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PubMed2006

Adsorption of dansylated amino acids on molecularly imprinted surfaces: a surface plasmon resonance study.

Surface plasmon resonance spectroscopy (SPR) was used to measure the adsorption kinetics and isotherms of dansylated amino acids onto surface-confined molecularly imprinted polymer films (MIP-Fs) and the corresponding non-imprinted polymer control films (NIP-Fs). The surface-confined polymer films were grafted from flat gold surfaces using atom transfer radical polymerization (ATRP). This approach allowed uniform nanothin films to be grown, thereby ensuring that the amino acids see a uniform surface during adsorption. N,N'-Didansyl-l-cystine (DDC) and didansyl-l-lysine (DDK) were used as the template molecules to form the MIP-Fs. Adsorption kinetics data were analyzed using single- and dual-site Langmuir adsorption models. It was found that, within the experimental measurement range, adsorption isotherm data were well described by any of four isotherm models: Langmuir, dual-site Langmuir, Freundlich, or Langmuir-Freundlich (LF). The relatively high heterogeneity index values regressed using the Freundlich and LF isotherms suggest the formation of fairly homogeneous MIP-Fs; although Scatchard analysis reveals binding site heterogeneity does exist. Selectivity studies showed that the MIP-Fs display cross-reactivity between DDC and DDK; nevertheless, MIP-Fs prepared against one template showed selectivity for that template. Solution pH and polymer layer thickness were studied as independent parameters to determine their impacts on amino acid adsorption, as monitored by SPR.

Adsorption↗
PubMed2004

Adsorption of phenolics on activated carbon--impact of pore size and molecular oxygen.

The impact of pore size of activated carbon fibers (ACFs) on adsorption capacity and on the potential for oligomerization of phenolic compounds on the surface of ACFs in the presence of molecular oxygen has been investigated in this study. Compared with granular activated carbon (GAC), ACFs have unique pore size distributions, suitable to be used to elucidate the effect of pore structure on adsorption. Adsorption isotherm data were collected for o-cresol and 2-ethylphenol on four ACFs (ACC-10, ACC-15, ACC-20, and ACC-25) with different micropore volumes and BET surface area and on one type of GAC bituminous base. These isotherms were collected under anoxic (absence of molecular oxygen) and oxic (presence of molecular oxygen) conditions. No significant impact of the presence of molecular oxygen on adsorption capacity was noted for ACC-10. ACC-10 has an average pore width of 19.2 A and total pore volume of 0.43 cm3g(-1). On the other hand, for the remaining ACFs, which have larger average pore width and larger pore volume, significant increase in the adsorptive capacity had been observed when molecular oxygen was present. The GAC gave the greatest difference between anoxic and oxic conditions when compared to all the ACFs studied. Binary adsorption of o-cresol and 2-ethylphenol on ACFs with the least pore size (ACC-10) also showed no significant differences between oxic and anoxic environment. The binary system under both anoxic and oxic conditions was well predicted by the ideal adsorbed solution theory (IAST).

Adsorption↗
PubMed2004

Competitive adsorption characteristics of Co2+, Ni2+, and Cr3+ by IRN-77 cation exchange resin in synthesized wastewater.

Adsorption properties of Co2+, Ni2+, and Cr3+ on an Amberlite IRN-77 cation exchange resin were investigated in batch systems. Levels of adsorption rapidly approached an equilibrium state within 1 h. The adsorption characteristics of each metal onto the resin were accurately represented by Langmuir isotherms. Co2+ and Ni2+, which have an equivalent electrovalence, displayed similar levels of adsorption onto the resin when they coexisted in the solution. However, when Cr3+ was added to the solution it competitively replaced Co2+ and Ni2+ ions that had been previously adsorbed onto the resin, resulting in the desorption of these metals into the solution. The result was likely due to a higher adsorption affinity of Cr3+ relative to Co2+ and Ni2+. This implies that interactively competitive adsorption of multi-cations onto the resin should be thoroughly considered when contemplating the efficient operation of an ion exchange process in the treatment of industrial wastewater.

