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PubMed1981

Adsorptive bonding to hydroxyapatite I: adsorption of anthranilic acid - the effect of solvents. Search for surface bonding groups for coupling agents to teeth.

A study was initiated to explore the nature of surface-active groups of model compounds that might cause chemisorption of comonomers used in the polymerization of dental resins on hydroxyapatite (the main constituent of bone) and thus effect a strong and durable bond between the resins and hard tooth tissues. In an effort to accomplish this objective, adsorption of anthranilic acid on hydroxyapatite was studied from three solvents: 95% aq. ethanol, dimethyl sulphoxide and methylene chloride. The adsorption is reversible from the first two solvents and the isotherms follow Langmuir plots. Adsorption is irreversible from methylene chloride; a constant amount of adsorbate is removed from different solutions above a certain threshold concentration but all adsorbate is removed from solutions below this threshold concentration. The saturation amounts obtained from the two Langmuir plots and the maximum irreversibly adsorbed amount in the above three solvents are 11.4, 6.0 and 17.2 mmol/100 g, respectively. These, together with the surface area (41.0 m2/g; BET, N2) of the hydroxyapatite, yield the effective molecular areas of 60, 114, and 40 A2, respectively. These areas can be matched, on geometrical considerations, with areas of 60, 110, and 40 A2 of the model adsorbate molecule rotating about; (i) its centre, lying flat on the surface, (ii) its carboxyl group at 45 degrees to the surface, and (iii) the carboxyl group in an upright position, respectively.

Adsorption↗
PubMed1986

Characterization of protein adsorption on soft contact lenses. IV. Comparison of in vivo spoilage with the in vitro adsorption of tear proteins.

Tear protein and gamma-globulin mixtures were adsorbed on soft contact lenses of different chemical composition, surface quality and water content. The adsorption process was followed by Fourier transform infrared-attenuated total reflectance spectroscopy (ATR-FTIR). It was found that gamma-globulin underwent a conformational and orientational change after its adsorption and the extent of structural change appeared to be proportional to the binding strength of the protein with the hydrogel surface. Electrostatic interactions play a major role in the protein adsorption on lenses containing methacrylic acid. Lysozyme is selectively adsorbed on all of the high water content hydrogels and mucin is the major protein component for the pure PHEMA type of lenses. Studies on in vivo spoiled PHEMA and PVP/MMA lenses indicate that lysozyme is the major adsorbed deposit. Papain cleaning of in vivo spoiled lenses shows that although a portion of the deposits is desorbed, the enzyme itself becomes irreversibly adsorbed to the contact lens which may cause harmful effects to the eye.

Adsorption↗
PubMed2004

Modeling chromatographic columns non-equilibrium packed-bed adsorption with non-linear adsorption isotherms.

In this work a new mathematical model, based on non-equilibrium conditions, describing the dynamic adsorption of proteins in columns packed with spherical adsorbent particles is used to study the performance of chromatographic systems. Simulations of frontal chromatography, including axial dispersion, for non-equilibrium systems with non-linear adsorption isotherms are made and compared to those of the experimentally determined protein A affinity chromatography breakthrough curves of hIgG, gathered from the literature. The non-equilibrium model developed here combines external mass transfer and intra-particle transport by solid (surface) diffusion, and permits the prediction of (time and bed height dependent) interface and average solid concentrations, along with interface and bulk liquid concentrations. The present non-equilibrium approach significantly improved the model predictions of experimentally observed distended breakthrough fronts over local equilibrium based models, and can be used to evaluate the influence of system parameters on the performance of chromatographic packed-bed adsorption columns.

Adsorption↗
PubMed2006

Application of surface molecular imprinting adsorbent in expanded bed for the adsorption of Ni(2+) and adsorption model.

A new surface molecular imprinting adsorbent (SMIA) was used in an expanded bed. The expansion ratio and adsorption performance were studied at different volumetric rates, inlet concentrations, and pH values. A model based on the Adams-Bohart adsorption model of breakthrough curves was established. The predicted curves had good agreement with the experimental curves. The breakthrough time (T(1/2)) decreased with increasing inlet concentration when the outlet concentration was half the initial concentration (C/C(0)=0.5). The inlet concentration had little effect on the adsorption rate constant (k(1)) value when the initial concentration (C(0)) was above 150 mg/L. However, T(1/2) values increased with increasing initial pH of the inlet solution, and the k(1) value decreased due to the competition between H(+) and Ni(2+).

Adsorption↗
PubMed2006

Applicability of the various adsorption models of three dyes adsorption onto activated carbon prepared waste apricot.

