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Effect of diffusion boundary layers on the initial uptake of O2 by red cells. Theory versus experiment.

We have applied theories of mass transfer, in laminar and turbulent flow, to red cells in the stopped-flow apparatus in order to estimate the effect of extracellular diffusion boundary layers on the initial rate of O2 uptake. We compared the theoretical predictions with the results of our previous stopped-flow experiments with suspensions of red cells to which bovine serum albumin (BSA) had been added to decrease O2 solubility and diffusivity (Huxley and Kutchai, 1981). Models of red cells in laminar flow (Friedlander, 1957, 1961; Harriott, 1962) predict a significant retardation of the rate of O2 entry into red cells by diffusion boundary layers. Mixing in the stopped-flow apparatus occurs by convective and turbulent mechanisms in addition to simple molecular diffusion. The more complex theory of mass transfer to particles in turbulent flow (Levich, 1962) shows, because the red cells are highly entrained in the flow, that mixing is not complete on the time scale of initial O2 uptake. The O2 permeability of the diffusion boundary layer, predicted by both laminar and turbulent flow theories, approximates the experimentally obtained value. The theories of mass transfer to particles in laminar flow predict the dependence of the rate of O2 uptake on red cell size observed by other investigators. This suggests that these experimental results may be primarily due to the effect of diffusion boundary layers. Our studies are consistent with the interpretation that red cells in rapid mixing devices may be mixed incompletely with the suspending fluid; thus O2 transfer is limited by molecular diffusion in the immediate vicinity of the erythrocyte. We conclude that the rates of respiratory gas exchange by red cells in flowing systems may be partly limited by diffusion boundary layers.

Biophysical Phenomena↗

Knudsen diffusivity of a hard sphere in a rough slit pore.

An analytic theory for the Knudsen self-diffusivity D(s) of hard spheres in an atomically rough slit-shaped pore is presented which quantitatively matches simulation results. The theory assumes that, due to chaotic molecular trajectories caused by surface morphology, collisions of gas molecules with the wall are partly diffuse and partly specular, the relative magnitude of each depending upon the magnitude of the tangential momentum accommodation coefficient f. The theory thus represents a universal Knudsen fluctuation-dissipation correlation between longitudinal momentum loss and diffusivity that can simplify efforts to estimate D(s). It is also found that D(s) computed using Maxwell's theory of slip, in which collisions with the walls are assumed to be purely diffuse or specular, overpredicts the simulated D(s) by a large margin.

Journal Article↗

Free volumes and the anomalous self-diffusivity of attractive colloids.

Free volume theories for the dynamics of dense fluids commonly assume (i) that diffusivity increases with average free volume per particle and (ii) that the size distribution of free volumes can be approximated by that of an equivalent hard-sphere reference system. We use molecular simulations to demonstrate that these assumptions break down when one considers concentrated suspensions of particles with short-range attractions. In these systems, self-diffusivity shows nonmonotonic dependencies on both average free volume and the strength of the interparticle attraction. Moreover, when interparticle attractions are strong, the shape of the free volume distribution is qualitatively different than that of the corresponding hard-sphere reference fluid. We propose a conceptual revision to the traditional free volume perspective that takes into account both the size distribution and the persistence time of the free volumes, and we demonstrate that it can qualitatively capture the disparate behaviors of a model fluid with short-range attractions and its hard-sphere reference fluid.

Algorithms↗

Understanding macroscopic diffusion of adsorbed molecules in crystalline nanoporous materials via atomistic simulations.

The diffusion rates of molecules inside nanoporous materials lie at the heart of many large-scale industrial applications of these materials. Quantitatively describing this diffusion, particularly diffusion of chemical mixtures in situations leading to net mass transport, remains challenging. Molecular dynamics (MD) simulations can play an important complementary role to experiments in this area. This Account describes applications of MD to diffusion in nanoporous materials with a particular focus on macroscopic diffusion, that is, diffusion involving mass transport. These methods have made useful contributions to developing mixing theories for predicting multicomponent diffusion from single-component data and to screening new classes of materials for practical applications.

Journal Article↗

Theory of spike spiral waves in a reaction-diffusion system.

We discovered a type of spiral wave solutions in reaction-diffusion systems--spike spiral wave, which significantly differs from the spiral waves observed in the models of FitzHugh-Nagumo type. We present an asymptotic theory of these waves in the Gray-Scott model [Chem. Sci. Eng. 38, 29 (1983)]. We derive the kinematic relations describing the shape of this spiral, and find the dependence of its main parameters on the control parameters. The theory does not rely on the specific features of the Gray-Scott model and thus is expected to be applicable to a broad range of reaction-diffusion systems.

