Theories of ion permeation: a chaser.
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Diffusion↗
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Results for “diffusion theory”
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The evolution of diabetes knowledge in relation to the theory of scientific revolutions.
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Diabetes Mellitus↗
Is diffusion, thermodiffusion, or advection a primary mechanism of indoor radon entry?
Revision of the current theory of indoor radon entry is given. It is shown that there is insufficient evidence to accept the pressure-driven mechanism as the dominant mechanism of radon infiltration in homes. The criticism of the US Environmental Protection Agency's policy is presented. The similitude theory of gas transfer in Knudsen's and transition zones is developed. Comparison of the theory with experimental data confirms the validity of the assumptions made. Application of the theory to air flow in clay is shown. This theory allows the average pore radius in the clay sample to be estimated. That radius was found to be of the order of the mean free path of air molecules at atmospheric pressure. It is shown that thermodiffusion gas flow in clay and concrete can greatly exceed the pressure-driven flow. The necessity of including thermodiffusion gas flow in a general model of radon indoor entry is substantiated.
Air Pollution, Indoor↗
Electroacoustic theory for concentrated colloids with overlapped DLs at arbitrary kappa alpha. I. Application to nanocolloids and nonaqueous colloids.
Existing theories of electroacoustic phenomena in concentrated colloids neglect the possibility of double layer overlap and are valid mostly for the "thin double layer," when the double layer thickness is much less than the particle size. In this paper we present a new electroacoustic theory which removes this restriction. This would make this new theory applicable to characterizing a variety of aqueous nanocolloids and of nonaqueous dispersions. There are two versions of the theory leading to the analytical solutions. The first version corresponds to strongly overlapped diffuse layers (so-called quasi-homogeneous model). It yields a simple analytical formula for colloid vibration current (CVI), which is valid for arbitrary ultrasound frequency, but for restricted kappa alpha range. This version of the theory, as well the Smoluchowski theory for microelectrophoresis, is independent of particle shape and polydispersity. This makes it very attractive for practical use, with the hope that it might be as useful as classical Smoluchowski theory. In order to determine the kappa alpha range of the quasi-homogeneous model validity we develop the second version that limits ultrasound frequency, but applies no restriction on kappa alpha. The ultrasound frequency should substantially exceed the Maxwell-Wagner relaxation frequency. This limitation makes active conductivity related current negligible compared to the passive dielectric displacement current. It is possible to derive an expression for CVI in the concentrated dispersion as formulae inhering definite integrals with integrands depending on equilibrium potential distribution. This second version allowed us to estimate the ranges of the applicability of the first, quasi-homogeneous version. It turns out that the quasi-homogeneous model works for kappa alpha values up to almost 1. For instance, at volume fraction 30%, the highest kappa alpha limit of the quasi-homogeneous model is 0.65. Therefore, this version of the electroacoustic theory is valid for almost all nonaqueous dispersions and a wide variety of nanocolloids, especially with sizes under 100 nm.
Journal Article↗
Iontophoretic transport across a synthetic membrane and human epidermal membrane: a study of the effects of permeant charge.
The effects of permeant charge (z) on iontophoretic-enhanced transport were investigated with synthetic Nucleopore membranes and with human epidermal membranes using a four-electrode potentiostat with side-by-side diffusion cells. The modified Nernst-Planck model (Nernst-Planck theory with an additional transport term to correct for the effect of the convective solvent flow due to electroosmosis) was first examined in a Nuclepore membrane system with model permeants calcein (z = -4), salicylate (z = -1), and a series of polystyrene sulfonates (from monomer to molecular weight of approximately 8000 with a z range of -1 to approximately -40). The flux enhancement (E) for each permeant was determined at 470 mV. Mannitol (a neutral molecule) was used as a probe to determine a correction for convective solvent flow under the same applied voltage conditions. Good agreement between the experimental results and the predictions from the modified Nernst-Planck model was found for calcein, salicylate, and polystyrene sulfonates up to molecular weight of approximately 1800 (z approximately -8). The flux enhancements for the higher molecular weight polystyrene sulfonates with greater z values were more than a factor of three lower than theoretical predictions; the electrophoretic effect and counterion binding to the permeants are proposed as possible explanations for these discrepancies between experiment and the modified Nernst-Planck theory. In the studies with human epidermal membranes, iontophoretic flux enhancements for calcein, salicylate, and taurocholate were determined at 250 and/or 470 mV. The flux enhancements were generally consistent with the results calculated from the modified Nernst-Planck model.
