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At least 19 recordsLinked to original sources
PubMed1996

Adsorption of Poly(butyl methacrylate) and Its Mixtures with Polystyrene from Solutions: Adsorption Kinetics and Structure of Adsorption Layers

Using IR spectroscopy of attenuated total inner reflectance (ATIR) the adsorption kinetics and structure of the adsorption layer of poly(butyl methacrylate) on the Ge surface from solutions in CCl4 of pure polymer and its mixtures with polystyrene have been investigated. It was shown that at the first stage of adsorption of poly(butyl methacrylate) from diluted solution, a layer of high connectivity of macromolecules with Ge surface is formed. The diffusion coefficient of macromolecules on this part of the kinetic curve corresponds to that for the glassy state. With increasing adsorption, the fraction of bonded segments diminishes and macromolecules in the adsorption layer become more mobile. On this part of the kinetic curve there is observed a sharp increase in both the diffusion coefficient of macromolecules and the adsorption rate. On transition from diluted to semidiluted solutions the mechanism of adsorption changes. The coefficient of diffusion of macromolecules coincides with that for reptation movement of macromolecules in the entanglement network. It was shown that introduction of polystyrene into solutions affects the adsorption value and structure of the adsorption layer. This effect is supposed to be connected to possible changes in combinatorial entropy of the system.

Journal Article↗
PubMed1990

The adsorption of 99mTc(Sn)-diphosphonate complexes on tri-calciumphosphate: the influence of preparation conditions, ligand-type, incubation media and adsorption conditions. The reversibility of the adsorption.

The influence of several variables on the adsorption of 99mTc(Sn)-diphosphonate complexes on tri-calciumphosphate was determined. The composition of the incubation medium influenced the percentage adsorption: with Hank's balanced salt solution (a medium frequently used for bone cell cultures) and Tris buffer lower percentage adsorption was obtained than with physiological saline as the incubation medium. The influence of addition to the incubation medium of some ions and neutral species, some of which occur in bone fluid, is very specific. Addition of Sn(II) or Mg(II) (a component of HBSS) reduces the amount of adsorption. Addition of Ca(II) and Al(III) had no effect. Addition of sodium-citrate and MDP to the medium and an increase of the pH of the medium decreased the percentage adsorption. The ligand that was used in the preparation of the complex mixture influences the percentage adsorption considerably. The Sn(II) concentration used during the preparation of the 99mTc(Sn)-MDP and 99mTc(Sn)-MHDP complexes showed no definite influence on the percentage adsorption. The pH and ligand concentration, used in the preparation, however, did effect the percentage adsorption. It was concluded that the 99mTc(Sn)-disphosphonate mixtures are part reversibly and part irreversibly bound to tri-calcium-phosphate.

Adsorption↗
PubMed1991

Interfacial thermodynamics of protein adsorption and ion co-adsorption. III. Electrochemistry of bovine serum albumin adsorption on silver iodide.

An experimental analysis of charge regulation in protein adsorption is presented. The model system consists of colloidal particles of the slightly water soluble salt silver iodide as the adsorbent and the protein bovine serum albumin as the adsorbate. Protein adsorption experiments corroborate earlier findings that albumin adsorbs maximally close to the isoelectric point of the protein. The adsorption is reversible with respect to protein-protein exchange. The charge regulation is studied by novel potentiometric titrations. The Galvani potential of the adsorbent, partially covered with protein, is varied by the addition of AgNO3/KI while the pH is kept constant by means of a pH-stat. It is shown that the ion co-adsorption is a linear decreasing function of the blank surface charge density. The results are consistent with thermodynamics: for the first time a few phenomenological linkage relations between the ion co-adsorptions and chemical potentials are verified experimentally. The charge regulation is interpreted in terms of a contact layer model, which explains the ion co-adsorption by compounded ion exchange equilibria in the small layer of atomic contact between adsorbed protein and surface.

Adsorption↗
PubMed2002

Effect of temperature on the structure of adsorption layers formed by adsorption of polymers in the transition region from dilute to semidilute solutions.

