Increasing Gel Concentration Research Articles

Diffusion of hydrophilic to hydrophobic forms of Nile red in aqueous C12EO10 gels by variable area fluorescence correlation spectroscopy.

Solute diffusion within lyotropic liquid crystal gels prepared from a series of water and decaethylene glycol monododecyl ether (C12EO10) mixtures was explored by variable area fluorescence correlation spectroscopy. Aqueous C12EO10 gels were prepared in concentrations ranging from 55 : 45 to 70 : 30 wt% of surfactant and water. Small angle X-ray scattering revealed that these gels comprise hexagonal mesophases of cylindrical micelles. Micelle spacing was found to decrease with increasing C12EO10 concentration. Three different Nile red (NR) dyes were employed as model solutes and were separately doped into the gels at nanomolar levels. These include a hydrophilic form of NR incorporating an anionic sulfonate group (NRSO3-), a hydrophobic form incorporating a fourteen-carbon alkane tail (NRC14), and commercial NR as an intermediate case. FCS data acquired from the gels revealed that NRSO3- diffused primarily in 3D. Its diffusion coefficient exhibited a monotonic decrease with increasing gel concentration and micelle packing density, consistent with confinement of its motions by its exclusion from the micelle cores. NRC14 exhibited the smallest diffusion coefficient, most likely due to its larger size and enhanced interactions with the micelle cores. NR yielded an intermediate diffusion coefficient and the most anomalous behavior of the three dyes, attributable to its facile partitioning between core and corona regions, and greater participation by 1D diffusion. The results of these studies afford an improved understanding of molecular mass transport through soft-matter nanomaterials like those being developed for use in drug delivery and membrane based chemical separations.

Micro-nanoparticle gels obtained from bark for their use alone and with chitosan and Na-CMC in paper coatings

Abstract The effect of coatings on paper sheets has been studied. For this purpose gels were prepared from unextracted and extracted bark. The gels represented dispersions of micro- and nanoparticles. The coatings were also prepared from mixtures of gels with chitosan solutions in 1% acetic acid and aqueous Na-carboxymethylcellulose (Na-CMC) solutions. The properties – Gurley air resistance, water vapour sorption, and mechanical properties of paper sheets – were tested. For obtaining the gels, the bark was destructed by a thermocatalytic method and then dispersed in water in a ball mill. The gels contained mainly nanoparticles with an average size of about 300 nm. Paper sheets produced by the Ligatne Paper Mill (Latvia) were coated on both sides. Gurley air resistance increases with increasing thickness of the coatings and with increasing gel concentration. At a gel concentration of 10% and a coating thickness of 35 μm, air resistance increases by 57% (gel from unextracted bark) and 72% (gel from extracted bark) compared to uncoated paper sheets. The coatings from bark gels in combination with Na-CMC and chitosan solutions increase further the air resistance. The coatings at gel concentrations up to 6% elevate the burst strength and tensile strength in a dry state. The coatings from mixtures of bark gel and chitosan and Na-CMC heighten further the mechanical properties and elevate the water vapour sorption of paper sheets.

Drying dissipative structures of gelatin solution

Macroscopic and microscopic drying patterns formed from aqueous gelatin solutions on a cover glass were studied as a function of gelatin concentration and temperature. Specific drying patterns were observed within the circular dried film resulting from a droplet of the solution (0.1 ml) placed on the cover glass surface when the droplet evaporated. Two broad rings formed at the outside edge of the dried film and the inner area. df/di values of the inner broad rings decreased sharply with increasing gel concentration, where df is the final size of the broad ring in the dried film and di is the size of initial liquid in diameter. Thickness profiles of the dried film changed sharply from the broad ring to the round hill at the center as gelatin concentration increased. The sharpness parameter S (or S′) were evaluated from the ratio of the film size (diameter) against the full widths at half maximum (or the full widths at the bottom layer) in the thickness profiles of the broad ring and/or the round hill. The S (or S′) values changed transitionally at the critical concentration and temperature of gelation. The gelation of gelatin collagen was resulted in the disturbed convectional diffusion of solutes during dryness. The round hill-like thickness profile at the high polymer concentration and at low temperature also supports the gelation. These observations support that gelation process of collagen molecules is followed from decrease in S (or S′) values in the macroscopic patterns. Dendritic, hedrite, and/or spherulite microscopic drying patterns were observed especially in the central area and at low temperatures.

