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PubMed2004

Study of hexane adsorption in nanoporous MCM-41 silica.

We study here the adsorption of hexane on nanoporous MCM-41 silica at 303,313, and 323 K, for various pore diameters between 2.40 and 4.24 nm. Adsorption equilibria, measured thermogravimetrically, show that all the isotherms, that are somewhat akin to those of type V, exhibit remarkably sharp capillary adsorption phase transition steps and are reversible. The position of the phase transition step gradually shifts from low to high relative pressure with an increase in the temperature as well as the pore sizes. The isosteric heats of adsorption derived from the equilibrium information using the Clapeyron equation reveal a gradual decrease with increasing adsorbed amount because of the surface heterogeneity but approach a constant value near the phase transition. A decrease in the pore size results in an increase in the isosteric heat of adsorption because of the increased dispersion forces. A simple strategy, based on the Broekhoff and De Boer adsorption theory, successfully interprets the hexane adsorption isotherms for the different pore size MCM-41 samples. The parameters of an empirical expression, used to represent the potential of interaction between the adsorbate and adsorbent, are obtained by fitting the monolayer region prior to capillary condensation and the experimental phase transition simultaneously, for some pore sizes. Subsequently, the parameters are used to predict the adsorption isotherm on other pore size samples, which showed good agreement with experimental data.

Journal Article↗
PubMed2005

Effect of the carbon surface layer chemistry on benzene adsorption from the vapor phase and from dilute aqueous solutions.

We present a complex study of benzene adsorption on chemically modified commercial activated carbons. The porosity of studied carbons is almost the same, whereas the chemical composition and the acid-base properties of surface layers differ drastically from amphoteric (initial de-ashed carbon D43/1, Carbo-Tech, Essen, Germany) and acidic (carbon modified with concentrated HNO3 and fuming H2SO4) to strongly basic (carbon modified with gaseous NH3). Benzene adsorption isotherms measured from aqueous solution at three temperatures (298, 313, and 323 K) and at the neutral pH level are reported. They are supported by studies of water and benzene adsorption from the gaseous phase (volumetric and calorimetric data) and the data of benzene temperature-programmed desorption (TPD). Moreover, the data of the enthalpy of immersion in water and benzene are also presented. Obtained data of benzene adsorption from the gaseous phase are approximated by applying the method of Nguyen and Do (ND) and the Dubinin-Astakhov (DA) equation. The data of adsorption from solution are described by the hybrid DA-Freundlich (DA-F) model. We show that there are similarities in the mechanisms of benzene adsorption from the gaseous phase and from aqueous solutions and that the pore-blocking effect is the main stage of the adsorption mechanism. This effect strongly depends on the polarity of the carbon surface. The larger the ratio of the enthalpy of carbon immersion in water to the enthalpy of immersion in benzene, the larger the reduction in adsorption from solution, compared to that in the gaseous phase, that is observed.

Journal Article↗
PubMed2006

Ethanol, acetic acid, and water adsorption from binary and ternary liquid mixtures on high-silica zeolites.

Adsorption isotherms were measured for ethanol, acetic acid, and water adsorbed on high-silica ZSM-5 zeolite powder from binary and ternary liquid mixtures at room temperature. Ethanol and water adsorption on two high-silica ZSM-5 zeolites with different aluminum contents and a high-silica beta zeolite were also compared. The amounts adsorbed were measured using a recently developed technique that accurately measures the changes in adsorbent/liquid mixture density and liquid concentration. This technique allows the adsorption of each compound in a liquid mixture to be measured. Adsorption data for binary mixtures were fit with the dual-site extended Langmuir model, and the parameters were used to predict ternary adsorption isotherms for each compound with reasonable accuracy. In ternary mixtures, acetic acid competed with ethanol and water for adsorption sites and reduced ethanol adsorption more than it reduced water adsorption.

Journal Article↗
PubMed2006

Adsorption of hydrophobically modified starch at oil/water interfaces during emulsification.