In this study, activated carbon (WA11Zn5) was prepared from waste apricot, which is waste in apricot plants in Malatya, by chemical activation with ZnCl(2). BET surface area of activated carbon is determined as 1060 m(2)/g. Activated carbon includes both micro and mesopores. Percentages of micropores and mesopores area are determined 36% and 74%, percentage of micropores and mesopores volume is 19% and 81%, respectively. The ability of WA11Zn5, to remove three dyes, methylene blue (MB), malachite green (MG), and crystal violet (CV), from effluent solutions by adsorption has been studied. The adsorption capacities of WA11Zn5 decreases in the order malachite green (MG)>methylene blue (MB)>crystal violet (CV). Equilibrium isotherms for the adsorption of three dyes on activated carbon were measured experimentally. Results were analyzed by the Langmiur, Freundlich, Dubinin-Redushkevich (D-R), Temkin, Frumkin, Harkins-Jura, Halsey and Henderson equation using linearized correlation coefficient at different temperature. The characteristic parameters for each isotherm have been determined. Models and the isotherm constant were evaluated depending on temperature. Langmiur and Frumkin equation is found to best represent the equilibrium data for three dye-WA11Zn5 systems.

Adsorption↗
PubMed2006

Adsorption of benzene and toluene from aqueous solutions onto activated carbon and its acid and heat treated forms: influence of surface chemistry on adsorption.

The influence of surface chemistry and solution pH on the adsorption of benzene and toluene on activated carbon and its acid and heat treated forms were studied. A commercial coal-based activated carbon F-400 was chosen as carbon parent. The carbon samples were obtained by modification of F-400 by means of chemical treatment with HNO3 and thermal treatment under nitrogen flow. The treatment with nitric acid caused the introduction of a significant number of oxygenated acidic surface groups onto the carbon surface, while the heat treatment increases the basicity of carbon. The pore characteristics were not significantly changed after these modifications. The dispersive interactions are the most important factor in this adsorption process. Activated carbon with low oxygenated acidic surface groups (F-400Tox) has the best adsorption capacity.

Adsorption↗
PubMed1998

The adsorption of phloretin to lipid monolayers and bilayers cannot be explained by langmuir adsorption isotherms alone.

Phloretin and its analogs adsorb to the surfaces of lipid monolayers and bilayers and decrease the dipole potential. This reduces the conductance for anions and increases that for cations on artificial and biological membranes. The relationship between the change in the dipole potential and the aqueous concentration of phloretin has been explained previously by a Langmuir adsorption isotherm and a weak and therefore negligible contribution of the dipole-dipole interactions in the lipid surface. We demonstrate here that the Langmuir adsorption isotherm alone is not able to properly describe the effects of dipole molecule binding to lipid surfaces--we found significant deviations between experimental data and the fit with the Langmuir adsorption isotherm. We present here an alternative theoretical treatment that takes into account the strong interaction between membrane (monolayer) dipole field and the dipole moment of the adsorbed molecule. This treatment provides a much better fit of the experimental results derived from the measurements of surface potentials of lipid monolayers in the presence of phloretin. Similarly, the theory provides a much better fit of the phloretin-induced changes in the dipole potential of lipid bilayers, as assessed by the transport kinetics of the lipophilic ion dipicrylamine.

Adsorption↗
PubMed2002

Protein adsorption on novel acrylamido-based polymeric ion-exchangers. IV. Effects of protein size on adsorption capacity and rate.

The effects of protein size on the adsorption capacity and rate is determined for an acrylamido-based polymeric anion-exchanger. The proteins lactalbumin, myoglobin, ovalbumin, BSA, conalbumin, IgG, and ferritin with molecular masses ranging from 15,000 to 450,000 were investigated. At high salt concentration (50 mM Tris-HCl containing 500 mM NaCl), only the smaller proteins lactalbumin and myoglobin gained access to a significant portion of the particle volume. The larger proteins were nearly completely excluded, in agreement with the results obtained for neutral macromolecules. By contrast, at low salt concentration (50 mM Tris-HCl), the adsorption capacity was very large (280-400 mg/ml of particle volume) for all the proteins studied except for ferritin, for which the capacity was much lower. This suggests that, provided the solute is not too large, the favorable electrostatic interaction overcomes the size exclusion effect. Adsorption rate measurements showed that mass transfer rates are also quite fast at low salt concentration. Effective diffusivities were determined by matching model and experimental results and were found to decrease substantially as the protein size increased. As previously observed, the homogeneous diffusion model was found to predict the experimentally observed trends with respect to protein concentration and boundary layer mass transfer effects.

Acrylamides↗
PubMed1999

Protein adsorption at the oil/water interface: characterization of adsorption kinetics by dynamic interfacial tension measurements.