Adsorption↗
PubMed2004

Investigation on the influence of methanol on adsorption and leaching of pesticides with soil column liquid chromatography.

The effect of methanol of low concentration on adsorption and leaching of atrazine and tebuconazole was studied in this paper. The adsorption coefficients and the retardation factors (R(m)) of pesticides on EUROSOIL 3# log-linearly decreased as volumetric fraction of methanol (f(c)) was increased in the binary solvent mixtures of methanol and water. These data are consistent with solvophobic theory formerly outlined for describing the adsorption and transport of hydrophobic organic chemicals from mixed solvents. Nevertheless, the adsorption of these pesticides in soil-water system slightly increased when the soil was pre-washed with methanol in comparison with that pre-washed with water (pure water system). Furthermore, their adsorption coefficients were still higher in binary solvent systems with methanol of very low concentrations, i.e. f(c) < 0.03 for atrazine and f(c) < 0.01 for tebuconazole, than those in pure water system. The adsorption coefficients (log K(w)) of atrazine and tebuconazole predicted by solvophobic theory were 0.5792 and 1.6525, respectively, and their experimental log K(w) were 0.3701 and 1.6275 in pure water system. Obviously, the predicted log K(w) of the two pesticides was higher than the experimental log K(w) in pure water system. The predicted K(w) and the retardation factor (R(w)) in pure water system by solvophobic theory are thus possibly inaccurate.

Adsorption↗
PubMed2005

Adsorption characteristics of pesticides methamidophos and glyphosate by two soils.

Contributions of organic matter and minerals in soil were evaluated by comparing changes in adsorption of methamidophos (MDP) and glyphosate (GPS) before and after removal of organic matter from argaltoll (mollisol) and typustalf (alfisol) soils. Adsorption isotherms of MDP and GPS by the two soils comforted to Freundlich equation, and the adsorption capacity of GPS by argaltoll soil was higher than that of MDP. Due to the removal of organic matter from soils, K(f) values of MDP and GPS adsorbed by argaltoll soil, which were calculated from Freundlich equations and the measure of adsorption capacity, decreased by 46.1% and 75.0%, and these by typustalf soil decreased by 34.9% and 52.5%, respectively. Results from this study suggested that soil organic matter made greater contributions to adsorption of GPS, but soil minerals could provide more available adsorption sites for MDP.

Adsorption↗
PubMed2005

Adsorption kinetics and isotherms of pesticides onto activated carbon-cloth.

Adsorption of pesticides ametryn, aldicarb, dinoseb and diuron from aqueous solution onto high specific area activated carbon-cloth was studied. Kinetics of adsorption was followed by in situ UV-spectroscopy and the data were treated according to various rate models. The extent of adsorption was determined at the end of 125 min adsorption period. Rate constants and the extent of adsorption for the four pesticides were found to follow the order: dinoseb > ametryn > diuron > aldicarb. Adsorption isotherms were derived at 25 degrees C on the basis of batch analysis. Isotherm data were treated according to Langmuir and Freundlich models. The fits of experimental data to these equations were examined. The types of interactions between the surface and pesticide molecules were discussed.

2,4-Dinitrophenol↗
PubMed2005

Removal of a cationic dye from aqueous solutions by adsorption onto bentonite clay.

The ability of bentonite to remove malachite green from aqueous solutions has been studied for different adsorbate concentrations by varying the amount of adsorbent, temperature, pH and shaking time. Maximum adsorption of the dye, i.e. >90% has been achieved in aqueous solutions using 0.05 g of bentonite at a pH of 9. Thermodynamic parameters such as DeltaH degrees, DeltaS degrees and DeltaG degrees were calculated from the slope and intercept of the linear plots of lnK(D) against 1/T. Analysis of adsorption results obtained at 298, 308, 318 and 328 K showed that the adsorption pattern on bentonite seems to follow the Langmuir, Freundlih and D-R isotherms. The temperature increase reduces adsorption capacity by bentonite, due to the enhancement of the desorption step in the mechanism. The numerical values of sorption free energy (E(a)) of 1.00-1.12 kJ mol(-1) indicated physical adsorption. The kinetic data indicated an intraparticle diffusion process with sorption being first order. The rate constant k was 0.526 min(-1). The concentration of malachite green oxalate was measured before and after adsorption by using UV-Vis spectrophotometer.