The adsorption of starch that had been hydrophobically modified with octenyl succinate anhydride (OSA) at the oil/water interface during emulsification was studied. The starch samples were of waxy barley origin and were varied in molar mass and degree of substitution (DS). The particle size of the emulsions was measured and the adsorbed amount of starch was determined through serum depletion. The results show that adsorption is governed by the relationship between interfacial area and OSA-starch concentration. The surface load of OSA-starch can in some cases become very high, reaching 16 mg/m(2). The emulsification occurs under nonequilibrium and turbulent flow conditions. Under these conditions kinetic factors are likely to play an important role in the adsorption process. Turbulent flow favors transport to the interface of larger molecules over small ones, which could lead to higher surface loads by causing jamming at the interface. A model that treats the adsorption as a collision between particles in turbulent flow has been used, and it shows that the adsorption time of a polymer decreases with increasing polymer radius. It also shows that the time scale of adsorption is shorter than the time scales for configurational changes of macromolecules at interfaces and that emulsion droplet-droplet collisions are of similar time scales as adsorption, which gives further indications that kinetic factors are important during adsorption. The simulation results give a reasonable explanation to why large molecules such as OSA-starch can be efficient as emulsifiers.

Journal Article↗
PubMed2006

Consistent approach to adsorption thermodynamics on heterogeneous surfaces using different empirical energy distribution models.

Adsorption on heterogeneous surfaces with three basic energy distribution models (uniform model, exponential model, and normal-like model) is studied. Exact analytical solutions of the adsorption isotherms and the heats of adsorption are derived for the uniform and exponential models, and, with these solutions including a numerical solution for the normal-like model, the behavior of the differential heat of adsorption and the "apparent" standard adsorption entropy concerning the overall surface is described as a function of coverage and temperature. The approximations underlying the isotherms and heats of adsorption in the Temkin, Freundlich, and Langmuir-Freundlich types of adsorption are rationalized. By comparing these empirical formulas to the exact solutions, the level of these approximations is found to be identical, which is similar to the "condensation approximation". Their preconditions are that either the temperature is low enough, or the surface is strongly heterogeneous. Generally, they are suitable for the middle coverage range. The exact solutions provide a method to obtain more information on the heats, entropy, and heterogeneity of the catalyst surface from the calorimetric measurement of the heat of adsorption.

Journal Article↗
PubMed2003

Blood response to plasticized poly(vinyl chloride): dependence of fibrinogen adsorption on plasticizer selection and surface plasticizer level.

The high level of plasticizer in plasticized poly(vinyl chloride) (PVC) ensures that plasticizer selection has an important influence on the suitability of PVC to function in blood-contacting applications. In this study, three types of plasticized PVC in sheet form, with di-(2-ethylhexyl)phthalate (DEHP), tri-(2-ethylhexyl)trimellitate (TEHTM) and n-butyryltri-n-hexyl citrate (BTHC) as plasticizer, were selected for assessment and single solute fibrinogen adsorption was utilized as an initial index of interactions with blood components. Fibrinogen adsorption behavior shows a strong dependence on the plasticizer selection, plasticizer level at the surface and the adsorption conditions, such as adsorption time and fibrinogen solution concentration. Results indicate that BTHC plasticized PVC possesses the lowest adsorption capacity in the three types of plasticized PVC, while TEHTM plasticized PVC seems to have the strongest reactivity in certain fibrinogen solution concentrations. The alteration of surface plasticizer level was achieved by a methanol-cleaning treatment with a variety of cleaning times and the fibrinogen adsorption on plasticized PVC decreases with the reduction of surface plasticizer level. The migration behavior of two phthalate esters (DEHP and TEHTM) was evaluated using UV-Spectrophotometer to determine the plasticizer level at the surfaces. In addition, the fibrinogen adsorption mechanism was examined with Freundlich adsorption modeling.

Journal Article↗
PubMed2006

Microkinetic modeling of CO TPD spectra using coverage dependent microcalorimetric heats of adsorption.

