The diffusion coefficient of caffeine through agar gels containing a hyaluronic acid-protein complex. A model system for the study of the permeability of connective tissues.
ABSTRACT: A hyaluronic acid-protein complex was embedded into agar gel. This gel complex resembles in some respects the physiological situation in connective tissue, but still permits precise physicochemical measurements to be made. The diffusion coefficient of caffeine into and from such gels has been measured as a function of both agar and hyaluronate concentration. The value for the diffusion coefficient of caffeine was also measured by using a Gouy type diffusiometer. From both types of measurement the value for D (Fick) for caffeine when extrapolated to zero caffeine and agar concentrations agreed at (6.79+/-0.01)x10(-6)cm(2).s(-1) at 25 degrees C. Although agar concentration had only a small effect on caffeine diffusion, hyaluronic acid caused a large decrease in caffeine diffusion co-efficient. The presence of the hyaluronic acid-protein complex within the gel tended to oppose gel syneresis, a concentration of 1.7mg/ml abolishing the effect and higher concentrations reversing it. The possible physiological implications of these results are discussed.
Project description:Diffusion of methane diluted in supercritical carbon dioxide is studied by experiment and molecular simulation in the temperature range from 292.55 to 332.85 K along the isobars 9.0, 12.5 and 14.7 MPa. Measurements of the Fick diffusion coefficient are carried out with the Taylor dispersion technique. Molecular dynamics simulation and the Green-Kubo formalism are employed to obtain Fick, Maxwell-Stefan and intradiffusion coefficients as well as shear viscosity. The obtained diffusion coefficients are on the order of 10-8 m2/s. The composition, temperature and density dependence of diffusion is analyzed. The Fick diffusion coefficient of methane in carbon dioxide shows an anomaly in the near-critical region. This behavior can be attributed to the crossing of the so-called Widom line, where the supercritical fluid goes through a transition between liquid-like and gas-like states. Further, several classical equations are tested on their ability to predict this behavior and it is found that equations that explicitly include the density are better suited to predict the sharp variation of the diffusion coefficient near the critical region predicted by molecular simulation.
Project description:The generalized Fick-Jacobs equation is widely used to study diffusion of Brownian particles in three-dimensional tubes and quasi-two-dimensional channels of varying constraint geometry. We show how this equation can be applied to study the slowdown of unconstrained diffusion in the presence of obstacles. Specifically, we study diffusion of a point Brownian particle in the presence of identical cylindrical obstacles arranged in a square lattice. The focus is on the effective diffusion coefficient of the particle in the plane perpendicular to the cylinder axes, as a function of the cylinder radii. As radii vary from zero to one half of the lattice period, the effective diffusion coefficient decreases from its value in the obstacle free space to zero. Using different versions of the generalized Fick-Jacobs equation, we derive simple approximate formulas, which give the effective diffusion coefficient as a function of the cylinder radii, and compare their predictions with the values of the effective diffusion coefficient obtained from Brownian dynamics simulations. We find that both Reguera-Rubi and Kalinay-Percus versions of the generalized Fick-Jacobs equation lead to quite accurate predictions of the effective diffusion coefficient (with maximum relative errors below 4% and 7%, respectively) over the entire range of the cylinder radii from zero to one half of the lattice period.
Project description:Three different bioadhesive gels were evaluated in a double-blind randomized clinical trial in which microbial growth in the suture thread was assessed following post-surgical application of the aforementioned gels. Also assessed in this trial were, the intensity of post-surgical pain as well as the degree of healing of the patients' surgical wounds. A total of 21 patients (with 42 wisdom teeth) participated in this trial. Chlorhexidine gel, chlorhexidine-chitosan gel, and hyaluronic acid gel were evaluated, with a neutral water-based gel serving as the control agent. The aerobic and facultative anaerobic bacterial recovery on blood agar was lower in the placebo group than in the experimental groups. The most significant difference (p?=?0.04) was observed in the chlorhexidine-chitosan group. in which the growth of Blood Agar and Mitis Salivarius Agar was significantly higher than in the placebo group. The intensity of post-surgical pain was very similar among all the groups. Significantly better healing rates were observed in the patients treated with chlorhexidine-chitosan gel when compared with those who used the placebo gel (p?=?0.03), and in particular when compared with those patients who used hyaluronic acid gel (p?=?0.01). Through our microbiological analyses, we were able to conclude that none of the bioadhesive gels tested resulted in beneficial reductions in the bacterial/fungal populations. However, the healing rates of patients who were treated with chlorhexidine-chitosan were better than those of the patients who used either the placebo gel or the hyaluronic acid gel.