Stiffness of Extracellular Matrix Components Modulates the Phenotype of Human Smooth Muscle Cells in Vitro and Allows for the Control of Properties of Engineered Tissues

Smooth muscle cells (SMCs) play a significant role in the pathogenesis of atherosclerosis. 2D cultures elucidated valuable information about the interaction between SMCs and extracellular matrix (ECM) components. However, 3D constructs better represent the native vascular environment. Furthermore, a limited number of studies addressed the effect of ECM stiffness on SMCs phenotype. We investigated the effect of stiffness of different ECM substrates by modulating their concentrations, including the effect on morphology, proliferation, expression of the contractile protein α-smooth muscle actin (α-SMA) and deposition of collagen type I (Col I) and collagen type III (Col III) proteins. At low concentrations of Col I gels and Col I gels supplemented with 10% fibronectin (Fn), SMCs exhibited non-elongated, ‘hill-and-valley’ shape and large mean cellular area, indicating a hypertrophic morphology, characteristic of the synthetic phenotype. However, with increasing concentration, mean cellular area and proliferation relative to cells cultured in 2D dropped. Whole protein secretion into the culture media and deposition of Col I and Col III generally decreased with increasing stiffness. Moreover, percentage of α-SMA+ SMCs decreased with increasing gel concentration, pointing to a shift towards the synthetic phenotype. Supplementing Col I with 10% Laminin (Ln) maintained higher cellular area and aspect ratio at all gel concentrations and did not change α-SMA expression significantly, compared to Col I alone or Col I + Fn. Overall, these results demonstrate that ECM components and stiffness could provide the tools to modulate the phenotype and function of SMCs in vitro, which allows for the control of properties of engineered tissues.

Rheological characterization of high concentrated MFC gel from kenaf unbleached pulp

Microfibrillated Cellulose (MFC) was isolated from unbleached kraft pulp derived from kenaf bast fiber. MFC gels with different concentrations were manufactured from pulp with varying initial consistencies. The MFC was diluted to a consistency of around one percent using distilled water and was further homogenized by passing through a microfluidizer. In order to gain an understanding of the relative changes in behavior of the resulting MFC gels, their rheological properties were characterized. Results show that all of the gels exhibit a shear-thinning behavior. It was also determined that the rheological characteristics improved with increasing gel concentration, which was achieved by using higher pulp suspension consistencies. Diluted MFC that was derived from highly concentrated MFC had more variable modulus under the same strain and frequency compared to poorly concentrated MFC. But such a strong effect was not observed for viscosity. Additionally, the value of G′, ranging from 76 to 5325 Pa under the studied concentrations, was found to be fourfold the value of G″. In the low frequency range, G′ was almost independent of frequency, but was dependent on gel consistency with a coefficient of 3, indicating that MFC gels are elastic. These results show that it is possible to produce MFC gels with good rheological properties from high consistency kenaf pulp suspensions.

Diffusion of sodium dodecyl sulfate micelles in agarose gels

The gradient diffusion of ionic sodium dodecyl sulfate micelles in agarose gel was investigated at moderate concentrations above the CMC. Of particular interest were the effects of micelle, gel, and sodium chloride concentration on the micelle diffusivity. Holographic interferometry was used to measure the gradient diffusion coefficient at three sodium chloride concentrations (0, 0.03, 0.10 M), three gel concentrations (0, 1, 2 wt%), and several surfactant concentrations. Time-resolved fluorescence quenching was used to measure aggregation numbers both in solution and gel. The micelle diffusivity increased linearly with surfactant concentration at the two larger sodium chloride concentrations and all gel concentrations. In general, the strength of this effect increased with decreasing sodium chloride concentration and increased with gel concentration. This behavior is evidence of decreasing micelle–micelle electrostatic interactions with increasing sodium chloride concentrations, and increasing excluded volume effects and hydrodynamic screening with increasing gel concentration, respectively. The only exception was at 0.1 M sodium chloride and 2 wt% agarose, which showed a slight reduction in the slope compared to 1 wt% agarose. It was found that the concentration effect is quite strong for charged solutes: at a NaCl concentration of 0.03 M in a 2% agarose gel, in a solution with 3% SDS micelles by volume, the micelle diffusion coefficient is doubled relative to its value in the same gel at infinite dilution. The extrapolated, infinite-dilution diffusion coefficients and the rate at which the micelle diffusivity increased with surfactant concentration were compared with predictions of previously published theories in which the micelles are treated as charged, colloidal spheres and the gel as a Brinkman medium. The experimental data and theoretical predictions were in good agreement.