CO adsorption on the ternary methanol synthesis Cu/ZnO/Al2O3 catalyst was studied in detail by means of adsorption microcalorimetry and flow temperature-programmed desorption (TPD). Based on these experimental data, we established a microkinetic analysis method, which provides information about the adsorption kinetics of CO on the catalyst surface. Experimentally derived microcalorimetric heats of adsorption were applied in a microkinetic model to simulate TPD curves with varying initial coverage. Two approaches were used: an integral approach based on evaluation of the integral heats of adsorption which predicts the experimental TPD curves roughly and provides first approximations for the preexponential factors. The second, more detailed approach was based on the simulation of the adsorption isotherm taking the experimentally determined coverage-dependence of the heat of adsorption into account. This approach led to a significantly improved agreement between experimental and simulated TPD curves. Moreover, it was possible to derive the standard entropy of adsorption. The general applicability of our approaches is demonstrated by analyzing the CO TPD and microcalorimetry data obtained with a binary ZnO-free Cu/Al2O3 catalyst.

Journal Article↗
PubMed2005

Adsorption dynamics of CO2 on Zn-ZnO(0001): a molecular beam study.

Presented are initial S(0) and coverage Theta dependent, S(Theta), adsorption probability measurements, respectively, of CO(2) adsorption on the polar Zn-terminated surface of ZnO, parametric in the impact energy E(i), the surface temperature T(s), the impact angle alpha(i), varied along the [001] azimuth, the CO(2) flux, and the density of defects, chi(Ar(+)), as varied by rare gas ion sputtering. S(0) decreases linearly from 0.72 to 0.25 within E(i)=0.12-1.33 eV and is independent of T(s). Above E(i)=0.56 eV, S(0) decreases by approximately 0.2 with increasing alpha(i). The shape of S(Theta) curves is consistent with precursor-mediated adsorption (Kisliuk shape, i.e., S approximately const) for low E(i); above E(i)=0.56 eV, however, a turnover to adsorbate-assisted adsorption (S increases with Theta) has been observed. The initial slope of S(Theta) curves decreases thereby with increasing alpha(i), chi(Ar(+)), and T(s), i.e., the adsorbate-assisted adsorption is most distinct for normal impact on the pristine surface at low T(s) and is independent of the CO(2) flux. The S(Theta) curves have been parametrized by analytic precursor models and Monte Carlo simulations have been conducted as well. The temperature dependence of the saturation coverage shows two structures which could be assigned to adsorption on pristine and intrinsic defect sites, respectively, in agreement with a prior thermal desorption spectroscopy study. The heat of adsorption E(d) for the pristine sites amounts to 34.0-5.4Theta, whereas for adsorption on the intrinsic defect sites E(d) of approximately 43.6 kJ/mol could be estimated. Thus, a kinetic structure-activity relationship was present.

Journal Article↗
PubMed2006

Irreversible adsorption of tethered chains at substrates: Monte Carlo study.

The irreversible adsorption of single chains grafted with one end to the surface is studied using scaling arguments and computer simulations. We introduce a two-phase model, in which the chain is described by an adsorbate portion and a corona portion formed by nonadsorbed monomers. The adsorption process can be viewed as consisting of a main stage, during which monomers join by "zipping" (along their order in the chain) the surface, and a late stage, in which the remaining corona collapses on the surface. Based on our model we derive a scaling relation for the time of adsorption t(M) as a function of the number M of adsorbed monomers; t(M) follows a power law, M(alpha), with alpha > 1. We find that alpha is related to the Flory exponent nu by alpha = 1 + nu. Using further scaling arguments we derive relations between the overall time of adsorption, the characteristic time of adsorption (given by the crossover time between the main and the last stage of adsorption), and the chain length. To support our analysis we perform Monte Carlo simulations using the bond fluctuation model. In particular, the sequence of adsorption events is very well reproduced by the simulations, and an analysis of the various density profiles supports our theoretical model. Especially the loop formation during adsorption clearly shows that the growth of the adsorbate is dominated by zipping. The simulations are also in almost quantitative agreement with our theoretical scaling analysis, showing that here the assumption of a linear relation between Monte Carlo steps and time is well obeyed. We conclude by also discussing the geometrical shape of the adsorbate.

Journal Article↗
PubMed2006

Adsorption of model surfactantlike copolymers on nanopatterned surfaces.