Project description:A fluorescence-based method for simultaneously determining the diffusion coefficients of two proteins is described, and the diffusion coefficient of insulin-like growth factor (IGF-I) and ribonuclease (RNase) in a 0.27% fibrin hydrogel is reported. The method is based on two-color imaging of the relaxation of the protein concentration field with time and comparing the results with a transport model. The gel is confined in a thin (200 microm) capillary and the protein is labeled with a fluorescent dye. The experimentally determined diffusion coefficient of RNase (D = 1.21 x 10(-6) cm(2)/s) agrees with literature values for dilute gels and bulk aqueous solutions, thus indicating the gel and the dye had a negligible effect on diffusion. The experimental diffusion coefficient of IGF-I (D = 1.59 x 10(-6) cm(2)/s), in the absence of binding to the fibrin matrix, is consistent with the dimensions of the molecule known from x-ray crystallography and a correlation between D and molecular weight based on 14 other proteins. The experimental method developed here holds promise for determining molecular transport properties of biomolecules under a variety of conditions, for example, when the molecule adsorbs to the gel or is convected through the gel by fluid transport.
Project description:During enhanced oil recovery (EOR), reservoir heterogeneities and fluids distributions promote preferential flow channels formation. Therefore, different types of gels have been proposed to improve swept efficiency on chemical flooding by plugging high permeability zones. The purpose of this article is to evaluate the effect that nanotechnology has on the inhibition of syneresis and the rheological properties of the Acrylamide Sodium Acrylate Copolymer/Chromium (III) Acetate gel system for conformance applications in mature reservoirs. Thus, a methodology is proposed in four stages: First, (I) nanoparticles synthesis, and characterization, followed by (II) bottle tests to monitor gelation kinetics and syneresis degree at 70 °C, then (III) description of the rheological evaluation on static and dynamic conditions to calculate gelation time and viscoelastic modulus (G' and G"), and finally (IV) the displacement test with the best gel system in the presence of nanoparticles. Results showed that the best nanoparticle was the chromium oxide (Cr2O3), which represented the lesser syneresis degree and increased gelation time. Syneresis of gel samples in the presence of Cr2O3 at day 30 was under 1% for gels prepared with 4000, 6000, and 8000 mg·L-1 of polymer, and polymer to crosslinker ratio (p/c) of 40:1. Regarding SiO2, MgO, and Al2O3 nanoparticles, results show an improvement of gel strength. However, their thermal stability in terms of syneresis was lower. Displacement test in a triple parallel Slim Tube was able to recover an additional 37% of oil of the total oil present in the sandpacks, confirming the effectivity of the system when 100 mg·L-1 of Cr2O3 nanoparticles are included.
Project description:In the present study the amount of whey protein to casein ratio (W/C ratio) (0.22-0.7), fat content (FC) (0.5-1.5%) and microbial transglutaminase (mTGase) (0.0-1.0 U/g substrate protein) in the formulation of low fat set type yoghurt, prepared from reconstituted milk, were optimized by response surface method to achieve the best rheological properties and sensory characteristics. The selected parameters consisted of higher consistency coefficient, consistency, texture and mouth feeling and lower syneresis and pH. The optimum condition was found to be 0.97, 0.46 and 0.5% of the enzyme concentration, W/C ratio and FC respectively. Results showed that thermal denaturation increased up to 33% with increasing W/C ratio significantly. All samples showed non-Newtonian shear thinning behavior. Increasing in W/C ratio from 0.22 to 0.7 raised the consistency coefficient, yield stress and textural parameters such as hardness and consistency of yoghurt. Enzyme addition (together with starter culture addition) increased yoghurt viscosity and yield stress. In sensory evaluation W/C ratio affected the texture and mouth feeling of yoghurt samples and the influences of FC and mTGase were not significant. Yoghurt syneresis was highly affected by FC, W/C ratio and mTGase.