Adsorption↗
PubMed2006

Studies on the adsorption and kinetics of photodegradation of a model compound for heterogeneous photocatalysis onto TiO(2).

An investigation was made on the adsorption and kinetics of photodegradation of potassium hydrogenphthalate in an aqueous suspension of TiO(2). Two models, Langmuir and Freundlich, were used to describe the adsorption process and the model proposed by Langmuir-Hinshelwood (L-H) was employed to describe the kinetics of the photodecomposition reactions of hydrogenphthalate. The results of the adsorptions were fitted to the models proposed by Langmuir and Freundlich. Adsorption was found to be a function of the temperature, with adsorption capacity increasing from 2.4 to 4.5 mg/g when the temperature rose from 20 to 30 degrees C. The kinetic model indicates that the rate constant, k, of the first order reaction, is high in the 10.0 to 100 mg/l interval, which is coherent with the low value of the adsorption constant, K. The results fitted to the L-H model led to an equation that, within the range of concentrations studied here, theoretically allows one to evaluate the photodegradation rate.

Adsorption↗
PubMed2006

Adsorption of basic dyes onto MCM-41.

The adsorption of two basic dyes, Basic Green 5 (BG5) and Basic Violet 10 (BV10), onto MCM-41 was studied to examine the possible effect of interactions between large adsorbates and MCM-41 on the pore structure stability of MCM-41 and the potential of MCM-41 for the removal of basic dyes from wastewater. The revolutions of surface characteristics and pore structure of MCM-41 induced by dyes adsorption were characterized based on the analyses of the nitrogen isotherms, the XRD patterns, and the FTIR spectra. It was experimentally concluded that when the effect of interactions between large dyes (such as BV10) and MCM-41 on the pore structure stability of MCM-41 was insignificant, MCM-41 might be a good adsorbent for the removal of basic dyes from wastewater. The adsorption of BV10 on MCM-41 with respect to contact time, pH, and temperature was then measured to provide more information about the adsorption characteristics of MCM-41. Both Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms and the pseudo-second-order kinetic model was used to describe the kinetic data, from which some adsorption thermodynamic parameters were also evaluated.

Adsorption↗
PubMed2007

Adsorption behavior of 2,4-dichlorophenol and pentachlorophenol in an allophanic soil.

The adsorption of 2,4-dichlorophenol (2,4-DCP) and pentachlorophenol (PCP) by a variable-charge soil from southern Chile was studied in a series of batch equilibration experiments. 2,4-DCP and PCP adsorption behavior was evaluated as a function of pH (pH values of 4.5, 6.0 and 7.5) in a 0.1M KCl (25 degrees C) background solution for soil material collected at three different depths (0-20 cm, 20-40 cm, and 40-60 cm). 2,4-DCP and PCP adsorption decreased with increasing soil pH, suggesting that the undissociated species were adsorbed more readily and that electrostatic repulsion may inhibit partitioning as pH increases. The PCP adsorption was greater than observed for 2,4-DCP and decreased with soil depth. Multiple regression analysis between K(d) and various soil properties indicated that the soil organic carbon content is a strong indicator of chlorophenol adsorption, and in addition to organic carbon, the soil pH is an important property controlling adsorption behavior.

Adsorption↗
PubMed2005

Systematic errors in the measurement of adsorption isotherms by frontal analysis Impact of the choice of column hold-up volume, range and density of the data points.