An investigation into the behaviour of air rifle pellets in ballistic gel and their interaction with bone

Although air weapons are considerably lower in power than other firearms, there is increasing concern that serious injuries can result from their misuse. The present study was therefore carried out to improve understanding of the terminal ballistic behaviour of air rifle pellets. Pellets were fired into ballistic gel under a variety of conditions. The pellets penetrated further than anticipated from their low cross-sectional density, and Bloom number was not necessarily a good guide to gel behaviour. Pellet penetration into the gel decreased with increasing gel concentration, and appeared to be linear at higher concentrations. Pointed pellets penetrated up to 50% further than rounded pellets. Power and range affect penetration, but other factors are also important, and power alone is not a simple guide to potential penetration. Test firings were also carried out firing pellets into ballistic gel that contained sections of animal bone. Computed tomography (CT) and visual observation were employed to record the interactions. CT scanning showed potential as a tool for examining pellet damage. The bone appeared to be undamaged, but the pellets were severely deformed on impact. If the pellet strikes the bone at an angle, less energy is absorbed by the impact and the pellet fragments may ricochet and cause further damage in the gel. A tentative model is proposed for estimating the energy absorbed by the impact.

Determination of Activation Energy for the Diffusion of Fe3+ Ions in Agar Gel Medium Containing Various Transition Metal Sulfates

The study of the diffusion of ferric ions in agar gel containing transition metal sulfates was carried out. The effect of gel concentration, electrolyte concentration and temperature on the diffusion of Fe3+ ions in various transition metal sulfates was studied with a view to verify Wang’s model of diffusion and the applicability of transition state theory to diffusion in a gel medium. The diffusion coefficients were measured using the zone diffusion technique. For a given concentration of electrolyte the activation energy (E) is found to decrease with an increase in the charge density of the cation of the supporting electrolyte and for a given system it is found to decrease with increasing electrolyte concentration in agreement with Wang’s model. This observation is explained on the basis of the distortion in the water structure caused by ions and agar molecules. At a given electrolyte concentration the magnitude of the Arrhenius parameters, E and Do, is found to decrease with increasing gel concentration in agreement with the transition state theory of diffusion.

Self-Assembly and Stress Relaxation in Acrylic Triblock Copolymer Gels

The structure and relaxation behavior of thermoreversible gels made with poly(methyl methacrylate)−poly(n-butyl acrylate)−poly(methyl methacrylate) [PMMA−PnBA−PMMA] triblock copolymers in 2-ethylhexanol, a midblock selective solvent, were studied by small-angle X-ray scattering (SAXS) and rheology. Effects of endblock length, endblock fraction, and gel concentration on the gel properties were investigated. A dramatic decrease in SAXS intensity was observed over a 20 °C interval where the gel transitions smoothly from elastic to viscous behavior. SAXS patterns were fit with a Percus−Yevick disordered hard-sphere model from which aggregation number and average domain spacing were calculated. Aggregation number increases with increasing gel concentration and endblock length. Increasing the endblock length from 9K to 25K increases the relaxation time of a gel with a polymer volume fraction of 0.15 by a factor of 10^6. For a given triblock endblock fraction and molecular weight, the micelle aggregation number is strongly correlated to the gel relaxation time. Arrhenius behavior with an effective activation energy of ~550 kJ/mol was observed for all triblocks and concentrations. This very high effective energy barrier describes gels relaxation behavior over a 40 °C temperature range, where the relaxation times vary by a factor of 10^(10).

