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PubMed1977

Amphiphile diffusion in model membrane systems studied by pulsed NMR.

The translational diffusion of the amphiphilic molecules in a number of lyotropic liquid crystalline phases has been measured with the pulsed NMR pulsed magnetic field gradient method. The amphiphiles studied were soaps, monoglycerids and lecithins. Measurements were performed both for oriented lamellar and for cubic phases. The order of magnitude of the diffusion coefficients was found to be the same as in neat liquids of analogous compounds. It was also found that the difussion coefficient depend markedly on the amphiphile end group in a way that parallels the area per polar head group as determined in X-ray studies. When corrections for geometrical factors has been made the diffusion rate is approximately equal in cubic and lamellar phases containing the same amphiphile.

Chemical Phenomena↗
PubMed2006

Microbially-influenced degradation of solidified/stabilized metal waste.

In the present study, a refined microbially-influenced degradation method was used to evaluate the stability of a solidified synthetic waste containing chromium salt, cement and fly ash in two different proportions. The experimental samples showed evidence of microbial growth by leaching of sulfate. Chromium leached by Thiobacillus thiooxidans from the experimental samples 'C1' (10.26% CrCl3 .6H2O; 89.74% cement) and 'FC1' (10.26% CrCl3 .6H2O; 10% fly ash; 79.74% cement), after 30 days of exposure was 14.53 mg/g and 9.53 mg/g, respectively. The corresponding concentration of chromium in the leachate was 0.189 mg/l and 0.124 mg/l, respectively, which was lower than the toxicity characteristic leaching procedure (TCLP), regulatory limit (5 mg/l). Replacement of cement by 10% fly ash in FC1 restricted the leaching of chromium more effectively. Model equations based on two shrinking core models namely, acid dissolution and bulk diffusion model, were used to analyze the kinetics of microbial degradation. Of the two approaches, the bulk diffusion model fit the data better than the acid dissolution model as indicated by the correlation coefficients of >0.97.

Acidithiobacillus thiooxidans↗
PubMed2006

Analysis of electron transfer processes across liquid/liquid interfaces: estimation of free energy of activation using diffuse boundary model.

The evaluation of the free energy of activation pertaining to the electron-transfer reactions occurring at liquid/liquid interfaces is carried out employing a diffuse boundary model. The interfacial solvation numbers are estimated using a lattice gas model under the quasichemical approximation. The standard reduction potentials of the redox couples, appropriate inner potential differences, dielectric permittivities, as well as the width of the interface are included in the analysis. The methodology is applied to the reaction between [Fe(CN)6](3-/4-) and [Lu(biphthalocyanine)](3+/4+) at water/1,2-dichloroethane interface. The rate-determining step is inferred from the estimated free energy of activation for the constituent processes. The results indicate that the solvent shielding effect and the desolvation of the reactants at the interface play a central role in dictating the free energy of activation. The heterogeneous electron-transfer rate constant is evaluated from the molar reaction volume and the frequency factor.

Journal Article↗
PubMed2006

Complete breakdown of the Debye model of rotational relaxation near the isotropic-nematic phase boundary: effects of intermolecular correlations in orientational dynamics.

The Debye-Stokes-Einstein (DSE) model of rotational diffusion predicts that the orientational correlation times tau l vary as [l(l+1)]-1, where l is the rank of the orientational time correlation function (given in terms of the Legendre polynomial of rank l). One often finds significant deviation from this prediction, in either direction. In supercooled molecular liquids where the ratio tau 1/tau 2 falls considerably below 3 (the Debye limit), one usually invokes a jump diffusion model to explain the approach of the ratio tau 1/tau 2 to unity. Here we show in a computer simulation study of a standard model system for thermotropic liquid crystals that this ratio becomes much less than unity as the isotropic-nematic phase boundary is approached from the isotropic side. Simultaneously, the ratio tau 2/eta, eta, being the shear viscosity of the liquid, becomes much larger than the hydrodynamic value near the I-N transition. We also analyze the breakdown of the Debye model of rotational diffusion in ratios of higher order orientational correlation times. We show that the breakdown of the DSE model is due to the growth of orientational pair correlation and provide a mode coupling theory analysis to explain the results.

