Lipase surface diffusion studied by fluorescence recovery after photobleaching

We have analyzed surface diffusion properties of a variant of Thermomyces lanuginosa lipase (TLL) on hydrophilic silica and silica methylated with dichlorodimethylsilane (DDS) or octadecyltrichlorosilane (OTS). For this study a novel method for analysis of diffusion on solid surfaces was developed. The method is based on fluorescence recovery after photobleaching using confocal microscopy. When a rectangular area of the sample was photobleached, fluorescence recovery could be analyzed as one-dimensional diffusion, resulting in simplified mathematical expressions for fitting the data. The method was initially tested by measuring bovine serum albumin diffusion on glass, which led to a diffusion coefficient in good correspondence to earlier reports. For the analysis of TLL diffusion, ellipsometry data of TLL adsorption were used to calibrate fluorescence intensity to surface density of lipase, enabling measurements of the diffusion coefficient at different surface densities. The average diffusion coefficient was calculated in two time intervals after adsorption. Mobile fraction and diffusion coefficient were lowest on the OTS surface, when extrapolated to infinite surface dilution. Moreover, the diffusion rate decreased with time on the hydrophobic surfaces. Our observations can be explained by the surface dependence on the distribution of orientations and conformations of adsorbed TLL, where the transition from the closed to the catalytically active open and more hydrophobic structure is important.     

Diffusion study of a polymer–diluent system using the optical mass transport method

Thermotropic polymers and low-molecular-weight mesogens share many common textural features. This circumstance is exploited to determine diffusion coefficents in a system consisting of a cholesteric polymer and a low-molecular-weight nematogen using the recently developed optical mass transport method. The self-diffusion coefficient and its concentration dependence were determined by using a distance–time approach, whereas the time dependence of the mutual diffusion coefficient was evaluated by a conventional concentration–distance analysis of the diffusion profile. Comparison with literature data indicates satisfactory agreement. The coefficient of the scaling law relating the self-diffusion coefficient and concentration is in accord with the value predicted by de Gennes for semidilute polymer solutions.     

Light scattering measurement and theoretical interpretation of mutual diffusion coefficients in binary liquid mixtures

Mutual diffusion coefficients for eleven binary systems of simple organic liquids have been measured by laser light scattering. By separating the mutual diffusion coefficient into a kinetic diffusion coefficient and a thermodynamic factor, we have been able to analyze the dynamical information contained in the kinetic coefficient in terms of a simple hard sphere theory of molecular motion. The hard sphere model of the kinetic diffusion coefficient is shown to be accurate for ideal and moderately nonideal solutions, and for both spherical and very nonspherical molecules. Only for extremely nonideal solutions were we unable to interpret diffusion coefficient data by our methods of analysis.     

Diffusion coefficient of Brownian particle in rough micro-channel

This study examines the feasibility of using of the lattice Boltzmann method to determine how the surface roughness of a quadrate channel affects the diffusion coefficient of Brownian particle(s). The surface was represented by a regular array of spheres. Surface roughness reduced the diffusion coefficient of the Brownian particle(s) because of a change in the velocity autocorrelation function decay and in pressure. Additionally, the neighboring particles increased the diffusion coefficient of Brownian particle.     

Effect of Modification on the Fluid Diffusion Coefficient in Silica Nanochannels

The diffusion behavior of fluid water in nanochannels with hydroxylation of silica gel and silanization of different modified chain lengths was simulated by the equilibrium molecular dynamics method. The diffusion coefficient of fluid water was calculated by the Einstein method and the Green–Kubo method, so as to analyze the change rule between the modification degree of nanochannels and the diffusion coefficient of fluid water. The results showed that the diffusion coefficient of fluid water increased with the length of the modified chain. The average diffusion coefficient of fluid water in the hydroxylated nanochannels was 8.01% of the bulk water diffusion coefficient, and the diffusion coefficients of fluid water in the –(CH₂)₃CH₃, –(CH₂)₇CH₃, and –(CH₂)₁₁CH₃ nanochannels were 44.10%, 49.72%, and 53.80% of the diffusion coefficients of bulk water, respectively. In the above four wall characteristic models, the diffusion coefficients in the z direction were smaller than those in the other directions. However, with an increase in the silylation degree, the increased self-diffusion coefficient due to the surface effect could basically offset the decreased self-diffusion coefficient owing to the scale effect. In the four nanochannels, when the local diffusion coefficient of fluid water was in the range of 8 Å close to the wall, Dz was greater than Dxy, and beyond the range of 8 Å of the wall, the Dz was smaller than Dxy.     