Diffusion↗
The Dispersal System of a Butterfly: A Test of Source-Sink Theory Suggests the Intermediate-Scale Hypothesis.
Theory predicts source-sink dynamics can occur in species with the ideal preemptive distribution but not with the ideal free distribution. Source-sink dynamics can also occur in species with passive dispersal, in which a fixed fraction of the population disperses each generation. However, in nature, dispersal often approximates random diffusion rather than ideal choices or fixed probabilities. Here, I ask which dispersal system occurred in a butterfly (Euphydryas editha) known to have source-sink dynamics. The study used 13 experimental sites, where vacant and occupied habitat patches were juxtaposed. I estimated movement during the flight season and tested hypotheses about the type of dispersal system. Ideal free and ideal preemptive models were rejected because per capita movement rates were density independent. Passive dispersal was rejected because per capita rates were related to patch area and habitat preference. The diffusion model best explained the data because it predicted both the area relationship and an odd feature of the habitat preference: immigration was not higher in preferred habitat; rather, emigration was lower. The diffusion model implied that source-sink dynamics were driven by diffusion from areas of high to low population density. Existing source-sink theory assumes fine-scale patchiness, in which animals have perfect knowledge and ease of mobility. The results from the butterfly suggest that source-sink dynamics arise at coarser spatial scales, where diffusion models apply.
diffusion↗
Rotational and translational diffusion of peptide-coated CdSe/CdS/ZnS nanorods studied by fluorescence correlation spectroscopy.
CdSe/CdS/ZnS nanorods (NRs) of three aspect ratios were coated with phytochelatin-related peptides and studied using fluorescence correlation spectroscopy (FCS). Theoretical predictions of the NRs' rotational diffusion contribution to the correlation curves were experimentally confirmed. We monitored rotational and translational diffusion of NRs and extracted hydrodynamic radii from the extracted diffusion constants. Translational and rotational diffusion constants (D(trans) and D(rot)) for NRs were in good agreement with Tirado and Garcia de la Torre's as well as with Broersma's theories when accounting for the ligand dimensions. NRs fall in the size range where rotational diffusion can be monitored with higher sensitivity than translational diffusion due to a steeper length dependence, D(rot) approximately L(-)(3) versus D(trans) approximately L(-)(1). By titrating peptide-coated NRs with bovine serum albumin, we monitored (nonspecific) binding through rotational diffusion and showed that D(rot) is an advantageous observable for monitoring binding. Monitoring rotational diffusion of bioconjugated NRs using FCS might prove to be useful for observing binding and conformational dynamics in biological systems.
Amino Acid Sequence↗
Whole range of chain dynamics in entangled polystyrene melts revealed from creep compliance: thermorheological complexity between glassy-relaxation region and rubber-to-fluid region. 1.
The rubber(like)-to-fluid region of the creep compliance J(t) results reported by Plazek of two nearly monodisperse polystyrene melts in the entanglement region have been quantitatively analyzed in terms of the extended reptation theory (ERT), giving the frictional factor K (= zetab2kTpi2m2) in quantitative agreement with the values obtained previously from analyzing the relaxation modulus Gt line shapes as well as calculated from the viscosity and diffusion data-a quantity shown independent of molecular weight as expected from the theory. Using the successful description of Jt in terms of ERT in the rubber(like)-to-fluid region as the reference frame in time, the glassy-relaxation process microG(t) that occurs in the small-compliance short-time region of J(t) can be studied in perspective. As shown from the analysis in terms of a stretched exponential form for microG(t) incorporated into ERT, the temperature dependence of the energetic interactions-derived microG(t) process being stronger in a simple manner than that of the entropy-derived ERT processes accounts fully for the uneven thermorheological complexity occurring in J(t) as initially observed by Plazek. When the results of analysis being displayed in the G(t) form, the relative roles of the energetic interactions-derived dynamic process and the entropy-derived ones in polystyrene are clearly revealed. It is shown that at the calorimetric glass transition temperature (Tg) the contribution from energetic interactions among segments to G(t) at the time scale of the highest Rouse-Mooney normal mode greatly exceeds that derived from entropy, indicating vitrification at the Rouse-segmental level. At the same time the Rouse-Mooney normal modes provide an internal yardstick for estimating the characteristic length scale of a polymer at Tg, giving approximately 3 nm for polystyrene. On the basis of the obtained results, the basic mechanism for the thermorheological complexity occurring in polystyrene is analyzed. It is shown that this basic mechanism should be also responsible for the breakdown of the Stoke-Einstein equation in relating the translational diffusion constant and viscosity as observed in glass-forming liquids, such as OTP and TNB, in approaching Tg from above.
