of protein adsorbed on a surface in contact with plasma as functions of contact time and plasma concentration. We find a complex behavior, with regimes during which small and large proteins are not necessarily competing between them, but are both competing with others in solution ("cooperative" adsorption). We show how the Vroman effect can be understood, controlled and inverted.
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Interaction models of atomic Al with Si4H9, Si4H7, and Si6H9 clusters have been studied to simulate Al chemisorption on the Si(111) surface in the atop, fourfold atop, and open sites. Calculations were carried out using nonempirical pseudopotentials in the framework of the ab initio Hartree-Fock procedure. Equilibrium bond distances, binding energies for adsorption, and vibrational frequencies of the adatoms are calculated. Several basis sets were used in order to show the importance of polarization effects, especially in the binding energies. Final results show the importance of considering adatom-induced relaxation effects to specify the order of energy stabilities for the three different sites, the fourfold atop site being the preferred one, in agreement with experimental findings.
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A critical issue in brain energy metabolism is whether lactate produced within the brain by astrocytes is taken up and metabolized by neurons upon activation. Although there is ample evidence that neurons can efficiently use lactate as an energy substrate, at least in vitro, few experimental data exist to indicate that it is indeed the case in vivo. To address this question, we used a modeling approach to determine which mechanisms are necessary to explain typical brain lactate kinetics observed upon activation. On the basis of a previously validated model that takes into account the compartmentalization of energy metabolism, we developed a mathematical model of brain lactate kinetics, which was applied to published data describing the changes in extracellular lactate levels upon activation. Results show that the initial dip in the extracellular lactate concentration observed at the onset of stimulation can only be satisfactorily explained by a rapid uptake within an intraparenchymal cellular compartment. In contrast, neither blood flow increase, nor extracellular pH variation can be major causes of the lactate initial dip, whereas tissue lactate diffusion only tends to reduce its amplitude. The kinetic properties of monocarboxylate transporter isoforms strongly suggest that neurons represent the most likely compartment for activation-induced lactate uptake and that neuronal lactate utilization occurring early after activation onset is responsible for the initial dip in brain lactate levels observed in both animals and humans.