The adsorption of polymers, copolymers, surfactants, and biopolymers is often used to engineer surfaces. Towards improving our understanding of polymer adsorption we report simulation results for the adsorption of model copolymers, resembling surfactants, on nanoscale patterned hydrophobic surfaces at infinitely dilute concentrations. The surfactants are composed by a hydrophobic tail and a hydrophilic head. Surfactant adsorption on the hydrophobic surface occurs in the tail-down configuration in which the tail segments are in contact with the surface. We investigate how the presence of a solid hard mask, used to create the nanoscale pattern on the underlying hydrophobic surface, affects the surfactant adsorption. We find that surfactant adsorption on the underlying hydrophobic surface is prevented when the characteristic dimensions of the solid hard mask are less than twice the radius of gyration. We also show that details about mask-surfactant head effective interactions have the potential to alter the characteristics of adsorption. When the mask repels the head segments, the surfactants hardly adsorb on the underlying hydrophobic surface. When the mask strongly attracts the surfactant heads, the surfactants may preferentially adsorb on the mask rather than on the underlying hydrophobic surface. Under these latter circumstances the adsorbed surfactants in some cases assume a head-down configuration in which the head segments are in contact with the mask and the tail segments extend towards the bulk solution. We explain our results in terms of enthalpy and entropy of adsorption and discuss practical implications.

Journal Article↗
PubMed2006

CO adsorption on pure and binary-alloy gold clusters: a quantum chemical study.

We performed density-functional theory analysis of nondissociative CO adsorption on 22 binary Au-alloy (Au(n)M(m)) clusters: n=0-3, m=0-3, and m+n=2 (dimers) or 3 (trimers), M=Cu/Ag/Pd/Pt. We report basis-set superposition error corrections to adsorption energies and include both internal energy of adsorption (DeltaU(ads)) and Gibbs free energy of adsorption (DeltaG(ads)) at standard conditions (298.15 K and 1 atm). We found onefold (atop) CO binding on all the clusters except Pd2 (twofold/bridged), Pt2 (twofold/bridged), and Pd3 (threefold). In agreement with the experimental results, we found that CO adsorption is thermodynamically favorable on pure Au/Cu clusters but not on pure Ag clusters and also observed the following adsorption affinity trend: Pd>Pt>Au>Cu>Ag. For alloy dimers we found the following patterns: Au2>M Au>M2 (M=Ag/Cu) and M2>M Au>Au2 (M=Pd/Pt). Alloying Ag/Cu dimers with (more reactive) Au enhanced adsorption and the opposite effect was observed for PdPt dimers. The Ag-Au, Cu-Au, and Pd-Au trimers followed the trends observed on dimers: Au3>M Au2>M2Au>M3 (M=Ag/Cu) and Pd3>Pd2Au>PdAu2>Au3. Interestingly, Pt-Au trimers reacted differently and alloying with Au systematically increased the adsorption affinity: PtAu2>Pt2Au>Pt3>Au3. A strikingly different behavior of Pt is also manifested by the triplet spin state and onefold (atop) binding in Pt3-CO which is in contradiction with the singlet spin state and threefold binding in Pd3-CO. We found a linear correlation between CO binding energy (BE) and elongation of the CO bond. For Ag-Au and Cu-Au clusters, the increase in CO BE (and elongation of the C-O bond which is probably due to the back donation) is accompanied by the decrease in the cluster-CO distance suggesting that the donation (from 5sigma highest occupied molecular orbital in CO to cluster lowest unoccupied molecular orbital) mechanism also contributes to the BE. For Pd-Au clusters, the cluster-CO distance (and CO bond length) increases with increase in the BE, suggesting that the donation mechanism may not be important for those clusters. No clear trend was observed for Pt-Au clusters.

Journal Article↗
PubMed1967

Action of Plant Growth Regulators. IV. Adsorption of Unsubstituted and 2,6-Dichloro-aromatic Acids to Oat Monolayers.