The measurements of adsorption from solutions of polymers (poly(butyl methacrylate) and polystyrene) and their mixtures at various temperatures in the wide concentration region from dilute to semidilute solution have been made. The adsorption isotherms and fraction of bound segments confirm the existence of the transition concentration region near the critical concentration of the chain overlapping when the change of adsorption mechanisms take place. The effect of temperature on adsorption from the mixtures is different for both the polymers depending on the concentration regime. For PBMA, which adsorbs from the mixtures preferentially, the adsorption isotherms are of the same shape as for adsorption from binary solutions and are characterized by the presence of a small forepart in the transition region and by increasing adsorption with temperature. For less adsorbing PS by transition from dilute to semidilute regime the inversion of the temperature effect on adsorption is observed. These results are confirmed by the estimations of the parameters of preferential adsorption at various temperatures. The data on the fraction of bound segments for dilute regime corresponds to the extended conformation of chains at the surface. The transition to semidilute regime leads to the diminishing of the fraction of bound segments as a result of simultaneous adsorption of macromolecular aggregates. Values of adsorption layer thickness have been calculated for various solution regimes and concentration. The dependence of the adsorption layer thickness on the temperature and on the solution regime at which adsorption occurs was established.

Journal Article↗
PubMed1996

Adsorption behaviour of amphiphilic polymers at hydrophobic surfaces: effects on protein adsorption.

The adsorption of four different amphiphilic polymers to a model surface has been studied, and the effects of the adsorbed amphiphiles on the subsequent adsorption of fibrinogen (Fg) and human serum albumin (HSA) at the surfaces were investigated. The amphiphilic polymers were one commercially available ABA block copolymer, Pluronic PE9400 (PE94), composed of poly(ethylene oxide) (A-blocks) and poly(propylene oxide) (B-block), and three graft copolymers, two with backbones of poly(styrene-co-acrylamide) (STY) and one with a backbone of poly(methyl methacrylate-co-ethylhexyl methacrylate) (ACRY). The backbones carried poly(ethylene oxide) (PEO) grafts. The model surface was a hydrophobic methylated silica surface (HMS). The amphiphilic polymers were adsorbed at the HMS surface from an ethanol/water solution. The adsorption process was monitored by ellipsometry. After rinsing with phosphate buffered saline (PBS), protein was added and the continued adsorption measured by ellipsometry. Surfaces modified by adsorption of the amphiphilic polymers were also characterized by contact angle measurements and X-ray photoelectron spectroscopy (XPS). According to these measurements the amphiphilic polymers adsorbed in significant amounts at the HMS surface. A limited study by atomic force microscopy (AFM), as well as the XPS measurements, suggests that both single molecules and micellar aggregates adsorb at the surface. ACRY and PE94 gave the highest levels of adsorption. As compared to the Pluronic block copolymer the graft copolymers were more strongly attached to the HMS surface, as shown by less desorption on rinsing with solvent. The ellipsometric results show that the adsorption of HSA and Fg at HMS surfaces containing preadsorbed amphiphilic polymer was significantly reduced as compared to the bare HMS surface. ACRY and PE94 showed the largest effects. Both polymers gave more than a 20-fold reduction of the Fg adsorption and a 10-fold reduction of the HSA adsorption. The STY polymers reduced the protein adsorption by a factor of 2-3.

Adsorption↗
PubMed2004

Study of effect of adsorptive building material on formaldehyde concentrations: development of measuring methods and modeling of adsorption phenomena.

UNLABELLED: In this paper, a method is developed to assess the performance of adsorptive building materials that are used for reducing indoor pollutant concentrations. Mass transfer has a great influence on the materials' performance. To control the mass transfer rate precisely in the performance test, the authors have developed the Boundary-Layer-Type Small Test Chamber in which airflow along the test materials can be controlled precisely. A new index of adsorption performance, the equivalent ventilation rate (Q(ads)), is defined that corresponds to the mass transfer coefficient when the surface pollutant concentration is zero. Modeling and experimental verification of adsorption were done, demonstrating the pollutant concentration decrease caused by adsorptive building materials. The pollutant reduction phenomena were modeled, including pollutant degradation by chemical reaction and adsorption in building materials. Adsorption tests of gypsum board containing a substance that decomposes HCHO within the board are reported. The adsorption rate of the gypsum board predicted by numerical analysis (CFD, Computational Fluid Dynamics) corresponds well with experimental results. PRACTICAL IMPLICATIONS: Development and verification of a method to measure the decrease in indoor pollutant concentration caused by an adsorptive building material are reported. Mass transfer has a great influence on the material's performance. The equivalent ventilation rate (Q(ads)) of the adsorption performance is defined as a new index that corresponds to the mass transfer coefficient. The equivalent ventilation rate (Q(ads)) can be used directly to compare the effect of pollutant concentration decrease via adsorption with the effect of ventilation.