Journal Article↗
PubMed1998

Far-field analysis of coupled bulk and boundary layer diffusion toward an ion channel entrance.

We present a far-field analysis of ion diffusion toward a channel embedded in a membrane with a fixed charge density. The Smoluchowski equation, which represents the 3D problem, is approximated by a system of coupled three- and two-dimensional diffusions. The 2D diffusion models the quasi-two-dimensional diffusion of ions in a boundary layer in which the electrical potential interaction with the membrane surface charge is important. The 3D diffusion models ion transport in the bulk region outside the boundary layer. Analytical expressions for concentration and flux are developed that are accurate far from the channel entrance. These provide boundary conditions for a numerical solution of the problem. Our results are used to calculate far-field ion flows corresponding to experiments of Bell and Miller (Biophys. J. 45:279, 1984).

Biophysics↗
PubMed2002

New model of surface diffusion in reversed-phase liquid chromatography.

A new model of surface diffusion in reversed-phase liquid chromatography (RPLC) was derived by assuming a correlation between surface and molecular diffusion. Analysis of surface diffusion data under different conditions of sample compounds, mobile and stationary phases, and temperature in RPLC systems validates this assumption and shows that surface diffusion should be regarded as a molecular diffusion restricted by the adsorptive interactions between the adsorbate molecule and the stationary phase surface. A surface-restricted molecular diffusion model was proposed as a first approximation for the mechanism of surface diffusion. The model is formulated according to the absolute rate theory. The activation energy of surface diffusion (Es) was quantitatively interpreted assuming that Es consists of the contributions of two processes, a hole-making and a jumping one. The former contribution is nearly equal to the activation energy of molecular diffusion and is correlated with the evaporative energy of the mobile phase solvent. The latter contribution is a fraction of the isosteric heat of adsorption. An appropriate explanation based on this new model of surface diffusion is provided for two contradictory results related to the relationship between retention equilibrium and surface diffusion in RPLC and to the surface diffusion coefficient for weakly retained sample compounds.

Chromatography, Liquid↗
PubMed1999

Predictive Sagiv-Stroeve Model for Diffusion through Monolayer and Multilayer Films.

A one-parameter model has been derived by A. Sagiv and P. Stroeve for diffusion through crystalline monolayer and multilayer Langmuir-Blodgett films (J. Colloid Interface Sci. 204, 173 (1998)). The model can describe well a number of experimental observations. The parameter that is needed for the model, the activation rate constant (k), is obtained by fitting the experimental data. It is shown in this letter that the parameter can be calculated independently; hence, the model can be predictive. Examples for predictions are given. Copyright 1999 Academic Press.

Journal Article↗
PubMed1989

Axonal injury in the optic nerve: a model simulating diffuse axonal injury in the brain.

A new model of traumatic axonal injury has been developed by causing a single, rapid, controlled elongation (tensile strain) in the optic nerve of the albino guinea pig. Electron microscopy demonstrates axonal swelling, axolemmal blebs, and accumulation of organelles identical to those seen in human and experimental brain injury. Quantitative morphometric studies confirm that 17% of the optic nerve axons are injured without vascular disruption, and horseradish peroxidase (HRP) studies confirm alterations in rapid axoplasmic transport at the sites of injury. Since 95% to 98% of the optic nerve fibers are crossed, studies of the cell bodies and terminal fields of injured axons can be performed in this model. Glucose utilization was increased in the retina following injury, confirming electron microscopic changes of central chromatolysis in the ganglion cells and increased metabolic activity in reaction to axonal injury. Decreased activity at the superior colliculus was demonstrated by delayed HRP arrival after injury. The model is unique because it produces axonal damage that is morphologically identical to that seen in human brain injury and does so by delivering tissue strains of the same type and magnitude that cause axonal damage in the human. The model offers the possibility of improving the understanding of traumatic damage of central nervous system (CNS) axons because it creates reproducible axonal injury in a well-defined anatomical system that obviates many of the difficulties associated with studying the complex morphology of the brain.