Mass transport in a chiral nematic/nematic liquid crystal system

The optical microscopic mass transport technique has been used to study diffusion phenomenon in a chiral nematic/nematic solute/solvent mixture. Analysis of the concentration-distance, concentration-time and distance-time of the diffusion profile gave the diffusion coefficient of the system as a function of time, distance and concentration, respectively. The mutual diffusion coefficient of the system was independent of the distance and time, showing an average value of 2.65 × 10^-7 cm² s^-1. In non-steady state diffusion, the diffusion coefficient was dependent on both distance and time. The diffusion coefficient exhibited an inverse relation with the local concentration of the chiral solute. The self-diffusion coefficient of the nematic solvent gave a value of 3.4 × 10^-7 cm² s^-1 via extrapolation to zero concentration of the solute.     

Diffusion of water vapor through a hydrophilic polymer film

Multifilm techniques have been used to measure the diffusion coefficient of water vapor in cellophane, and the data have been compared with the integral diffusion coefficient obtained in previous work with single films. The multifilm techniques lead to a much sharper resolution of the effect of concentration on diffusion, and the maximum integral diffusion coefficient. The diffusion coefficient for water vapor in cellophane peaks at a moisture content corresponding to about 70% R. H., which is presumably the “critical concentration” discussed in previous work on the thermodynamics of water sorption by cellophane.     

Diffusion coefficients as a monitor of reaction kinetics of biological molecules

For revealing spectrally silent dynamics in chemical reactions, a new method, the time-dependent diffusion coefficient, is presented. Principles and typical examples of this method, in particular applications to biologically related reactions, are reviewed. The pulsed laser induced transient grating signal of the photo-decomposition reaction of caged ATP showed that the diffusion coefficient increases gradually with time reflecting the molecular size decrease by the dissociation. Hence, this rate should be a direct measurement of the photo-dissociation rate of ATP from the caged state. In an application to a protein folding reaction, the time-development of the diffusion coefficient was observed during the folding reaction. This time dependence was interpreted in terms of the intermolecular interaction change; i.e., conversion from the intermolecular hydrogen bonding to intramolecular one. It was found that the change of the hydrogen bonding network occurred by the two state manner in entire refolding process of cytochrome c. The unique feature of this time-dependent diffusion coefficient method is discussed.     

Adsorption kinetics in the polyethylenimine–cellulose fiber system

The rate of adsorption of fractionated polyethylenimine (PEI) from water onto regenerated cellulose fibers was studied as a function of the polymer diffusion coefficient. Differences in polymer molecular weight, salt concentration, and pH were employed to vary the diffusion coefficient which was measured independently by a free-diffusion technique. The sorption rate was measured at the same conditions and found to increase with decreasing molecular weight, increasing polymer concentration, decreasing salt concentration, and increasing pH. A simplified rate equation based on diffusion control with Langmuirian adsorption in stirred solution was developed by utilizing the concept of a Nernst diffusional film. The equation was successful in predicting the relationship between adsorption rate and diffusion coefficient for most cases studied. It was found, however, that a very large barrier to mass transfer retards the adsorption rate. For the system studied it was concluded that this barrier is a result of diffusion into and subsequent adsorption onto the internal porous structure of the cellulose.     

MH电极中氢扩散系数的测定及其应用

利用恒流放电法测定了金属氢化物(MH)电极中氢原子扩散系数的平均值. 通过恒电位法测定了MH电极中氢原子的扩散系数与其荷电态(SOC)的关系. 根据MH电极模型可知, 增大氢原子扩散系数或减小储氢合金粒径均能提高MH电极的快速充电性能, 并能计算出MH电极在不同的初始荷电态、不同充电倍率下, 表面氢原子浓度达到最大值所需的时间.     