Adsorption↗
PubMed2002

Adsorption of chloroacetanilide herbicides on soil and its components. III. Influence of clay acidity, humic acid coating and herbicide structure on acetanilide herbicide adsorption on homoionic clays.

Adsorption of chloroacetanilide herbicides on homoionic montmorillonite, soil humic acid, and their mixtures was studied by coupling batch equilibration and FT-IR analysis. Adsorption isotherms of acetochlor, alachlor, metolachlor and propachlor on Ca(2+)-, Mg(2+)-, Al(3+)- and Fe(3+)-saturated clays were well described by the Freundlich equation. Regardless of the type of exchange cations, Kf decreased in the order of metolachlor > acetolachlor > alachlor > propachlor on the same clay. FT-IR spectra showed that the carbonyl group of the herbicide molecule was involved in binding, probably via H-bond with water molecules in the clay interlayer. The type and position of substitutions around the carbonyl group may have affected the electronegativity of oxygen, thus influencing the relative adsorption of these herbicides. For the same herbicide, adsorption on clay increased in the order of Mg2+ < Ca2+ < Al3+ < or = Fe3+ which coincided with the increasing acidity of homoionic clays. Acidity of cations may have affected the protonation of water, and thus the strength of H-bond between the clay water and herbicide. Complexation of clay and humic acid resulted in less adsorption than that expected from independent adsorption by the individual constituents. The effect varied with herbicides, but the greatest decrease in adsorption occurred at a 60:40 clay-to-humic acid ratio for all the herbicides. Causes for the decreased adsorption need to be characterized to better understand adsorption mechanisms and predict adsorption from soil compositions.

Adsorption↗
PubMed1991

Protein adsorption at solid-liquid interfaces: Part II--Adsorption from binary protein mixture.

Extent of adsorption of proteins at alumina-water interface from solutions containing binary mixture of beta-lactoglobulin and bovine serum albumin (BSA), beta-lactoglobulin and gelatin, and gelatin and bovine serum albumin has been estimated as functions of protein concentrations at varying pH, ionic strength, temperature and weight fraction ratios of protein mixture. The extent of adsorption (gamma lacw) of lactoglobulin in the presence of BSA increases with increase of protein concentration (Clac) until it reaches a maximum but a fixed value gamma lacw(m). Extent of adsorption gamma serw also initially increases with increase of protein concentrations until it reaches maximum value gamma serw(m). Beyond these protein concentrations, adsorbed BSA is gradually desorbed due to the preferential adsorption of lactoglobulin from the protein mixture. In many systems, gamma serw at high protein concentrations even becomes negative due to the strong competition of BSA and water for binding to the surface sites in the presence of lactoglobulin. For lactoglobulin-gelatin mixtures, adsorption of both proteins is enhanced as protein concentration is increased until limiting values for adsorption are reached. Beyond the limiting value, lactoglobulin is further accumulated at the interface without limit when protein concentration is high. For gelatin-albumin mixtures, extent of gelatin adsorption increases with increase in the adsorption of BSA. The limit for saturation of adsorption for gelatin is not reached for many systems. At acid pH, adsorbed BSA appears to be desorbed from the surface in the presence of gelatin. From the results thus obtained the role of electrostatic and hydrophobic effects in controlling the adsorption process has been analysed.

Adsorption↗
PubMed2001

Development of Automatic Adsorption Apparatus for Binary Mixture: Measurement of Individual Adsorption Isotherms of Ethanol and Water from Their Mixed Vapors by Active Carbon Fiber.