Animals↗
PubMed2003

Developing the molecular modelling of diffusion in zeolites as a high throughput catalyst screening technique.

Molecular modelling techniques have been used to screen zeolite catalysts for their suitability for organic synthesis. For example, we have used these techniques to study the alkylation of aromatic molecules which are important in the fine-chemical and drug industries. A survey of all such efforts is reviewed in this article. The application of molecular modelling techniques in a systematic manner is an efficient first step in the design of zeolite catalysts. As a qualitative screening tool, molecular graphics is used to visualize how well the reactant and product molecules fit inside the pores of the zeolites. Using a hybrid of several molecular modelling methods, which combines molecular dynamics (MD) and Monte Carlo methods with energy minimization, it is possible to determine the minimum energy locations of the molecules inside the zeolites cages. The minimum energy configurations determined by this hybrid method are taken as a starting point for diffusion of the molecules through the zeolite channels. When a molecule is allowed to diffuse through zeolite channel, the molecule attains some maxima and minima in its diffusion energy profile. From the differences between a maximum and a minimum energy configuration, the diffusion energy barrier for the molecule can be calculated in the zeolites. By comparing the diffusion energy barriers for various isomers of a molecule in different zeolites, it is possible to find out the most suitable zeolite for achieving the required shape-selectivity. In addition, factors influencing the diffusivity of the molecules and consequently the shape selectivity are derived. The list of factors and their relative importance are analysed to derive valuable guidelines to design shape-selective zeolite catalysts for a given reaction. Thus, the ultimate aim of these studies is to develop a high throughput computational screening process for the selection of shape-selective zeolite catalysts for various reactions. The dynamic behaviour of molecules inside the pores of zeolites can be studied using MD methods. Since MD is computationally time consuming, it is more efficient to screen the possible zeolite catalysts by energy minimization methods and then perform MD in specific zeolites. More accurate values of diffusivity of the molecules can be calculated using MD methods, and these values can be correlated with the shape-selectivity observed experimentally and /or derived from diffusion energy barrier calculations.

Catalysis↗
PubMed1991

Kinetic analysis of cAMP-activated Na+ current in the molluscan neuron. A diffusion-reaction model.

cAMP-activated Na+ current (INa,cAMP) was studied in voltage-clamped neurons of the seaslug Pleurobranchaea californica. The current response to injected cAMP varied in both time course and amplitude as the tip of an intracellular injection electrode was moved from the periphery to the center of the neuron soma. The latency from injection to peak response was dependent on the amount of cAMP injected unless the electrode was centered within the cell. Decay of the INa,cAMP response was slowed by phosphodiesterase inhibition. These observations suggest that the kinetics of the INa,cAMP response are governed by cAMP diffusion and degradation. Phosphodiesterase inhibition induced a persistent inward current. At lower concentrations of inhibitor, INa,cAMP response amplitude increased as expected for decreased hydrolysis rate of injected cAMP. Higher inhibitor concentrations decreased INa,cAMP response amplitude, suggesting that inhibitor-induced increase in native cAMP increased basal INa,cAMP and thus caused partial saturation of the current. The Hill coefficient estimated from the plot of injected cAMP to INa,cAMP response amplitude was close to 1.0. An equation modeling INa,cAMP incorporated terms for diffusion and degradation. In it, the first-order rate constant of phosphodiesterase activity was taken as the rate constant of the exponential decay of the INa,cAMP response. The stoichiometry of INa,cAMP activation was inferred from the Hill coefficient as 1 cAMP/channel. The equation closely fitted the INa,cAMP response and simulated changes in the waveform of the response induced by phosphodiesterase inhibition. With modifications to accommodate asymmetric INa,cAMP activation, the equation also simulated effects of eccentric electrode position. The simple reaction-diffusion model of the kinetics of INa,cAMP may provide a useful conceptual framework within which to investigate the modulation of INa,cAMP by neuromodulators, intracellular regulatory factors, and pharmacological agents.