The adsorption of chloro-aromatic acids to monomolecular layers of oat squashes is reported in earlier papers but it was not possible by the technique used, to measure unambiguously the adsorption of unsubstituted and 2,6-dichloro-aromatic acids. This has now been achieved by a modification of the earlier method and involves assessments of competitive adsorption between the unknown acid and a standard acid, using measurements of surface potential.Benzoic and phenoxyacetic acids were not adsorbed but phenylacetic acid was weakly adsorbed. The second ring in naphthalene and naphthoxyacetic acids greatly increased adsorption. Substitution of the 2 and 6 positions in the phenyl and phenoxyacetic acids resulted in low adsorption but 2,6-disubstituted phenoxybutyric and benzoic acids were more highly adsorbed.The adsorption values from earlier work are combined and discussed in relation to the growth-regulating activity of the acids. It is conciuded that there is no direct relation embracing all acids between adsorption and activity, notable exceptions being those substituted by chlorine in the 3-position of the aromatic ring. However, for a number of acids it is suggested that activity is limited not only by their ability to interact at enzyme sites but also by the amount of acid immobilised by adsorption when moving to these sites. It is also concluded that the hydrophilic/lipophilic balance of a growth regulator sometimes used as a guide to its activity, is an unreliable indication of interfacial behaviour.

Journal Article↗
PubMed1994

Lactococcal bacteriophages require a host cell wall carbohydrate and a plasma membrane protein for adsorption and ejection of DNA.

The mechanism of the initial steps of bacteriophage infection in Lactococcus lactis subsp. lactis C2 was investigated by using phages c2, ml3, kh, l, h, 5, and 13. All seven phages adsorbed to the same sites on the host cell wall that are composed, in part, of rhamnose. This was suggested by rhamnose inhibition of phage adsorption to cells, competition between phage c2 and the other phages for adsorption to cells, and rhamnose inhibition of lysis of phage-inoculated cultures. The adsorption to the cell wall was found to be reversible upon dilution of the cell wall-adsorbed phage. In a reaction step that apparently follows adsorption to the cell wall, all seven phages adsorbed to a host membrane protein named PIP. This was indicated by the inability of all seven phages to infect a strain selected for resistance to phage c2 and known to have a defective PIP protein. All seven phages were inactivated in vitro by membranes from wild-type cells but not by membranes from the PIP-defective, phage c2-resistant strain. The mechanism of membrane inactivation was an irreversible adsorption of the phage to PIP, as indicated by adsorption of [S] methionine-labeled phage c2 to purified membranes from phage-sensitive cells but not to membranes from the resistant strain, elimination of adsorption by pretreatment of the membranes with proteinase K, and lack of dissociation of S from the membranes upon dilution. Following membrane adsorption, ejection of phage DNA occurred rapidly at 30 degrees C but not at 4 degrees C. These results suggest that many lactococcal phages adsorb initially to the cell wall and subsequently to host cell membrane protein PIP, which leads to ejection of the phage genome.

Journal Article↗
PubMed1999

Production of biogenic Mn oxides by leptothrix discophora SS-1 in a chemically defined growth medium and evaluation of their Pb adsorption characteristics

Biogenic Mn oxides were produced by the bacterium Leptothrix discophora SS-1 (= ATCC 3182) in a chemically defined mineral salts medium, and the Pb binding and specific surface area of these oxides were characterized. Growth of SS-1 in the defined medium with pyruvate as a carbon and energy source required the addition of vitamin B12. Complete oxidation of Mn(II) within 60 h required the addition of >/=0.1 &mgr;M FeSO4. Pb adsorption isotherms were determined for the biogenic Mn oxides (and associated cells with their extracellular polymer) and compared to the Pb adsorption isotherms of cells and exopolymer alone, as well as to abiotic Mn oxides. The Pb adsorption to cells and exopolymer with biogenic Mn oxides (0.8 mmol of Mn per g) at pH 6.0 and 25 degreesC was 2 orders of magnitude greater than the Pb adsorption to cells and exopolymer alone (on a dry weight basis). The Pb adsorption to the biogenic Mn oxide was two to five times greater than the Pb adsorption to a chemically precipitated abiotic Mn oxide and several orders of magnitude greater than the Pb adsorption to two commercially available crystalline MnO2 minerals. The N2 Brunauer-Emmet-Teller specific surface areas of the biogenic Mn oxide and fresh Mn oxide precipitate (224 and 58 m2/g, respectively) were significantly greater than those of the commercial Mn oxide minerals (0.048 and 4. 7 m2/g). The Pb adsorption capacity of the biogenic Mn oxide also exceeded that of a chemically precipitated colloidal hydrous Fe oxide under similar solution conditions. These results show that amorphous biogenic Mn oxides similar to those produced by SS-1 may play a significant role in the control of trace metal phase distribution in aquatic systems.