Journal Article↗

Phase velocity and phase diffusion in periodically driven discrete-state systems.

We develop a theory to calculate the effective phase diffusion coefficient and the mean phase velocity in periodically driven stochastic models with two discrete states. This theory is applied to a dichotomically driven Markovian two-state system. Explicit expressions for the mean phase velocity, the effective phase diffusion coefficient, and the Pe clet number are analytically calculated. The latter indicates as a measure of phase-coherence forced synchronization of the stochastic system with respect to the periodic driving and exhibits a "bona fide" resonance. In a second step, the theory is applied to a non-Markovian two-state system modeling excitable systems. The results prove again stochastic synchronization to the periodic driving and are in good agreement with simulations of a stochastic FitzHugh-Nagumo system.

Journal Article↗

Dynamics of conformal maps for a class of non-Laplacian growth phenomena.

Time-dependent conformal maps are used to model a class of growth phenomena limited by coupled non-Laplacian transport processes, such as nonlinear diffusion, advection, and electromigration. Both continuous and stochastic dynamics are described by generalizing conformal-mapping techniques for viscous fingering and diffusion-limited aggregation, respectively. The theory is applied to simulations of advection-diffusion-limited aggregation in a background potential flow. A universal crossover in morphology is observed from diffusion-limited to advection-limited fractal patterns with an associated crossover in the growth rate, controlled by a time-dependent effective Péclet number. Remarkably, the fractal dimension is not affected by advection, in spite of dramatic increases in anisotropy and growth rate, due to the persistence of diffusion limitation at small scales.

Journal Article↗

Diffusion of the D.A.R.E and syringe exchange programs.

We examined the diffusion of the D.A.R.E program to reduce use of illicit drugs among school-aged children and youths and the diffusion of syringe exchange programs to reduce HIV transmission among injection drug users. The D.A.R.E program was diffused widely in the United States despite a lack of evidence for its effectiveness; there has been limited diffusion of syringe exchange in the United States, despite extensive scientific evidence for its effectiveness. Multiple possible associations between diffusion and evidence of effectiveness exist, from widespread diffusion without evidence of effectiveness to limited diffusion with strong evidence of effectiveness. The decision theory concepts of framing and loss aversion may be useful for further research on the diffusion of public health innovations.

Adolescent↗

Reverse-selective diffusion in nanocomposite membranes.

The permeability of certain polymer membranes with impenetrable nanoinclusions increases with the particle volume fraction [T. C. Merkel, Science 296, 519 (2002)10.1126/science.1069580]. The discovery contradicts qualitative expectations based on Maxwell's classical theory of conduction or diffusion in composites with homogeneous phases. This Letter presents a theory based on an hypothesis that polymer chains are repelled from the inclusions during membrane casting. The accompanying increase in free volume, and hence solute diffusivity, yields bulk transport properties that are in good agreement with experiments.

Journal Article↗

Application of the method of images on electrostatic phenomena in aqueous Al2O3 and ZrO2 suspensions.

A new solution for the Poisson equation for the diffuse part of the double layer around spherical particles will be presented. The numerical results are compared with the solution of the well-known DLVO theory. The range of the diffuse layer differs considerably in the two theories. Also, the inconsistent representation of the surface and diffuse layer charge in the DLVO theory do not occur in the new theory. Experimental zeta potential measurements were used to determine the charge of colloidal Al2O3 and ZrO2 particles. It is shown that the calculated charge can be interpreted as a superposition of independent H+ and OH- adsorption isotherms. The corresponding Langmuir adsorption isotherms are taken to model the zeta potential dependence on pH. In the vicinity of the isoelectric point the model fits well with the experimental data, but at higher ion concentrations considerable deviations occur. The deviations are discussed. Furthermore, the numerical results for the run of the potential in the diffuse part of the double layer were used to determine the electrostatic interaction potential between the particles in correlation with the zeta potential measurements. The corresponding total interaction potentials, including the van der Waals attraction, were taken to calculate the coagulation half-life for a suspension with a particle loading of 2 vol%. It is shown that stability against coagulation is maintained for Al2O3 particles in the pH region between 3.3 and 7 and for ZrO2 only around pH 5. Stability against flocculation can be achieved in the pH regime between 4.5 and 7 for Al2O3, while the examined ZrO2 particles are not stable against flocculation in aqueous suspensions.

Journal Article↗

Finite dose percutaneous drug absorption: theory and its application to in vitro timolol permeation.