The automatic adsorption apparatus has been developed to measure the individual adsorption isotherms of constituent vapor from binary mixed vapor. The present adsorption apparatus consists of a combination of gravimetry and volumetry. The weight increase due to gas adsorption was determined by the magnetic suspension vacuum balance with a sensitivity of 0.01 mg, while the pressure decrease due to adsorption was measured by a high precision pressure gauge with a sensitivity of 0.2 Pa. The adsorption data obtained from both gravimetry and volumetry make it possible to determine the individual isotherms of the constituent vapors without chemical analysis, if the molecular weights of the constituent vapors are significantly different one another. In the later part of this work, the present adsorption apparatus has been applied to measure the individual adsorption isotherms of ethanol and water by active carbon fiber from their mixed vapor. The reliability of the individual isotherms measured by the present apparatus has been considered. The adsorption data obtained in the present work clearly indicate that ethanol molecules are preferentially adsorbed into the micropores of active carbon fiber with a pore width of 0.67 nm. The present adsorption result suggests the possibility of the energy-saving separation of ethanol from the mixed vapors of ethanol and water. Copyright 2001 Academic Press.

Journal Article↗
PubMed2004

Adsorption of water vapor by poly(styrenesulfonic acid), sodium salt: isothermal and isobaric adsorption equilibria.

Air conditioning and dehumidifying systems based on sorption on solids are of great interest, especially in humid climates, because they allow reduction of thermal loads and use of chlorofluorocarbons. Previous studies have shown that hydrophilic polymers such as sulfonic polymers can have very high performance in water adsorption from air. The aim of this study was to characterize the water vapor adsorption properties of fully sulfonated and monosulfonated poly(styrenesulfonic acid), sodium salt, and to elucidate the mechanism of adsorption on these materials. Adsorption isotherms have been determined by TGA between 298 and 317 K for pressures ranging from 0.1 to 45 hPa. They have type II of the IUPAC classification and a small hysteresis loop between adsorption and desorption processes was observed only for the monosulfonated sample. Water content is up to 80% weight at 80% relative humidity. Adsorption isotherms have been well fitted with the FHH model. Adsorption-desorption isobars have been determined by TGA under 37 hPa in the temperature range 298-373 K. They show that these polymers can be completely regenerated by heating at 313 K under humidified air. No degradation of the adsorption properties has been observed after several regenerations. Adsorption enthalpies and entropies have been deduced from the Clapeyron equation and from DSC measurements. A good agreement was found. A mechanism of adsorption is proposed considering two kinds of adsorbate: bounded water in electrostatic interaction with functional groups and free water resulting from condensation.

Journal Article↗
PubMed1991

Protein adsorption at solid-liquid interfaces: Part III--Adsorption from ternary protein mixture.

Simultaneous adsorption of bovine serum albumin (BSA), beta-lactoglobulin and gelatin from aqueous solutions of their ternary mixture to the alumina-water interface has been studied as a function of protein concentration at different values of pH, ionic strength, temperature and weight fraction ratios of proteins. At a fixed weight fraction of beta-lactoglobulin, preferential adsorption (gamma w(lac)) of this protein significantly depends on the amounts of BSA and gelatin present in the solution before adsorption. At higher ranges of protein concentrations, extent of adsorption (gamma w(ser)) of BSA decreases sharply with increase of gamma w(lac) until gamma w(ser) becomes significantly negative, thereby indicating that beta-lactoglobulin and water preferentially adsorbed at the interface are responsible for complete displacement of BSA from the surface. On the other hand, adsorption (gamma w(gel)) of gelatin under similar situation increases mutually with increase in the values of gamma w(lac) in many systems. In few systems, gamma w(gel) also decreases with increase of gamma w(lac) depending upon solution parameters. At pH 5.2, increase of ionic strength and temperature, respectively, increases the extent of adsorption of each protein in the mixture considerably. Extents of adsorption of all proteins are observed to increase when pH is changed from 5.2 to 6.4. The affinities of different proteins in the mixture are expressed in unified scales either in terms of maximum extents of total adsorption or in terms of standard free energies of adsorption of protein mixtures with respect to surface saturation.