1-Methyl-3-isobutylxanthine↗
PubMed2005

Diffuse-interface model for rapid phase transformations in nonequilibrium systems.

A thermodynamic approach to rapid phase transformations within a diffuse interface in a binary system is developed. Assuming an extended set of independent thermodynamic variables formed by the union of the classic set of slow variables and the space of fast variables, we introduce finiteness of the heat and solute diffusive propagation at the finite speed of the interface advancing. To describe transformations within the diffuse interface, we use the phase-field model which allows us to follow steep but smooth changes of phase within the width of the diffuse interface. Governing equations of the phase-field model are derived for the hyperbolic model, a model with memory, and a model of nonlinear evolution of transformation within the diffuse interface. The consistency of the model is proved by the verification of the validity of the condition of positive entropy production and by outcomes of the fluctuation-dissipation theorem. A comparison with existing sharp-interface and diffuse-interface versions of the model is given.

Journal Article↗
PubMed1998

A model for diffusive transport through a spherical interface probed by pulsed-field gradient NMR.

In biological systems, because of higher intracellular viscosity and/or the restriction of the diffusion space inside cells, the (apparent) diffusion coefficient of an intracellular species (e.g., water) is generally smaller than when it is in the extracellular medium. This difference affects the spin-echo signal attenuation in the pulsed field gradient NMR experiment and thus affords a means of separating the intracellular from the extracellular species, thereby providing a basis for studying transmembrane transport. Such experiments have commonly been analyzed using the macroscopic model of Kärger (see Adv. Magn. Reson. 21:1-89 (1988)). In our previous study, we considered a microscopic model of diffusive transport through a spherical interface using the short gradient pulse approximation (J. Magn. Reson. A114:39-46 (1995)). The spins in the external medium were modeled with the "partially absorbing wall" condition or as having a small but finite lifetime. In the present paper, we extend our treatment to the case in which there is no limitation upon the lifetime in either medium. We also consider a simple modification of Kärger's model that more properly accounts for the restricted intracellular diffusion. Importantly, it was found that the exact solution within the short gradient pulse approximation developed here and the modified Kärger model are in close agreement in the (experimentally relevant) long-time limit. The results of this study show that when there is no limitation upon the lifetime of the transported species in either phase, the spin-echo attenuation curve is very sensitive to transport.

Diffusion↗
PubMed2003

Kinetic analysis of data obtained from studies on microbial degradation of cement waste forms, using shrinking core models.

Model equations based on analytical solutions of two shrinking core models (acid dissolution or shrinking unreacted core (SUC) model, and bulk diffusion model), were used to analyze the kinetics of microbial degradation of cement waste forms. Two current approaches of waste form microbial stability evaluation (Nuclear Regulatory Commission (NRC) method and refined biofilm formation) were used to generate the data. Good linear correlations with R(2)>0.95 were obtained for the leaching data from both the NRC and biofilm approaches, using the model equation based on the bulk diffusion concept. Analyses using the model equation based on the acid dissolution model generally gave poor correlations except when data obtained from biofilm formation method was normalized.

Biodegradation, Environmental↗
PubMed1999

Unconjugated bilirubin exhibits spontaneous diffusion through model lipid bilayers and native hepatocyte membranes.

The liver is responsible for the clearance and metabolism of unconjugated bilirubin, the hydrophobic end-product of heme catabolism. Although several putative bilirubin transporters have been described, it has been alternatively proposed that bilirubin enters the hepatocyte by passive diffusion through the plasma membrane. In order to elucidate the mechanism of bilirubin uptake, we measured the rate of bilirubin transmembrane diffusion (flip-flop) using stopped-flow fluorescence techniques. Unconjugated bilirubin rapidly diffuses through model phosphatidylcholine vesicles, with a first-order rate constant of 5.3 s-1 (t(1)/(2) = 130 ms). The flip-flop rate is independent of membrane cholesterol content, phospholipid acyl saturation, and lipid packing, consistent with thermodynamic analyses demonstrating minimal steric constraint to bilirubin transmembrane diffusion. The coincident decrease in pH of the entrapped vesicle volume supports a mechanism whereby the bilirubin molecule crosses the lipid bilayer as the uncharged diacid. Transport of bilirubin by native rat hepatocyte membranes exhibits kinetics comparable with that in model vesicles, suggesting that unconjugated bilirubin crosses cellular membranes by passive diffusion through the hydrophobic lipid core. In contrast, there is no demonstrable flip-flop of bilirubin diglucuronide or bilirubin ditaurate in phospholipid vesicles, yet these compounds rapidly traverse isolated rat hepatocyte membranes, confirming the presence of a facilitated uptake system(s) for hydrophilic bilirubin conjugates.