The finite dose in vitro percutaneous absorption kinetics of timolol, a beta-blocker, was studied. The flux of timolol across excised human abdominal cadaver skin was measured over a period of 72 h following application of a 40-microns thickness patch containing 5, 10, or 20% (w/v) timolol free base. Amounts of timolol in the patch and skin were also determined at 6, 12, 24, 48, and 72 h after the application of the 20% (w/v) patch. The mean diffusion and partition parameters were estimated to be 0.018 h-1 and 125.9 microns, respectively, using a newly developed theory. Diffusion and partition parameters were estimated using the values for amounts of a drug eventually partitioning into the perfusing water, as well as two newly proposed conceptual parameter values, AUCAv and AUCAs which are the AUCs of drug amounts in vehicle and skin, respectively. The dose-dependent skin-timolol interaction is also discussed.

Administration, Topical↗

Self-diffusion of grains in a two-dimensional vibrofluidized bed.

The analogy of vibrofluidized granular beds with a thermal gas of hard discs has been tested. Analysis of the mean squared displacement behavior of the grains allowed comparison of the measured diffusion with the predicted value at a particular combination of granular temperature and packing fraction. High speed photography, image analysis, and particle tracking software enabled accurate location of the grains. Appropriate analysis of the three mean squared displacement regimes, ballistic, diffusive, and crossover between the two extremes, allowed both the diffusion coefficient and the granular temperature to be measured at the same packing fraction. Broad agreement between Chapman-Enskog theory relating temperature to self-diffusion and observation was observed up to packing fractions of eta approximately equal to 0.7. At higher packing fractions the grains showed evidence of caging and jump diffusion, with the observed diffusion rapidly diverging from that predicted by theory. Measurement of self-diffusion coefficients and subsequent use of kinetic theory was found to be an accurate method to determine the granular temperature for intermediate packing fractions (eta=0.4-0.6), and would be particularly suitable for those situations where the time resolution of the experimental facility is insufficient to resolve the speed of the grain between collisions.

Journal Article↗

Characterization of anisotropy in high angular resolution diffusion-weighted MRI.

The methods of group theory are applied to the problem of characterizing the diffusion measured in high angular resolution MR experiments. This leads to a natural representation of the local diffusion in terms of spherical harmonics. In this representation, it is shown that isotropic diffusion, anisotropic diffusion from a single fiber, and anisotropic diffusion from multiple fiber directions fall into distinct and separable channels. This decomposition can be determined for any voxel without any prior information by a spherical harmonic transform, and for special cases the magnitude and orientation of the local diffusion may be determined. Moreover, non-diffusion-related asymmetries produced by experimental artifacts fall into channels distinct from the fiber channels, thereby allowing their separation and a subsequent reduction in noise from the reconstructed fibers. In the case of a single fiber, the method reduces identically to the standard diffusion tensor method. The method is applied to normal volunteer brain data collected with a stimulated echo spiral high angular resolution diffusion-weighted (HARD) acquisition.

Anisotropy↗

An approach to the method for determination of surface potential on solid/liquid interface: theory.

The electrochemical properties on solid particle surfaces in an aqueous system have found wide application in many fields. However, for some of them there are no reliable methods of determination. What is particularly worth mentioning is the surface potentials of solid particles. Though this is a most important property and a most basic parameter in colloid interface electrochemistry, no reliable method for its determination is available yet. In the present paper, based on the diffuse double-layer theory, mathematical relations are constructed between the average concentration of ions positively adsorbed in the diffuse double layer and the surface potential of solid particles, thus transforming the determination of surface potential of solid particles into that of the average concentration of ions in the diffuse double layer, and then by applying the standard relationships of Gouy-Chapman theory, the mathematical relations of the average concentration of ions in the diffuse double layer with surface charge density, electrical field strength at surface, and specific surface area of solid particles are constructed.

Journal Article↗

Temperature dependence of water transport into the mineralized matrix of freeze-dried human dentine.

Ten dentine sections cut perpendicular to the dentinal tubules from human mature non-carious third molars, were freeze-dried and then rehydrated by immersion in water at four temperatures, 10, 25, 40 and 70 degrees C. The uptake of water by the sections was assessed as a function of rehydration time. The data were analysed using a theoretical model in which the uptake is ascribed to two processes. The first is capillary suction of water into the dentinal tubules, the second is the diffusion of water from the two faces of the section into the mineralized matrix. By fitting theory to experiment the diffusion coefficient of water in intertubular dentine at the different temperatures was found. Using the Arrhenius relation the activation energy of diffusion of water in intertubular dentine was calculated as Ea = 29.5 +/- 2.2 kJ/mol, which is of the order of the strength of a hydrogen bond. Transport of water in the mineralized matrix during rehydration is thus most likely a hopping of water molecules along the surfaces of the collagen and/or mineral, each jump involving the breaking of one hydrogen bond.

Dentin↗