Besides the accuracy and the precision of the measurements of the data points, several important parameters affect the accuracy of the adsorption isotherms that are derived from the data acquired by frontal analysis (FA). The influence of these parameters is discussed. First, the effects of the width of the concentration range within which the adsorption data are measured and of the distribution of the data points in this range are investigated. Systematic elimination of parts of the data points before the calculation of the nonlinear regression of the data to the model illustrates the importance of the numbers of data points (1) within the linear range and (2) at high concentrations. The influence of the inaccuracy of the estimate of the column hold-up volume on each adsorption data point, on the selection of the isotherm model, and on the best estimates of the adsorption isotherm parameters is also stressed. Depending on the method used to measure it, the hold-up time can vary by more than 10%. The high concentration part of the adsorption isotherm is particularly sensitive to errors made on t(0,exp) and as a result, when the isotherm follows bi-Langmuir isotherm behavior, the equilibrium constant of the low-energy sites may change by a factor 2. This study shows that the agreement between calculated and experimental overloaded band profiles is a necessary condition to validate the choice of an adsorption model and the calculation of its numerical parameters but that this condition is not sufficient.

Adsorption↗
PubMed2006

Adsorption behavior of the (+/-)-Tröger's base enantiomers in the phase system of a silica-based packing coated with amylose tri(3,5-dimethyl carbamate) and 2-propanol and molecular modeling interpretation.

The binary adsorption isotherms of the enantiomers of Tröger's base in the phase system made of Chiral Technologies ChiralPak AD [a silica-based packing coated with amylose tri(3,5-dimethyl carbamate)] as the chiral stationary phase (CSP) and 2-propanol as the mobile phase were measured by the perturbation method. The more retained enantiomer exhibits a S-shaped adsorption isotherm with a clear inflection point, the concentration of the less retained enantiomer having practically no competitive influence on this isotherm: In the entire range of concentrations studied, dq2/dC1 approximately 0. By contrast, the less retained enantiomer has a Langmuir adsorption isotherm when pure. At constant mobile phase concentrations, however, its equilibrium concentration in the adsorbed phase increases with increasing concentration of the more retained enantiomer and dq1/dC2 > 0. This cooperative adsorption behavior, opposed to the classical competitive behavior, is exceedingly rare but was clearly demonstrated in this case. Two adsorption isotherm equations that account for these physical observations were derived. They are based on the formation of an adsorbed multi-layer, as suggested by the isotherm data. The excellent agreement between the experimental overloaded elution profiles of binary mixtures and the profiles calculated with the equilibrium-dispersive model validates this binary isotherm model. The adsorption energies calculated by molecular mechanics (MM) and by molecular dynamics (MD) indicate that the chiral recognition arising from the different interactions between the functional groups of the CSP and the molecules of the Tröger's base enantiomers are mainly driven by their Van der Waals interactions. The MD data suggest that the interactions of the (-)-Tröger's base with the CSP are more favored by 8+/-(5) kJ/mol than those of (+)-Tröger's base. This difference seems to be a contributing factor to the increased retention of the - enantiomer on this chromatographic system. The modeling of the data also indicates that both enantiomers can form high stoichiometry complexes while binding onto the stationary phase, in agreement with the results of the equilibrium isotherm studies.

2-Propanol↗
PubMed2004

Attenuated total reflectance infrared studies of liposome adsorption at the solid-liquid interface.

Interfacial interactions between liposomes and the solid-liquid interface (i.e. a ZnSe internal reflection element, modified to mimic a biological surface) were studied by Fourier transform infrared (FTIR) spectroscopy in attenuated total reflectance (ATR) mode. Both conventional liposomes, containing lecithin and cholesterol and Stealth liposomes containing poly(ethylene)glycol (PEG)5000- or PEG2000-lipids were investigated. IR bands due to the liposome components were observed to increase with time and enabled the liposome adsorption kinetics and thermodynamics to be quantified. The liposome solution conditions, surface properties and compositions have all been shown to influence liposome adsorption. Free energies of adsorption were determined to be in the range from -10.0 to -11.0 kJ mol(-1) and slightly reduced by PEG incorporation. The adsorption rate constant is decreased with increased solution pH and decreased ionic strength; this reflects the importance of electrostatics in controlling liposome adsorption. Increasing the level and molecular weight of PEG incorporation in the liposomes significantly reduced both the rate and extent of liposome adsorption; steric hindrance is considered to play a key role. Findings from this research will improve the understanding of liposome interaction during drug delivery, give insight into the actions of liposomes in the body and may form the basis for improved liposome formulations.