Adsorption↗
PubMed2004

Adsorption of alpha-chymotrypsin onto mica in laminar flow conditions. Adsorption kinetic constant as a function of tris buffer concentration at pH 8.6.

We examined the adsorption kinetics of alpha-chymotrypsin (pH 8.6, 10(-2) to 0.5 M Tris buffer) on muscovite mica in conditions of laminar flow through a slit. The range of buffer concentrations is between two limits: (i) no adsorption in 1 M Tris and (ii) no desorption in 10(-3) M Tris. Studying the dependence of adsorption kinetics on the wall shear rate leads to the determination of the interfacial adsorption kinetic constant ka and the diffusion coefficient. The obtained value for the diffusion coefficient is close to the one expected from the molecular size of alpha-chymotrypsin. The interfacial adsorption kinetic constant of alpha-chymotrypsin decreases when ionic strength increases, while the initial desorption constant (over a part of all the adsorbed population) shows the contrary. Although alpha-chymotrypsin is almost at its isoelectric point, the effect of ionic strength on the adsorption kinetics suggests the importance of electrostatic interactions between the protein and mica. We observed an increase in the adsorption rate, at a surface coverage near 0.14 microg cm(-2), for adsorption in 10(-2) M Tris and the low wall shear rates (<300 s(-1)). This change in the adsorption rate suggests a structural transition, that we assume again to be due to electrostatic interactions, but between proteins. The large dipole moment of the protein may induce this transition, illustrated here by the ferroelectric/antiferroelectric pattern. The variation of the zeta potential with interfacial concentration seems to be in agreement with such a model.

Journal Article↗
PubMed1996

Divalent cations modify adsorption of 5'-AMP onto precipitated calcium phosphate: a model for cation modulation of adsorptive processes in primitive aqueous environments.

The adsorption of 5'-AMP onto precipitated calcium phosphate (CaPi) requires the presence of soluble calcium and this dependence exhibits a Michaelian-like behavior. This result suggests that the formation of a complex between 5'-AMP and free Ca2+ (CaAMP) is a prelude to the adsorption of the nucleotide in the solid matrix. At concentrations one order of magnitude higher, Mn2+ and Mg2+ can substitute for soluble Ca2+ in the adsorption of 5'-AMP onto solid CaPi. However, when added simultaneously with 5'-AMP to a heterogeneous mixture that contains CaPi and soluble Ca2+, Mn2+ and Mg2+ inhibit the adsorption of 5'-AMP in a concentration-dependent manner. This suggests the formation of complexes that are much less effective for 5'-AMP adsorption than the CaAMP complex. On the other hand, Mn2+ and Mg2+ cannot promote desorption of the nucleotide attached to the precipitate in the presence of soluble Ca2+ if they are added after adsorption has attained equilibrium. Although desorption of 5'-AMP can be obtained by a sequential dilution of the soluble phase with buffer and no nucleotide in a process that obeys a Langmuir equation, the lack of effect of Mn2+ or Mg2+ when adsorption has attained its maximal value suggests strong interactions between the CaAMP complex and the solid matrix when adsorption equilibrium is reached. The divalent cations present in the matrix also participate with different selectivity in the attachment of the CaAMP complex, indicating that a cation-exchange mechanism could have acted in the modulation of adsorptive/desorptive processes involving biomonomers and phosphate surfaces in primitive aqueous environments.

Adenosine Monophosphate↗
PubMed2004

Adsorption of zinc on bed sediment of River Hindon: adsorption models and kinetics.

The paper presents a study of zinc adsorption using the experimental data on bed sediments of River Hindon in western Uttar Pradesh (India). The effect of various operating variables, viz., initial concentration, solution pH, sediment dose, contact time, and particle size, have been studied. The optimum contact time needed to reach equilibrium was of the order of 60 min and was independent of initial concentration of zinc ions. The extent of adsorption increased with an increase of pH. Furthermore the adsorption of zinc increases with increasing adsorbent doses and decreases with the adsorbent particle size. The content of iron, manganese and organic matter in various fraction of sediment decreases with increasing particle size indicating the possibility of the two geochemical phases to act as the active support material for the adsorption of zinc ions. The adsorption data follows both Langmuir and Freundlich adsorption models. Isotherms were used to determine thermodynamic parameters, viz., free energy change, enthalpy change and entropy change. The negative values of free energy change indicate spontaneous nature of the adsorption while positive values of enthalpy change suggest the endothermic nature of the adsorption of zinc on bed sediment of the River Hindon. The positive values of entropy change indicate randomness at the solid/solution interface.