The dynamics of protein adsorption at an oil/water interface are examined over time scales ranging from seconds to several hours. The pendant drop technique is used to determine the dynamic interfacial tension of several proteins at the heptane/aqueous buffer interface. The kinetics of adsorption of these proteins are interpreted from tension/log time plots, which often display three distinct regimes. (I) Diffusion and protein interfacial affinity determine the duration of an initial induction period of minimal tension reduction. A comparison of surface pressure profiles at the oil/water and air/water interface reveals the role of interfacial conformational changes in the early stages of adsorption. (II) Continued rearrangement defines the second regime, where the resulting number of interfacial contacts per protein molecule causes a steep tension decline. (III) The final regime occurs upon monolayer coverage, and is attributed to continued relaxation of the adsorbed layer and possible build-up of multilayers. Denaturation of proteins by urea in the bulk phase is shown to affect early regimes.

Adsorption↗
PubMed2005

A modified Poisson-Boltzmann model including charge regulation for the adsorption of ionizable polyelectrolytes to charged interfaces, applied to lysozyme adsorption on silica.

The equilibrium adsorption of polyelectrolytes with multiple types of ionizable groups is described using a modified Poisson-Boltzmann equation including charge regulation of both the polymer and the interface. A one-dimensional mean-field model is used in which the electrostatic potential is assumed constant in the lateral direction parallel to the surface. The electrostatic potential and ionization degrees of the different ionizable groups are calculated as function of the distance from the surface after which the electric and chemical contributions to the free energy are obtained. The various interactions between small ions, surface and polyelectrolyte are self-consistently considered in the model, such as the increase in charge of polyelectrolyte and surface upon adsorption as well as the displacement of small ions and the decrease of permittivity. These interactions may lead to complex dependencies of the adsorbed amount of polyelectrolyte on pH, ionic strength, and properties of the polymer (volume, permittivity, number, and type of ionizable groups) and of the surface (number of ionizable groups, pK, Stern capacity). For the adsorption of lysozyme on silica, the model qualitatively describes the gradual increase of adsorbed amount with pH up to a maximum value at pHc, which is below the iso-electric point, as well as the sharp decrease of adsorbed amount beyond pHc. With increasing ionic strength the adsorbed amount decreases (for pH > pHc), and pHc shifts to lower values.

Adsorption↗
PubMed2006

X-ray microscopy studies of protein adsorption on a phase-segregated polystyrene/polymethyl methacrylate surface. 1. Concentration and exposure-time dependence for albumin adsorption.

X-ray photoemission electron microscopy using synchrotron radiation illumination has been used to measure the spatial distributions of albumin on a phase-segregated polystyrene/poly(methyl methacrylate) (PS/PMMA) polymer thin film following adsorption from unbuffered, deionized aqueous solutions under a range of solution concentrations and exposure times. Chemical mapping of the albumin, PS, and PMMA shows that the distribution of albumin on different adsorption sites (PS, PMMA, and the interface between the PS and PMMA domains) changes depending on the concentration of the albumin solution and the exposure time. The preferred sites of absorption at low concentration and short exposure are the PS/PMMA interfaces. Albumin shows a stronger preference for the PS domains than the PMMA domains. The exposure-time dependence suggests that a dynamic equilibrium between albumin in solution and adsorbed on PS domains is established in a shorter time than is required for equilibrating albumin between the solution and the PMMA domains. The explanation of these preferences in terms of possible adsorption mechanisms is discussed.

Adsorption↗
PubMed2004

Adsorption of organic matter at mineral/water interfaces. 2. Outer-sphere adsorption of maleate and implications for dissolution processes.

The effects of the adsorption of a simple dicarboxylate low molecular weight organic anion, maleate, on the dissolution of a model aluminum oxide, corundum (alpha-Al2O3), have been examined over a range of different maleate concentrations (0.125-5.0 mM) and pH conditions (2-10). In situ attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopic measurements indicate that maleate binds predominantly as an outer-sphere, fully deprotonated complex ([triple bond]AlOH2+ -Mal2-) at the corundum surface over the entire range of maleate concentrations and pH conditions investigated. In accordance with the ATR-FTIR findings, macroscopic adsorption data can be modeled as a function of maleate concentration and pH using an extended constant capacitance approach and a single [triple bond]AlOH2+ -Mal2- species. Outer-sphere adsorption of maleate is found to significantly reduce the protolytic dissolution rate of corundum under acidic conditions (pH < 5). A likely mechanism involves steric protection of dissolution-active surface sites, whereby strong outer-sphere interactions with maleate hinder attack on those surface sites by dissolution-promoting species.

Adsorption↗
PubMedDate not supplied

Adsorption of chitin derivatives onto liposomes: optimization of adsorption conditions.