Adsorption↗
PubMed2006

Human fibrinogen adsorption onto single-walled carbon nanotube films.

The adsorption behavior of human fibrinogen (Hfg) on single-walled carbon nanotube (SWNT) films was investigated using scanning electron microscopy (SEM) and near edge X-ray absorption fine structure (NEXAFS) spectroscopy. It was shown in the SEM images that fibrinogen was adsorbed strongly on the surface of SWNT when the samples were incubated in the Hfg solutions for 10 min. The dependence of adsorption on the concentration of fibrinogen was also investigated and it was found that adsorption increased with increasing concentration. In order to further explore the adsorption of fibrinogen on SWNT surface, NEXAFS spectra were obtained at the N K-edge and the C K-edge. The results confirmed the conclusion regarding the dependence of adsorption on fibrinogen concentration. It is demonstrated that, due to its high sensitivity to the surface elements, NEXAFS spectroscopy is a powerful tool to investigate the adsorption of fibrinogen on SWNT films.

Adsorption↗
PubMed2006

Surface functionalized titanium thin films: zeta-potential, protein adsorption and cell proliferation.

The relationship between electric charge at a material surface and protein adsorption is essential to understand the mechanism of biological integration of materials with tissues. This study investigated the influence of titanium thin films' surface chemistry and surface electric charge (zeta-potential) properties on protein adsorption and cell proliferation. Titanium thin films were surface functionalized with different functional end groups, such as -CH=CH2, -NH2 and -COOH groups in order to produce surfaces with a variety of electric charge properties. The chemical compositions, electric charges and wettability were investigated by using X-ray photoelectron spectroscopy (XPS), zeta-potential measurements and water contact angle measurements, respectively. XPS revealed the surface functionalization of titanium films with -CH=CH2, -NH2, and -COOH groups, which were converted from -CH=CH2 groups. Ti-COOH samples showed the lowest water contact angles and zeta-potential compared to all other samples investigated in this study. NH2-terminated titanium films displayed intermediate contact angles of 70.3+/-2.5 degrees . Fibrinogen adsorption on titanium films and surface functionalized titanium films were investigated in this study. Ti-COOH samples displayed a lower protein adsorption than all other groups, such as NH2-, -CH=CH2-terminated titanium thin films. A tendency that the lower zeta-potential of the samples, the lower the protein adsorption at their surfaces was observed. In vitro cell proliferation tests were also performed on the different surface functionalized titanium films. NH2-terminated titanium films displayed good cell proliferation and cell viability tendency. However, a lower cell proliferation on COOH-terminated titanium films was observed compared with NH2-terminated titanium films. This effect was attributed to the difference in protein adsorption of these samples.

Adsorption↗
PubMed2006

Adsorption of cadmium on husk of Lathyrus sativus: physico-chemical study.

Adsorption of cadmium (II) from aqueous solution by low-cost biosorbents was investigated. Husk of Lathyrus sativus (HLS) was found to be the most efficient in this respect and removed approximately 95% of the metal. The influence of pH, temperature, contact time and metal ion concentration on the adsorption process by HLS was studied. Hydrogen ion concentration of the solution greatly influenced the process with an optimum at pH 5.0-6.0, whereas temperature had no significant effect. The process was very fast and more than 90% of the total adsorption took place within the first 5 min and was found to follow pseudo-second order rate kinetics. The adsorption data can better be explained by Langmuir isotherm model and the calculated maximum adsorption capacity was 35 mg/g of HLS at pH 5.0 and 30 degrees C. Scanning electron micrographs showed that cadmium was present as micro precipitate on the surface of the adsorbent. Cadmium replaced calcium of the biomass as revealed from the EDX analysis indicating that the adsorption proceeds through ion exchange mechanism. Cadmium could be desorbed from the loaded biomass by lowering pH approximately 1.0 with mineral acid.