Adsorption↗
PubMed1991

[Adsorption of pesticides on synthetic adsorption polymers].

On the basis of adsorption of selected pesticides on synthetic adsorption polymers it has been shown that both the adsorption balances as well as kinetics and dynamics of the adsorption strongly depend on the concentration of hydrogen ions of the liquid phase. The dependence of adsorption isotherms on pH value was demonstrated with sufficient accuracy by resorting to the models having been suggested on the ground of IAS theory and the potential one. The kinetic investigations have revealed that the surface diffusion proceeds extremely rapidly in pH ranges that lodge between sorptive pK value and the isoelectric point of the adsorbent surface. The known solutions of transportation and balance equations, which in this case were transferred on the pH-dependent adsorption processes, were implemented for simulating the breakthrough curves. The investigation, covering the effect of the presence of heavy metals in a solution exerted on the pesticides adsorption properties, has shown that the formation of model-pesticide type connections improves the adsorption properties of pesticides to a lesser or greater extent.

2,4-Dichlorophenoxyacetic Acid↗
PubMed2004

Adsorption of gases and vapors on nanoporous Ni2(4,4'-Bipyridine)3(NO3)4 metal-organic framework materials templated with methanol and ethanol: structural effects in adsorption kinetics.

Desolvation of Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2CH(3)OH and Ni(2)(4,4'-bipyridine)(3)(NO(3))(4).2C(2)H(5)OH give flexible metal-organic porous structures M and E, respectively, which have the same stoichiometry, but subtly different structures. This study combines measurements of the thermodynamics and kinetics of carbon dioxide, methanol, and ethanol sorption on adsorbents M and E over a range of temperatures with adsorbent structural characterization at different adsorbate (guest) loadings. The adsorption kinetics for methanol and ethanol adsorption on porous structure E obey a linear driving force (LDF) mass transfer model for adsorption at low surface coverage. The corresponding adsorption kinetics for porous structure M follow a double exponential (DE) model, which is consistent with two different barriers for diffusion through the windows and along the pores in the structure. The former is a high-energy barrier due to the opening of the windows in the structure, required to allow adsorption to occur, while the latter is a lower-energy barrier for diffusion in the pore cavities. X-ray diffraction studies at various methanol and ethanol loadings showed that the host porous structures E and M underwent different scissoring motions, leading to an increase in unit cell volume with the space group remaining unchanged during adsorption. The results are discussed in terms of reversible adsorbate/adsorbent (host/guest) structural changes and the adsorption mechanism involving hydrogen-bonding interactions with specific surface sites for methanol and ethanol adsorption in relation to pore size and extent of filling. This paper contains the first evidence for individual kinetic barriers to diffusion through windows and pore cavities in flexible porous coordination polymer frameworks.

Journal Article↗
PubMed1984

Adsorption of pepsin by aluminum hydroxide I: Adsorption mechanism.

Adsorption of pepsin by gibbsite and boehmite, non-acid-reactive forms of aluminum hydroxide, was observed and related to the surface area of the adsorbent. Adsorption was pH dependent, with maximum adsorption occurring between pH 2.7-3.3 for gibbsite and pH 2.7-4.3 for boehmite. Electrostatic attraction was an important adsorption mechanism at the pH conditions encountered in the GI tract; the isoelectric point of pepsin was approximately 1, giving it a negative charge, and the point of zero charge for the adsorbents was greater than 9, giving them a positive charge. However, the pH-adsorption profile can not be fully explained by electrostatic considerations. Desorption studies indicate the importance of specific adsorption because pepsin was not desorbed by washing with acidified water, but was partly desorbed by exchange with phosphate. The IR spectrum of adsorbed pepsin also suggested that specific adsorption of pepsin occurred through anionic ligand exchange involving carboxylate groups of pepsin and surface aluminum ions.

Adsorption↗