Dynamics of Cellulose Whiskers Spatially Trapped in Agarose Hydrogels

The motion of cellulose whiskers trapped in agarose hydrogels is measured by depolarized dynamic light scattering (DDLS) under conditions of optical heterodyning, in which the rigid polymer network provides a static depolarized reference signal. At low concentration in free suspension, the rotational relaxation rate ϑ of the whiskers is decoupled from the osmotic properties of the suspension. When incorporated inside a gel, however, as the agarose concentration increases, ϑ first increases beyond that in the free suspension, reflecting a reduced amplitude of rotational fluctuations of the whiskers due to the repulsive interactions with their surroundings. At the same time, the dynamic light scattering Rayleigh ratio RVH obtained from DDLS decreases with increasing gel concentration. At high gel concentrations, however, ϑ tends to decrease due to the steric hindrance of the network. Except at the lowest whisker concentrations, ϑ is governed by the same fluctuations as those associated with RVH.

Fast internal dynamics in polyelectrolyte gels measured by dynamic light scattering

Dynamic light scattering was used to investigate the dynamics of sodium poly(styrene sulfonate) and fully neutralized poly(acrylic acid) gels as a function of the degree of swelling and weight ratio of cross-linking agent. It was shown that the collective diffusion coefficient increases with increasing degree of swelling and that the diffusion coefficient shows stronger concentration dependence than predicted by scaling arguments. For gel samples measured at the swelling equilibrium, the diffusion coefficient increases with increasing gel concentration for both gel systems.

Diffusion coefficients of humic substances in agarose gel and in water.

Measurements of the diffusion coefficients of five different humic substances (HS) have been performed in water and in agarose hydrogels at several pH values (in the range of 3-10) and gel concentrations (in the range of 0.7-3% w/w). Fluorescence correlation spectroscopy (FCS) and classical diffusion cells were used in parallel to probe diffusion over both microscopic and mesoscopic distance scales. In general, agreement between the techniques was reasonable, which indicated that local nonhomogenities in the gel did not play an important role. Diffusion coefficients (D) in the gel were generally in the range of 0.9-2.5 x 10(-10) m2 s(-1) but were generally only 10-20% lower than in solution. At low pH values, one of the studied humic substances (a peat humic acid, PPHA) formed large aggregates that could not penetrate into the gel and therefore could not be defined by a single D value. The observed decreases of D in the gel for other HS were too large to be explained by the tortuousity and obstructive effects of the gel alone. D decreased slightly with increasing gel concentration and increased slightly with pH. Because modifications of D due to pH were similar in both the gel and the free solution, it is unlikely that complexation with the gel was greatly influenced by the pH. Rather, the main effect that appeared to decrease the diffusive flux in gels was likely small increases in the hydrodynamic radii of the humic macromolecules. An anomalous diffusion model was used to describe the FCS data in the gel. The characteristic exponent determined by fitting the autocorrelation functions with this model decreased only slightly (from 0.96 to 0.90) with increasing gel concentration providing support that HS complexation with the gel fibers was not very important. The results have important implications for our understanding of the fate and behavior of the HS and their associated pollutants and for interpreting metal speciation data obtained using gel-covered analytical sensors.

Salbutamol Sulfate Suppositories: Influence of Formulation on Physical Parameters and Stability

Purpose. To prepare and evaluate a suppository dosage form of salbutamol sulfate. The prepared formulae with and without different concentrations of gels were tested for hardness, melting time, content uniformity, and drug release. The stability of some of the selected formulae was assessed. Methods. Salbutamol sulfate was formulated as a rectal suppository with emulsifying fatty bases (suppocire and witepsol) and water-soluble bases (PEG) adopting the molding from a melt technique. Physical characteristics and dissolution profiles of the prepared formulations were determined as the responses. The effects of adding gels, methyl cellulose (MC), and Eudispert (Eud) and their concentrations (1, 3, and 6%) on these responses were also investigated. Formulations showing high rank order were scaled up for shelf-life stability study for one year. Results. The results showed that all the investigated formulae have acceptable physical characteristics with respect to hardness, melting time (except F7), and uniformity of drug content. The amount of drug dissolved in 100 min of dissolution time was inversely affected by the melting point of the fatty base. The release from PEG bases was found to be molecular weight dependent. Addition of 1% MC or Eud gel increased the release from all the investigated formulae. Increasing gel concentration to 3% then to 6% showed different effects on the release. The degradation of salbutamol sulfate in the investigated formulae was found to be a first-order reaction. Conclusions. Rectal suppository of salbutamol sulfate could be prepared as an alternative to the oral dosage form to circumvent the first-pass metabolism.