Animals↗
PubMed2002

Shear stress and vascular remodeling: study of cardiac allograft coronary artery disease as a model of diffuse atherosclerosis.

BACKGROUND: The assessment of remodeling in diffuse atherosclerosis by intravascular ultrasound is hampered by the lack of an appropriate reference segment. Transplant coronary artery disease is an accepted model of diffuse atherosclerosis. Flow-dependent remodeling is regulated by shear stress. Thus, normal levels of shear stress at baseline flow reflect adequate regulation and provide a functional assessment of flow-dependent remodeling. METHODS: The approach was evaluated in 91 patients with transplant coronary artery disease and in 9 non-transplanted controls and 16 control transplant recipients. Quantitative coronary angiography, intracoronary ultrasound and intracoronary velocity studies were performed at baseline and after pharmacologic intervention. Calculated shear stress was compared between these groups and a sub-group with coronary angioplasty at follow-up (8 of 60 patients with control angiography after 23 +/- 8 months). The relation of shear stress to flow, diameter, flow/area ratio and endothelial function was analyzed. RESULTS: Normal shear stress was found in non-transplanted controls and transplant recipients without coronary artery disease. Patients with coronary angioplasty at follow-up had elevated shear stress and enhanced endothelial dysfunction on the initial investigation. Shear stress was not correlated with flow (r = 0.062, non-significant), but with diameter (r = -0.654), flow/area ratio (r = 0.814) and endothelial dysfunction (r = 0.722). CONCLUSION: Calculated local shear stress appears to be useful for the assessment of the adequacy of flow-dependent macrovascular remodeling in diffuse atherosclerosis. Elevated blood flow/area ratio is a potential clinical marker of increased shear stress that reflects inadequate flow-dependent remodeling.

Adult↗
PubMed1995

On the comparison of Feller and Ornstein-Uhlenbeck models for neural activity.

Diffusion processes have been extensively used to describe membrane potential behavior. In this approach the interspike interval has a theoretical counterpart in the first-passage-time of the diffusion model employed. Since the mathematical complexity of the first-passage-time problem increases with attempts to make the models more realistic it seems useful to compare the features of different models in order to highlight their relative performance. In this paper we compare the Feller and Ornstein-Uhlenbeck models under three different criteria derived from the level of information available about their parameters. We conclude that the Feller model is preferable when complete knowledge of the characterizing parameters is assumed. On the other hand, when only limited information about the parameters is available, such as the mean firing time and the histogram shape, no advantage arises from using this more complex model.

Diffusion↗
PubMed2004

Pattern of cerebral edema and hemorrhage in a mice model of diffuse brain injury.

This study aims to examine the time course of the brain edema formation in relation with blood-brain barrier (BBB) disruption and cerebral hemorrhage in a murine model of diffuse brain injury. Brain water content increased at 1 h post-injury and persisted up to 7 days. This event was associated with electrolyte imbalance such as Na(+) increase within 24 h. Prominent Evans blue extravasation was also observed from 1 to 6 h post-injury. Concurrently, hemoglobin increased markedly by 1 h, reached a peak at 4 h and declined progressively within a week in association with a rise of parenchyma iron content between 24 h and 7 days. These results suggest that brain edema is vasogenic and that the hemorrhage process is involved in the BBB disruption and edema, both leading to post-traumatic secondary events.

Animals↗