Journal Article↗
Water absorption of poly(methyl methacrylate) containing 4-methacryloxyethyl trimellitic anhydride.
The amount of water absorption of poly(methyl methacrylate) (PMMA) containing 0, 1, 3 and 5 wt% of an adhesive monomer, 4-methacryloxyethyl trimellitic anhydride (4-META), was measured at 7 degrees C, 37 degrees C and 60 degrees C. After the water uptake reached equilibrium in specimens, they were desorbed to obtain a constant value and the absorption process was repeated. Mass changes in the second desorption were recorded for the storage temperatures of 37 degrees C and 60 degrees C. Multiple regression analyses were conducted on three independent variables, 4-META concentration, storage temperature and absorption-desorption cycle. A statistically significant relationship was found between the maximum water uptake and 4-META concentration, while there was no relationship between the maximum water uptake and diffusion coefficient obtained using the Fick's law. The negative relationship in the latter did not support the free space theory. The significant and positive relationship between the maximum water uptake and 4-META concentration demonstrates that water molecules diffuse through the formation of a hydrogen bond at polar sites. The maximum water uptake was not influenced by temperature, while the diffusion coefficient increased with the rise in temperature. The activation energy was 41-47 and 50-53 kJ/mol in the first and second absorption tests, respectively.
Absorption↗
Localization mechanisms in enzyme cytochemistry studied with alkaline phosphatase-loaded erythrocyte ghosts.
Erythrocyte ghosts containing varying amounts of alkaline phosphatase were used to study the localization mechanisms of three metal salt and one azo method for this enzyme. For the azo method, the minimal amount of alkaline phosphatase that can be visualized within the ghosts proved only to be limited by the optical properties of the azo compound. In contrast, for the metal salt methods, a certain threshold activity had to be present in the ghosts in order to obtain correct localization of the final reaction product. The localization properties of both azo and metal salt methods conformed to the theories of cytochemical enzyme localization presented to date. By determining the rate constant of the capture reaction and the diffusion constant of the primary product, the localization properties of the azo method could be predicted. Some remaining discrepancies between theory and practice are discussed.
Alkaline Phosphatase↗
Water vapor sorption and desorption by human callus I: Anomalous diffusion.
The rates of sorption and desorption of water in membranes of varying thickness of excised human callus were determined for several relative vapor pressures and temperatures. Under the conditions studied, the diffusion of water in these membranes was interpreted as non-Fickian in nature. It was concluded that at low water concentration this type of membrane exists in the glassy state. The effect of the relative vapor pressure on the water sorption rates was examined in the context of the free volume theory.
Adsorption↗
Rate enhancement by guided diffusion. Chain length dependence of repressor-operator association rates.
Association rates are calculated for cases where one reaction partner belongs to a chain that has an unspecific affinity to the other. Provided that the unspecific attachment does not completely suppress diffusion along the chain, this channeling may considerably speed up the association. Explicit formulae are derived to show how this effect depends on the chain length and other parameters. The influence of electrostatic forces and reaction barriers is discussed. Time dependent solutions of the diffusion equations are analyzed in order to test the usual steady state assumptions. Experiments on the repressor-operator system seem to be in good agreement with our theory.
Biophysical Phenomena↗
Hamiltonian theory for vibrational line shapes of atoms adsorbed on surfaces.
The vibrational motions of atomic adsorbates on surfaces can be probed by helium atom scattering. The experimental observable is the dynamic structure factor, which shows an inelastic peak around the vibrational frequency of the isolated adsorbates known as the frustrated translational or T-mode peak. In this paper we develop a theory for the line shape of this peak, as well as for its temperature-dependent shift and broadening, based on a Hamiltonian equivalent of the generalized Langevin equation. The theory can be used to infer physical parameters of the adatom-surface interaction, such as the friction coefficient, the barrier height to diffusion, and the anharmonicity parameter. Numerical simulations are used to ascertain the range of validity of the theory, which is also generalized to describe multidimensional systems and to include quantum corrections. We compare the theoretical predictions for the shift and broadening with experimental results for the Na/Cu(001) system, showing quantitative agreement within experimental resolution.
Journal Article↗
Kinematically irreversible acinar flow: a departure from classical dispersive aerosol transport theories.