Journal Article↗
PubMed1998

Expanded and packed bed albumin adsorption on fluoride modified zirconia.

The expanded bed characteristics of 75-103microm fluoride-modified zirconia (FmZr) particles synthesized by a fed batch oil emulsion process were investigated. These particles are distinguished from commercially available expanded-bed adsorbents by virtue of their high density (2.8 g/cc) and the mixed mode protein retention mechanism which allows for the retention of both cationic and anionic proteins. The linear velocity versus bed porosity data agree with the Richardson-Zaki relationship with the terminal velocity in infinite medium of 2858.4 cm/h and a bed expansion index of 5.1. Residence time distribution (RTD) studies and bovine serum albumin (BSA) adsorption studies were performed as a function of the height of the settled bed to the column diameter (H:D) ratio and degree of bed expansion with superficial velocities of 440 to 870 cm/h. The settled bed, a 2x expanded bed, and a 3x expanded bed were studied for the H:D ratios of 1:1, 2:1, and 3:1. The dynamic binding capacity (DBC) at 5% breakthrough was low (2-8 mg BSA/mL settled bed) and was independent of the H:D ratio or the degree of bed expansion. The saturation DBC was 32.3 +/- 7.0 mg BSA/mL settled bed. The adsorption-desorption kinetics and intraparticle diffusion for protein adsorption on FmZr (38-75 micrometer) were investigated by studying the packed bed RTD and BSA adsorption as a function of temperature and flow rate. The data show that the adsorption-desorption kinetics along with intraparticle diffusion significantly influence protein adsorption on FmZr. Low residence times ( approximately 0.8 min) of BSA result in a DBC at 5% breakthrough which is 3.5-fold lower compared to that at 6-fold higher protein residence time. At low linear velocity (45 cm/h) the breakthrough curve is nearly symmetrical and becomes asymmetrical and more dispersed at higher linear velocity (270 cm/h) due to the influence of slow adsorption-desorption kinetics and intraparticle diffusion. Bioeng 60: 333-340, 1998.

Adsorption↗
PubMed1999

Expanded bed adsorption of human serum albumin from very dense Saccharomyces cerevesiae suspensions on fluoride-modified zirconia.

The adsorption of proteins from high cell density yeast suspensions on mixed-mode fluoride-modified zirconia (FmZr) particles (38 to 75 microm, surface area of 29 m(2)/g and density of 2.8 g/cm(3)) was investigated using human serum albumin (HSA) added to Saccharomyces cerevesiae as the model expression host. Because of the high density of the porous zirconia particles, HSA (4 mg/mL) can be adsorbed from a 100 g dry cell weight (DCW)/L yeast suspension in a threefold-expanded bed of FmZr. The expanded bed adsorption of any protein from a suspension containing >50 g DCW/L cells has not been previously reported. The FmZr bed expansion characteristics were well represented by the Richardson-Zaki correlation with a particle terminal velocity of 3.1 mm/s and a bed expansion index of 5.4. Expanded bed hydrodynamics were investigated as a function of bed expansion using residence time distribution studies with sodium nitrite as the tracer. The adsorption of HSA on FmZr exhibited features of multicomponent adsorption due to the presence of dimers. The protein binding capacity at 5% breakthrough decreased from 22 mg HSA/mL settled bed void volume for 20 g DCW/L yeast to 15 mg HSA/mL settled bed void volume for 40 g DCW/L yeast and remained unchanged for the higher yeast concentrations (60 to 100 g DCW/L). However, the batch (or equilibrium) binding capacity decreased monotonically as a function of yeast concentration (20 to 100 g DCW/L) and the binding capacity at 100 g DCW/L yeast was fivefold lower compared with that at 20 g DCW/L yeast. The lower batch binding capacity at high cell concentrations resulted from the adsorption of cells at the surface of the particles restricting access of HSA to the intraparticle surface area. Batch (or equilibrium) and column HSA adsorption results indicated that the adsorption of HSA on FmZr occurred at a time scale that may be much faster than that of yeast cells. The zirconia particles were cleaned of adsorbed HSA and yeast with a total of 1500 to 2000 column volumes (over many cycles) of 0. 25 M NaOH, without any significant effect on the chromatographic performance.