Gel-Shift Assays: Migrative Dissociation of a RecA−Oligonucleotide Complex during Electrophoresis in Hydroxyethylated Agarose Gels

We investigate the dynamics of a protein-DNA complex under gel-shift assay conditions, in particular how the degree of gel confinement influences the complex stability during the electrophoretic analysis. The fiber-like complex between RecA proteins and a single-stranded oligonucleotide has been studied in hydroxyethylated agarose gels with the average pore radius being between 1 and 5 times larger than the radius of the rodshaped complex. The confining effect of the gel matrix slows down the dissociation of the complex, but in addition, migrative interactions (collisions) with the gel network during the electrophoresis perturbs the complex in two ways. At low gel concentrations, the protein-DNA complex is dismantled into free RecA and oligonucleotide with a half-time of the complex that decreases with increasing field strength in accordance with a migrative mechanism. At a given field strength, the half-time increases with increasing gel concentration despite more frequent interactions, probably because of a counteracting stabilizing cage effect from the gel. At high gel concentrations, a second type of perturbation is reflected in an increasing complex velocity over time, probably caused by trains of end-to-end attached fibers being broken up by interactions with the tight gels.

Frequency Domain Fluorescence Measurements of the Aggregation Properties of CnEm Surfactants in Agarose Gels

The micellar properties of C12E6, C12E8, and C12E10 surfactants in agarose gels were investigated. The aggregation number and the aggregate polarity were determined as a function of temperature, gel fiber volume fraction, and surfactant type by using steady-state fluorescence and frequency domain fluorescence quenching techniques. Application of the latter technique to the study of micellar properties in solution is described, including a method for accounting for the excitation light scattered by the gel fibers. The aggregation behavior in gels of surfactants which form spherical micelles in water is compared to those which form cylindrical micelles, and the results are interpreted by using a thermodynamic model for micelle formation in a gel matrix. For surfactants which form small spherical micelles in solution, there is little difference between the aggregation number and micelle polarity in an agarose gel and in pure solution. For surfactants which form large cylindrical micelles in solution, the aggregation number decreases with increasing gel concentration while the micelle polarity remains constant. The thermodynamic model shows that, if the agarose gel restricts the micelle size distribution, then the weight average aggregation number decreases for large cylindrical micelles and remains unchanged for small spherical micelles. The model results are consistent with the experimental results for the aggregation number of C12E6 in an agarose gel.

Self-Diffusion of Co2+ Ions in CoBr2, CoI2 and Electrolyte-Diffusion of ZnSO4 in Agar Gel Medium

Abstract Self-diffusion of Co2+ ions in CoBr2 and CoI2 is reported in the concentration range of 10–5 to 0.25M in 1% agar gel at 25 °C. The deviations observed between the experimental and theoretical values of diffusion coefficients are explained by considering different types of interactions occurring in the ion-gel water system. The applicability of the transition state theory to the diffusion of ZnSO4 in agar gel medium is tested by varying the temperature as well as the gel concentration at high concentration of the electrolyte. The activation energy E and D 0 value decrease with increasing gel concentration in agreement with the theory.

Use of holographic laser interferometry to study the diffusion of polymers in gels.