Adsorption↗
PubMed2006

Protein adsorption from flowing solutions on pure and maleic acid copolymer modified glass particles.

The adsorption of human serum albumin (HSA) and lysozyme (LSZ) on pure as well as maleic acid (MA) copolymer coated spherical soda lime glass particles was investigated under flowing conditions. Coating the glass particles with two different maleic acid copolymers alters the properties of the particle surface concerning its charge and hydrophobicity in a well-defined gradation. Frontal chromatography was used to determine the surface concentration of the adsorbed proteins and to establish adsorption isotherms. The introduced methodology was demonstrated to provide a powerful means to study protein adsorption at solid/liquid interfaces. Investigations with virginal and protein-preadsorbed glass particles revealed that even under streaming conditions HSA is irreversibly adsorbed, whereas LSZ partially desorbs. For LSZ and HSA the adsorbed amounts and the isotherms strongly depend on the surface "history", i.e. the presence or absence of preadsorbed protein layers, and the kind of surface modification of the glass. Compared to the soda lime glass surface the adsorption of HSA was strongly increased on surfaces modified with a hydrophobic maleic acid copolymer indicating a strong hydrophobic protein-surface interaction. By coating the surface with a hydrophilic and more negatively charged maleic acid copolymer the adsorption of HSA to that surface was lower and comparable to the adsorption onto plain glass due to the electrostatic repulsion between HSA and the modified surface. In contrast the affinity to any of the investigated particle surfaces was generally higher for LSZ than for HSA which can be mainly attributed to the electrostatic attraction between LZS and the surface. The adsorbed amount of LSZ on the copolymer coated particle surfaces was much higher than on the pure soda lime glass particles indicating superposed hydrophobic interactions in the case of the hydrophobic MA copolymer layer and an increased density of anionic sites as well as interactions of LSZ within the three-dimensional (swollen), hydrophilic MA copolymer layer.

Adsorption↗
PubMed2006

Adsorption behaviour and surfactant elution of cationic salivary proteins at solid/liquid interfaces, studied by in situ ellipsometry.

Adsorption of the cationic salivary proteins lactoferrin, lactoperoxidase, lysozyme and histatin 5 to pure (hydrophilic) and methylated (hydrophobized) silica surfaces was investigated by in situ ellipsometry. Effects of concentration (</=10 microgml(-1), for lysozyme </=200 microgml(-1)) and dependence of surface wettability, as well as adsorption kinetics and elutability of adsorbed films by buffer and sodium dodecyl sulphate (SDS) solutions were investigated. Results showed that the amounts adsorbed decreased in the order lactoferrin>/=lactoperoxidase>lysozyme>/=histatin 5. On hydrophilic silica, the adsorption was most likely driven by electrostatic interactions, which resulted in adsorbed amounts of lactoferrin that indicated the formation of a monolayer with both side-on and end-on adsorbed molecules. For lactoperoxidase the adsorbed amounts were somewhat higher than an end-on monolayer, lysozyme adsorption showed amounts corresponding to a side-on monolayer, and histatin 5 displayed adsorbed amounts in the range of a side-on monolayer. On hydrophobized substrata, the adsorption was also mediated by hydrophobic interactions, which resulted in lower adsorbed amounts of lactoferrin and lactoperoxidase; closer to side-on monolayer coverage. For both lysozyme and histatin 5 the adsorbed amounts were the same as on the hydrophilic silica. The investigated proteins exhibited fast adsorption kinetics, and the initial kinetics indicated mass transport controlled behaviour at low concentrations on both types of substrates. Buffer rinsing and SDS elution indicated that the proteins in general were more tightly bound to the hydrophobized surface compared to hydrophilic silica. Overall, the surface activity of the investigated proteins implicates their importance in the salivary film formation.

Adsorption↗