Adsorption↗
PubMed1999

Adsorption from solutions on synthetic hydroxyapatite: nonaqueous vs. aqueous solvents.

It is useful in restorative dentistry and etiology of bone diseases to know that certain general rules may be derived from a priori considerations of the adsorption of chemicals to synthetic hydroxyapatite (which is the structural prototype of tooth and bone mineral). This article systematically synthesizes the extensive studies on the subject by the author, and rationalizes and extends these rules. Though not a review article, the work of some researchers may not have found an adequate representation here, because they did not determine, in the case of nonaqueous solvents, the reversibility of adsorption; or, in the case of aqueous solvents, the concentration of all constituent ions of the system, thus missing the occurrence of processes other than adsorption. The adsorption of solutes from nonaqueous solvents on hydroxyapatite is mainly regulated by the interplay of hydrogen bonding between adsorbate, adsorbent, and solvent. It does not involve any significant role of ionic nature of the apatite surface, because it is masked by the chemisorbed and physisorbed water. This interplay of hydrogen bonding in conjunction with chemical and structural characteristics of the adsorbed molecules controls their reversibility and the orientation of the adsorbates on the surface. In general, the process may be considered as true adsorption, because no other material exchange process is involved. The "adsorption" of solutes from aqueous solutions generally involves ion-exchange with the apatite surface, and may be affected by the concentrations of potential determining ions (Ca(2+), phosphates, H(+), etc.) in the solution. The solute in aqueous solution may be removed by two other mechanisms, either by formation of a surface complex or by chemically reacting with calcium or phosphate ions to form a new phase that precipitates out of solution. Therefore, the concentration of calcium and phosphate ions in solution should also be monitored to elucidate the mechanism of the process. Adsorption of polymers seems to be determined primarily by their multiple hydrogen bonding, their relative molar mass, and their ability to self-associate. The hydrogen ion concentration plays a decisive role in each one of the above mechanisms.

Adsorption↗
PubMedDate not supplied

Monitoring fibrinogen adsorption kinetics by interfacial TIRF rheometry.

The adsorption kinetics of purified fibrinogen to unmodified and aminopropylsilane-modified quartz glass surfaces were studied under pseudo-first order (binding-unit excess) conditions by the total internal reflection fluorescence (TIRF) method. Fluorescence in the adsorbed protein layer (350 nm) was excited by the evanescent wave at 285-290 nm. In order to reduce and possibly eliminate the influence of mass transfer on the kinetics of fibrinogen adsorption, a novel protein adsorption chamber containing a cone-and-plate rheometer with total internal reflection technology was employed. The aim of the study was to obtain critical shear rates, at which the adsorption rate of fibrinogen became independent of diffusion. Therefore, shear rates were varied between 0 and 7200 s-1 at initial fibrinogen concentrations of c9 = 4.7 and 17.7 micrograms mL-1. The adsorption rate of fibrinogen increased 5-17-fold, depending on the surface, as the critical shear rate was approached. Above the critical shear rates the kinetic data of fibrinogen adsorption could be fitted at c9 = 4.7 micrograms mL-1 to a single exponential function, indicating the predominance of a single binding step with a half-life of ca 20 s. At the higher initial concentration of c9 = 17.7 micrograms/mL-, however, a significant deviation from the single exponential behavior was observed in the first 10 s of the adsorption reaction, indicating a very fast initial event with a half-life of ca 5 s in addition to a slower binding reaction with a half-life of ca 35 s. Thus the novel TIRF rheometer can resolve kinetics down to half-lives of 5 s and possibly even lower.

Adsorption↗