A 2(4) factorial design is used to optimize the adsorption conditions of the hydrophilic anionic polyelectrolytes. Carboxymethylchitin (CMC) and Carboxymethyl/Glycolchitin (CO) onto liposomes at physiological ionic strength (I) and pH using phosphate buffered saline (PBS, I = 154 mM, pH = 7.4). Positive ([+]) or high surface affinity liposomes (DSPC:CHOL:DMTAP, 5:4:1), and Neutral ([N]) or low surface affinity liposomes (DSPC:CHOL, 1:1) were used as adsorption surfaces. Results of the calculations of the main effects indicate that polymer molecular weight (mwt), Surface Affinity (S), Number of Adsorption Shots (Sh), Temperature (T), and the combinations mwt x S, mwt x Sh are the most important process parameters. Results of a study conducted at T = 37 degrees C show that no loss occurs from the positive surface at the highest particle concentration, Np = 4.043 x 10(11). Finally, the extent of polymer-induced particle aggregation is decreased when the diameter of the uncoated liposomes is doubled from 0.22 to 0.45 micron. These results are as expected, given the stiffness and the dimensions of the macromolecules.

Adsorption↗
PubMed1997

Kinetic aspects of polyelectrolyte adsorption: adsorption of chitin derivatives onto liposomes as a model system.

Carboxymethylchitin (CMC) and Carboxymethyl/Glycolchitin (CO) have been adsorbed onto liposomes at physiological ionic strength (I) and pH using phosphate buffer saline (PBS, I = 154 mM, pH = 7.4). Adsorption isotherms at different polymer weight average molecular weights (Mw), for Positive ([+]) or high surface affinity liposomes (DSPC:CHOL:DMTAP, 5:4:1), and Neutral ([N]) or low surface affinity liposomes (DSPC:CHOL, 1:1), have been obtained at T = 25 degrees C. For all CMCs, the adsorbed amount increases with polymer concentration ([P]zero) and no true plateau is observed. The CMC Mw = 4.19 x 10(5) adsorbed on a positive surface fits Langmuir kinetics with maximal coverage gamma max = 325.4 micrograms/mg (polymer/lipid), and inverse of equilibrium constant K* = 4.743 x 10(-4) mg/ml. For all isotherms the predicted amount of polymer needed to coat the entire surface based on the Radius of Gyration (Rg) is inferior to the amount adsorbed. This fact in conjunction with the dependence of gamma max on the number of adsorption shots, suggests that the adsorption is not thermodynamically but kinetically controlled.

Adsorption↗
PubMedDate not supplied

Adsorption of bovine serum albumin onto glassy carbon in a Couette flow. Effect of shear rate on the adsorption kinetics and on the structure of the adsorbed proteic layer.

Adsorption of bovine serum albumin onto glassy carbon is investigated by analysing the time-variation of the double-layer capacitance recorded during the adsorption process. The effect of shear rate is investigated under laminar conditions in a Couette flow. Stationary and sinusoidally modulated values of the shear rate are imposed over the (0-200 s-1) range. The flow conditions are shown to play an essential role by markedly modifying the rate of all the steps (three at most) involved in the adsorption mechanism. Moreover, the structure of the adsorbed layers in the intermediate and final states are also strongly modified, an increase of the shear rate increasing the interaction between the protein and the electrode. Piezoelectric properties of albumin are invoked to account for the experimental results.

Adsorption↗
PubMed2001

Protein adsorption on histidyl-aminohexyl-Sepharose 4B. I. Study of the mechanistic aspects of adsorption for the separation of human serum albumin from its non-enzymatic glycated isoforms (advanced glycosylated end products).

The characteristics of albumin adsorption on histidyl-aminohexyl-Sepharose 4B were investigated. In particular, the adsorption capacity of the gel was studied as a function of conductivity and pH of the running buffer. The adsorption was maximum at low salt concentration around neutral pH, involving electrostatic and hydrophobic interactions. Kinetic aspects were also investigated. Dissociation constant (KD) and maximum capacity (Qx) were, respectively, estimated to be 4.5 x 10(-5) M (medium affinity) and 93.3 mg (high capacity) of human serum albumin per ml of adsorbent. According to these preliminary results, separation of HSA and its non-enzymatically glycated isoforms (conventionally named advanced glycated end products: AGEs) was achieved. Chromatographic potential of this separation tool is discussed.

Adsorption↗
PubMed1997

Adsorption of Water Vapor by Homoionic Montmorillonites. Heats of Adsorption and Desorption

Adsorption isotherms for water vapor, basal spacing, and immersion heats and water desorption heats of Li+, Na+, Mg2+, Ca2+, Cu2+, and Fe3+ montmorillonite are measured at various relative humidities (r.h.). The amount of water adsorbed as a function of r.h. is found to increase gradually, whereas basal spacing increases and the adsorption heat decreases in steps. The water desorption heat also decreases in steps. The entropy of adsorbed water appears to be negative with respect to the entropy of liquid water. A theoretical model is proposed to describe the hydration process of Li+, Na+, Mg2+, Ca2+, Cu2+, and Fe3+ montmorillonites. The experimental adsorption heats are found to have a direct relationship with the sum of the hydration energy of the cations plus expansion energy.

Journal Article↗