Transient permeation of organic vapors through elastomeric membranes

The permeation of benzene and acetone vapors through sulfur-cured natural rubber was studied by the time-lag method. The experimental results were analyzed by a method suggested by Meares. The zero concentration diffusion coefficient D₀ was obtained by the early-time method. The Frisch time-lag equation was utilized to estimate both the solubility coefficient s and the additional parameter b required to define the concentration dependence of the diffusion coefficient: D(c) = D₀ exp {bc}. This form of concentration dependence was manifested by the corresponding permeability coefficient values. At low entering penetrant pressure, where the transport coefficients are constant, indirect evidence was obtained that D₀ is the mechanistically correct diffusion coefficient. The solubility coefficient values calculated for benzene vapor in natural rubber are in reasonable agreement with published equilibrium sorption data for a similar rubber compound. At higher entering penetrant pressures, average diffusion coefficients obtained at steady state tended to be larger than the corresponding average diffusion coefficients derived from the time lags. This same effect has been detected by other experimental approaches. Permeation experiments designed for this rapid method of analysis appear capable of yielding information consistent with that obtained by more time-consuming traditional methods.     

Estimation of concentration-dependent diffusion coefficient in pressure-decay experiment of heavy oils and bitumen

Molecular diffusion has been considered to be an underlying mechanism for many of oil recovery processes like miscible and immiscible gas injection projects. Reliable estimation of the molecular diffusion coefficient as a transport property is therefore important in studying the performance of such systems. Interpretation of pressure-decay data has been traditionally used to estimate the molecular diffusion coefficient and usually to simplify the interpretation, its concentration dependency has been neglected. A pressure-decay model with concentration-dependent diffusion coefficient leads to a non-linear problem in which an analytical solution is difficult if not impossible to obtain. In this study, we used the Heat Integral Method (HIM) to solve the non-linear diffusion problem as a forward model. Using that forward model, we have developed a simple methodology for estimating the diffusion coefficient regardless of the form of function used for the concentration dependency of the molecular diffusion. Three different forms of functions for diffusion coefficient were considered. In its simplest form, the diffusion coefficient is set to be a constant value. In the two other forms, the diffusion coefficient was evaluated as a concentration-dependent two parameter equation using exponential and power-law functions, respectively. The proposed methodology is verified and tested using direct numerical solutions of the non-linear diffusion problem. Many numerical examples with a wide range of input parameters demonstrate the effectiveness of the proposed approach.     

Diffusion measurements in chiral liquid crystals

Abstract

We present results of diffusion investigations in twisted nematics (nematic-cholesteric mixtures). The dependence of the diffusion coefficient along the helix on the concentration of the cholesteric compound, the sample temperature and the diffusion time are measured by a new nuclear magnetic resonance method. The diffusion coefficient was found to decrease with diffusion time in the studied range of about 0·5–50 ms. The results are consistent with data from ¹³C-N.M.R. experiments, and with field gradient measurements by other authors.     

Simulation and modelling of transient permeation of organic solvents through polymer films in the case of a concentration dependent diffusion coefficient

The measured transient permeation kinetics of acetic acid from a water-acetic acid mixture through poly(vinyl alcohol) films could not be accounted for by the Fick law with a constant diffusion coefficient. A new calculation procedure was developed on the basis of simulation results of the Fickian kinetics in which the diffusion coefficient was assumed to increase exponentially with the local permeant concentration. A fast and reliable fitting procedure, which was set up on a Personal Computer, involves an iterative numerical adjustment of (a) the value of the limiting diffusion coefficient D^* (i.e., difusion of the permeant in dry polymer) using the onset part of the permeation rate followed by (b) the value at the upstream face of the plasticization term (argument of the exponential function) using the shape of the experimental curve. The values obtained from fitting the model to the transient kinetics showed that the limiting diffusion coefficient increases drastically, but the plasticization term changes little, with increasing temperature.     

Sorption rate and thermal barriers in a gas-zeolite system: investigation of n-hexane sorption in MFI-type zeolite

The nonequilibrium gravimetric sorption method was used to determine diffusion coefficient values for n-hexane in MFI-type materials. Improvements in the measurement device and experimental conditions resulted in high values of the corrected diffusion coefficient, which are comparable to the literature data obtained by the methods of pulsed field gradient nuclear magnetic resonance (PFG NMR) and frequency response (FR). The results indicate that thermal effects of sorption affect practically neither the rate of the sorption nor the diffusion coefficient.     