Current theories describe aerosol transport in the lung as a dispersive (diffusion-like) process, characterized by an effective diffusion coefficient in the context of reversible alveolar flow. Our recent experimental data, however, question the validity of these basic assumptions. In this study, we describe the behavior of fluid particles (or bolus) in a realistic, numerical, alveolated duct model with rhythmically expanding walls. We found acinar flow exhibiting multiple saddle points, characteristic of chaotic flow, resulting in substantial flow irreversibility. Computations of axial variance of bolus spreading indicate that the growth of the variance with respect to time is faster than linear, a finding inconsistent with dispersion theory. Lateral behavior of the bolus shows fine-scale, stretch-and-fold striations, exhibiting fractal-like patterns with a fractal dimension of 1.2, which compares well with the fractal dimension of 1.1 observed in our experimental studies performed with rat lungs. We conclude that kinematic irreversibility of acinar flow due to chaotic flow may be the dominant mechanism of aerosol transport deep in the lungs.
Aerosols↗
Promoting health and preventing disease in health care settings: an analysis of barriers.
Changes in lifestyle that promote health-enhancing behaviors and inhibit health-compromising behaviors have been recommended by the U.S. Surgeon General as an integral component of our general strategy for improving the health of the nation. A variety of innovations including new knowledge, new products, and new services have been developed with this recommendation in mind, and a major objective of these efforts is to identify settings for the effective diffusion and adoption of these new approaches into population groups that can make use of them. Health care settings such as hospitals, clinics, community health centers, health maintenance organizations, and private physicians' offices offer unique possibilities in this regard. Though opportunities exist for promoting health and preventing disease in other settings like schools and worksites, the primary objectives of such organizations are unrelated to health. Despite the obvious potential, however, our health care system has, in general, retained as its primary emphasis the treatment of disease rather than the enhancement of health. This article reviews the opportunities for health promotion and disease prevention in health care settings and identifies a range of barriers to such efforts. These barriers are discussed within a framework that focuses on dissemination and implementation as critical steps in the knowledge transfer process. Strategies for overcoming these barriers are described within the context of general linkage theory.
Adolescent↗
Pulsed-field gradients: theory and practice.
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Chemical Phenomena↗
Simultaneous free-volume modeling of the self-diffusion coefficient and dynamic viscosity at high pressure.
In this work, a simultaneous modeling of the self-diffusion coefficient and the dynamic viscosity is presented. In the microstructural theory these two quantities are governed by the same friction coefficient related to the mobility of the molecule. A recent free-volume model, already successfully applied to dynamic viscosity, has been considered and generalized. In this generalized model the compound is characterized by only four parameters. But if the quadratic length is known, the number of adjustable parameters is three. The compounds considered in this work are benzene, carbon tetrachloride, chlorotrifluoromethane, cyclohexane, methylcyclohexane, and tetramethylsilane. For these pure compounds we have found in the literature several data for both the self-diffusion and the dynamic viscosity in large viscosity, diffusion, temperature, and pressure intervals (up to around 500 MPa for methylcyclohexane and tetramethylsilane). The average absolute deviation obtained by the modeling is generally less than 3% for the viscosity and 5% for the self-diffusion.
Journal Article↗
Steady-state diffusion of water through soft-contact-lens materials.
Water transport through soft contact lenses (SCL) is important for acceptable performance on the human eye. Chemical-potential gradient-driven diffusion rates of water through SCL materials are measured with an evaporation-cell technique. Water is evaporated from the bottom surface of a lens membrane by impinging air at controlled flow rate and humidity. The resulting weight loss of a water reservoir covering the top surface of the contact-lens material is recorded as a function of time. New results are reported for a conventional hydrogel material (SofLens One Day, hilafilcon A, water content at saturation w10 = 70 weight %) and a silicone hydrogel material (PureVision, balafilcon A, w10 = 36%), with and without surface oxygen plasma treatment. Also, previously reported data for a conventional 2-hydroxyethyl methacrylate (HEMA)-SCL (w10 = 38%) hydrogel are reexamined and compared with those for SofLens One Day and PureVision hydrogels. Measured steady-state water fluxes are largest for SofLens One Day, followed by PureVision and HEMA. In some cases, the measured steady-state water fluxes increase with rising relative air humidity. This increase, due to an apparent mass-transfer resistance at the surface (trapping skinning), is associated with formation of a glassy skin at the air/membrane interface when the relative humidity is below 55-75%. Steady-state water fluxes are interpreted through an extended Maxwell-Stefan diffusion model for a mixture of species starkly different in size. Thermodynamic nonideality is considered through Flory-Rehner polymer-solution theory. Shrinking/swelling is self-consistently modeled by conservation of the total polymer mass. Fitted Maxwell-Stefan diffusivities increase significantly with water concentration in the contact lens.
Biocompatible Materials↗