The aim of this study was to demonstrate the potential for holographic interferometry to be used for diffusion studies of large molecules in gels. The diffusion and partitioning of BSA (67,000 g/mol) and pullulans (5,900-112,000 g/mol) in agarose gel were investigated. The gel diffusion coefficients obtained for BSA were higher when distilled water was used as a solvent compared to those obtained with 0.1 M NaCl as the solvent. Furthermore, the gel diffusion coefficient increased with increasing BSA concentration. The same trend was found for liquid BSA diffusion coefficients obtained by DLS. BSA partition coefficients obtained at different agarose gel concentrations (2-6%, w/w) decreased slightly with increasing gel concentration. However, all BSA gel diffusion coefficients measured were significantly lower than those in pure solvent and they decreased with increasing agarose concentration. The gel diffusion coefficients obtained for pullulans decreased with increasing pullulan molecular weight. The same effect from increased molecular weight was seen in the liquid diffusion coefficients measured by DLS. The pullulan partition coefficients obtained decreased with increasing molecular weight. However, pullulans with a larger Stokes' radius than BSA had partition coefficients that were higher or approximately the same as BSA. This implied that the pullulan molecules were more flexible than the BSA molecules. The results obtained for BSA in this study agreed well with other experimental studies. In addition, the magnitude of the relative standard deviation was acceptable and in the same range as for many other methods. The results thereby obtained showed that holographic interferometry is a suitable method for studying diffusion of macromolecules in gels.

Characterization of UHMWPE sol–gel transition by parallel plate rheometer and pulsed NMR

The gel point and characterization of sol–gel transition of UHMWPE/decalin systems were investigated. In this study rheological method and DSC method were used to measure the gel point of UHMWPE gel at various concentrations. The result showed that the gel point increased with increasing gel concentration. Meanwhile pulsed NMR was also utilized to investigate 6 wt% UHMWPE gel. It was found that when sol–gel transition temperature was approximately 100°C, large amount of UHMWPE gel turned into solution state. Therefore, it produced re-entanglement and increased the random region within the UHMWPE molecular chain, which led to the decrease of interaction force among the polymer.

PhastSystem electrophoresis in beta-octylglucoside containing gels with immunodetection of a nondenatured vesicle-associated membrane protein.

Recombinant vesicle-associated membrane protein (rVAMP), implicated as a participant in membrane exocytosis and fusion (a "SNARE protein"), was subjected to gel electrophoresis in the miniaturized gels of the PhastSystem (Pharmacia) containing the nondenaturing, nonionic detergent beta-octylglucoside (OG), followed by immunodetection of the protein. Three major components of nondenatured rVAMP are detected by Western blotting both in 0.5% OG and in the absence of detergent. Their separation increases with increasing gel concentration above 7%T. Ferguson plot analysis indicates that the three species of VAMP are size isomers (i.e., they differ in size but share a common surface net charge density), the common point of intersection of the plots (mu-point) being a measure of their common free mobility. By the criteria of size and free mobility (related to surface net charge), VAMP components I, II and III in 0.5% OG-containing buffer are indistinguishable from components II, III and IV, respectively, observed in the absence of the detergent. The feasibility of immunodetection of nondenatured rVAMP on gels containing nondenaturing detergents opens up the possibility of gaining biochemical information regarding nondenatured SNARE protein complexes and SNARE proteins linked to membrane fragments.

Characterization of the rheological behavior of UHMWPE gels using parallel plate rheometry

The effects of shear flow, temperature, and gel concentration on the rheological behavior of the ultrahigh-molecular-weight polyethylene (UHMWPE) gel in gel spinning process were investigated. The gel point was determined using parallel plate rheometry in rotation mode with controlled stress. Likewise, the flow curves at various temperatures were determined with controlled shear rate from 10−2 to 10 s−1. Whereas the shear storage modulus (G′) was obtained in oscillation mode with controlled strain from 1 to 100%. The result shows that the gel point of the UHMWPE gel increases with increasing gel concentration. The result from the strain sweep indicates that G′ of the gel is 1.5 × 103 Pa, and it exhibits a plateau at low strain, but it is reduced with increasing strain. At low shear rates, for temperatures above gel point, all flow curves exhibit a plateau, then go down with increasing shear rate. Studying contributions from UHMWPE gel concentration, temperature, and shear rate for rheological view, we found that spinning at 6% UHMWPE (MW : 1.4 × 106 g/mol) gel and 140°C gives the best effect on formation of fiber structure. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 1009–1016, 1998