Project description:We describe the formation of structured liquids and gels from a functionalised dipeptide based on tetraphenylethylene. Tetraphenylethylene is well-known to be able to undergo aggregation-induced emission. We use the emission data to understand the behaviour of the dipeptide in water under a variety of conditions. The dipeptide forms viscous solutions at high pH. Gels can be formed by a pH-trigger, but syneresis occurs. Addition of a calcium salt also leads to a gel with slight syneresis. Addition of sodium chloride leads to a self-supporting material, but this is not a true gel from the rheological perspective. From the emission data, we infer that there are limited structural changes on addition of sodium chloride or acid, but there are significant changes in molecular packing when the gel is formed by addition of a calcium salt.
Project description:The system-size dependence of computed mutual diffusion coefficients of multicomponent mixtures is investigated, and a generalized correction term is derived. The generalized finite-size correction term was validated for the ternary molecular mixture chloroform/acetone/methanol as well as 28 ternary LJ systems. It is shown that only the diagonal elements of the Fick matrix show system-size dependency. The finite-size effects of these elements can be corrected by adding the term derived by Yeh and Hummer (J. Phys. Chem. B 2004, 108, 15873-15879). By performing an eigenvalue analysis of the finite-size effects of the matrix of Fick diffusivities we show that the eigenvector matrix of Fick diffusivities does not depend on the size of the simulation box. Only eigenvalues, which describe the speed of diffusion, depend on the size of the system. An analytic relation for finite-size effects of the matrix of Maxwell-Stefan diffusivities was developed. All Maxwell-Stefan diffusivities depend on the system size, and the required correction depends on the matrix of thermodynamic factors.
Project description:<h4>Background</h4>Colistin has become a last-resort antibiotic for the management of multidrug-resistant gram-negative bacteria. The disk diffusion test is cheap and easy to perform but may be unreliable for colistin susceptibility testing due to poor diffusion of the large colistin molecule. An improved agar diffusion test would increase the reliability of colistin susceptibility testing. This study aimed to modify Muller-Hinton agar (MHA) to improve colistin diffusion in agar.<h4>Methods</h4>MHA was modified by reducing the agar concentration from 100% to 30% and supplementing with protamine. We tested 60 gram-negative clinical isolates of <i>Pseudomonas aeruginosa</i> (N=27) and <i>Acinetobacter calcoaceticus-baumannii</i> complex (N=33). Disk diffusion test results were interpreted based on minimum inhibitory concentrations determined by broth microdilution.<h4>Results</h4>The modified MHA yielded the best performance metrics, including 94.7% sensitivity, 100% specificity, and an area under the curve of 0.995 (95% confidence interval, 0.982-1.000), <i>P</i><0.001, at a cut-off point of 13 mm.<h4>Conclusions</h4>A reduction of the agar concentration from 100% to 30% and the addition of protamine improved colistin diffusion in agar and allowed routine colistin susceptibility testing in a clinical microbiology laboratory, but should be handled with caution.
Project description:The quality of stored frozen products such as foods and biomaterials generally degrades in time due to the growth of large ice crystals by recrystallization. While there is ample experimental evidence that recrystallization within such products (or model systems thereof) is often dominated by diffusion-limited Ostwald ripening, the application of Ostwald-ripening theories to predict measured recrystallization rates has only met with limited success. For a model system of polycrystalline ice within an aqueous solution of sugars, we here show recrystallization rates can be predicted on the basis of Ostwald ripening theory, provided (1) the theory accounts for the fact the solution can be nonideal, nondilute and of different density than the crystals, (2) the effect of ice-phase volume fraction on the diffusional flux of water between crystals is accurately described, and (3) all relevant material properties (involving binary Fick diffusion coefficients, the thermodynamic factor of the solution, and the surface energy of ice) are carefully estimated. To enable calculation of material properties, we derive an alternative formulation of Ostwald ripening in terms of the Maxwell-Stefan instead of the Fick approach to diffusion. First, this leads to a cancellation of the thermodynamic factor (a measure for the nonideality of a solution), which is a notoriously difficult property to obtain. Second, we show that Maxwell-Stefan diffusion coefficients can to a reasonable approximation be related to self-diffusion coefficients, which are relatively easy to measure or predict in comparison to Fick diffusion coefficients. Our approach is validated for a binary system of water and sucrose, for which we show predicted recrystallization rates of ice compare well to experimental results, with relative deviations of at most a factor of 2.