Measurement of the infinite dilution diffusion coefficients of small molecule solvents in silicone rubber by inverse gas chromatography

The infinite dilution diffusion coefficients of n-hexane, n-heptane and n-decane in crosslinked silicone rubber with different crosslinking agent concentrations were measured in the temperature range of 348.15 K-368.15 K by inverse gas chromatography. The crosslinked silicone rubber was obtained by dissolving PDMS prepolymer, crosslinking agent and catalyst in n-heptane solvent and characterized by FTIR spectra. The Van Deemter equation was used to determine diffusion coefficients from the variation in chromatographic peak width with carrier gas flow rate. The good linear relation indicated the Van Deemter equation used in this work was reliable. The influences of small molecule solvent, crosslinking agent concentration and temperature on the infinite dilution diffusion coefficient were investigated. The results showed that the infinite dilution diffusion coefficient decreased with an increasing number of CH₂ group in the alkane series. The increase in crosslinking agent concentration resulted in decrease of the infinite dilution diffusion coefficient. The infinite dilution diffusion coefficient increased with the rising of temperature. The interdependence on the infinite dilution diffusion coefficient and temperature accorded with Arrhenius equation well. Diffusion constant and activation energy obtained from the Arrhenius equation provided straight lines with the specific critical volume and crosslinking agent concentration.     

Testing ion-neutral interaction potentials using calculated ion transport coefficients

Several commonly measured ion transport coefficients were investigated in order to determine their sensitivity for testing and comparing proposed ion-neutral interaction potentials. A variety of positive ions, negative ions, neutrals, and temperatures were included in order to draw as general a conclusion as possible. All transport coefficients considered were found to be sufficiently sensitive to be used to clearly distinguish between less and more accurate interaction potentials. It was also found that the longitudinal diffusion coefficient is the most sensitive test, followed by both the transverse diffusion coefficient and the ratio of the longitudinal diffusion coefficient to mobility, followed by the ratio of the transverse diffusion coefficient to mobility and that the mobility is the least sensitive test. When presently achievable levels of experimental error were also taken into account, however, there was no significant difference in the sensitivities.     

A NEW MODEL FOR ESTIMATION OF DIFFUSION COEFFICIENT OF PHENOL DESORPTION WITHIN POLYMERIC RESIN UNDER ULTRASOUND

1. INTRODUCTION Ultrasound is a kind of mechanical wave whose frequency is more than 20 kilohertz. It can enhance the mass transfer, increase the rate and conversion of chemical reaction, change the reaction pathway [1,2] and accelerate the conversion of…     

Mechanism of diffusion and sorption of carbon dioxide in poly(vinyl acetate) above and below the glass transition temperature

The pressure dependence below 1 atm of the apparent diffusion and permeation coefficients were observed by using the permeation time lag method for carbon dioxide in poly(vinyl acetate), which has a glass transition near room temperature, at temperatures ranging from 8 to 50°C. Above the glass transition temperature, pressure dependence of the diffusion and permeation coefficient has not been observed; hence, Fick's law with a concentration independent diffusion coefficient applies. On the other hand, in the glassy state, the apparent diffusion coefficient shows pressure dependence. Moreover, the behavior of the pressure dependence does not show a clear curve in the ranges between 30°C to 17°C. Above 17°C, the apparent diffusion coefficients show discontinuities, but below 17°C increase with pressure is regular. Using the theoretical prediction of Paul, a computer was used in the numerical calculation to determine the true diffusion coefficient and other dual sorption parameters. p]The compensated diffusion coefficients controlled only by Henry's law dissolution was described by three straight lines with two intersection in the form of Arrhenius plots, which give good agreement with both our results for He and Ar and those of Meares. It is assumed that beside the dual sorption mechanism, another effect, for instance some relaxation effect may also contribute to the diffusion for carbon dioxide in poly(vinyl acetate) near the glass transition temperature region.     

利用泰勒分析和动态涂层毛细管电泳系统快速测定蛋白质的扩散系数

以泰勒分散理论为基础, 首次采用动态涂层毛细管来准确和快速测定蛋白质分子的扩散系数.