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PubMed2000

A geometric approach to determine adsorption and desorption kinetic constants.

A geometric method based on Langmuir kinetics has been derived to determine adsorption and desorption kinetic constants. In the conventional procedure, either the adsorption kinetic constant (k(a)c) or desorption kinetic constant (k(d)c) is found from kinetic experiments and the other is calculated by their correlation with the equilibrium constant, i.e, k(d)c = Kcon/k(a)c, where Kcon has been known from equilibrium studies. The determined constants (Kcon, k(a)c, k(d)c), if based only on the conventional procedure, may not be accurate due to their mathematical dependence. Therefore, the objectives of this study are applying a geometric approach to directly determine Langmuir kinetic constants and describe adsorption behavior. In this approach, both adsorption kinetic constant (k(a)g) and desorption kinetic constant (k(d)g) are obtained only from data of kinetic experiments, and a geometric equilibrium constant (Kgeo) is calculated by Kgeo = k(a)g/k(d)g. The deviation between Kgeo and Kcon can prove the accuracy of k(a)g and k(d)g which were determined by this method. This approach was applicable to selenate, selenite and Mg2+ adsorption onto SiO2 regardless of whether the adsorbate formed inner- or outer-sphere complexes. However, this method showed some deviation between Kcon and Kgeo for Mn2+ adsorption because of the formation of surface Mn(II)-hydroxide clusters, which was inconsistent with the basic assumption of this method of monolayer adsorption.

Adsorption↗
PubMed2002

Adsorption and desorption of cadmium by goethite pretreated with phosphate.

The adsorption of Cd by oxides or soils have been extensively studied, however, the desorption has received relatively limited attention, especially in the presence of phosphate. In this study, a batch equilibration method was used to investigate Cd sorption and desorption by goethite pretreated with phosphate. Phosphate not only enhanced Cd adsorption, but also accelerated the adsorption process. Compared with Cd adsorption by goethite alone, phosphate substantially moved the adsorption curves (edges) to lower pH range, indicative of enhancement of Cd sorption. The Cd adsorption by the pretreated goethite reached apparent equilibrium within 24 h at 20 degrees C, while such equilibrium was not observed after 4 weeks in the absence of phosphate. Cadmium was more readily released from phosphate-treated goethite. It is believed that phosphate blocked the pores on goethite surface, which lead to the fast adsorption kinetics and high extraction percentage. These results provided strong support for the diffusion of Cd into goethite particles.

Adsorption↗
PubMed2002

Enhancement of copper and cadmium adsorption on kaolin by the presence of humic acids.

The competitive adsorption equilibrium isotherms of Cu2+ and Cd2+ on kaolin have been measured at 298 K, in the presence and the absence of humic acids (HAs). HAs were found to enhance the metal adsorption capacity of mineral surfaces, in particular kaolin. This enhancement was also observed in the competitive adsorption of copper and cadmium on kaolin and kaolin-HA complex. This competitive adsorption shows that the presence of Cd2+ has not an important effect on Cu2+ adsorption, whereas a dramatic decrease is observed on the adsorption of Cd2+ in the presence of Cu2+. The Freundlich isotherm equation was found to provide an excellent fit to the experimental data. These results were compared with the independent adsorption of both heavy metals.

Adsorption↗
PubMed2003

Adsorption behavior of reactive dye in aqueous solution on chemical cross-linked chitosan beads.

A batch system was applied to study the adsorption of reactive dye (reactive red 189) from aqueous solutions by cross-linked chitosan beads. The ionic cross-linking reagent sodium tripolyphosphate was used to obtain more rigid chitosan beads. To stabilize chitosan in acid solutions, chemical cross-linking reagent epichlorohydrin (ECH), glutaraldehyde and ethylene glycol diglycidyl ether was used and ECH shows a higher adsorption capacity. The Langmuir and Freundlich adsorption models were applied to describe the equilibrium isotherms at different particle sizes and isotherm constants were determined. The Langmuir model agrees very well with experimental data and its calculated maximum monolayer adsorption capacity has very large value of 1802-1840 (g/kg) at pH 3.0, 30 degrees C. The kinetics of the adsorption with respect to the initial dye concentration, temperature, pH, ionic strength, and wet/dry beads were investigated. The pseudo-first-order, second-order kinetic models and intraparticle diffusion model were used to describe the kinetic data and the rate constants were evaluated. The dynamical data fit well with the second-order kinetic model, except for the dry beads fitting better with the first-order model. The adsorption capacity increases largely with decreasing solution pH or with increasing initial dye concentration. Thermodynamic parameters such as change in free energy (deltaG(0)), enthalpy (deltaH(0)), entropy (deltaS(0)) and activation energy were also determined. The adsorption mechanism is shown to be the electrostatic interactions between the dye and chitosan beads. The desorption data shows that the removal percent of dye RR 189 from the cross-linked chitosan beads is 63% in NaOH solutions at pH 10.0, 30 degrees C. The desorbed chitosan beads can be reused to adsorb the dye and to reach the same capacity as that before desorption.

Adsorption↗
PubMed2003

Effects of several low-molecular weight organic acids and phosphate on the adsorption of acid phosphatase by soil colloids and minerals.

Adsorption of acid phosphatase on goethite, kaolinite and two colloids from the soils in central and south China in the presence of organic acids and phosphate was studied. With the increase of anion concentration, the ability in decreasing enzyme adsorption followed the sequence: phosphate>tartrate>oxalate>acetate. Acetate showed promotive effect on enzyme adsorption at lower anion concentrations whereas oxalate, tartrate and phosphate compete effectively with enzyme in a broad range of anion concentration. The adsorption isotherms of enzyme in most of the anionic systems studied conformed to the Langmuir equation. Phosphate reduced the affinity of enzyme on goethite more significantly than the other anions. However, tartrate decreased the affinity of enzyme on soil colloids and kaolinite to a greater extent than phosphate, oxalate and acetate. This observation suggested that the impact of anions on enzyme adsorption varies with anionic type and the surface characteristics of soil components. The influence of the addition order of ligand on enzyme adsorption was found greater in tartrate and phosphate systems. In general, simultaneous introduction of ligand and enzyme into the system had the lowest enzyme adsorption, showing more competition between ligand and enzyme molecules in this system. Data from this work indicated that the status and activity of enzyme in certain soil microenvironments especially the rhizosphere where various organic and inorganic ligands are active can be altered and may be completely different from the bulk soil.

Acid Phosphatase↗
PubMed2004

Adsorption of water-soluble dyes onto modified resin.

Adsorption behavior of five kinds of water-soluble dyes onto functionalized resin NKY has been dynamically and thermodynamically investigated. The results showed that the adsorption rates of dye K-GN, K-2BP, KN-R, AAB and 2G are all controlled by liquid film diffusion and particle diffusion. Equilibrium adsorption data can be well described by three-parameter equation. The first layer adsorption is the physical enhanced by chemical effect but multilayer adsorption is typically physical adsorption. Standard free energy change DeltaG(0) and standard entropy change DeltaS(0) indicate the adsorption of the dyes onto NKY can occur spontaneously.

Adsorption↗
PubMed2001

Adsorption of xenobiotics to plastic tubing incorporated into dynamic in vitro systems used in pharmacological research--limits and progress.

Commonly used materials incorporated into dynamic culture systems typically show the feature of adsorption of lipophilic xenobiotics. Yet, this phenomenon is strongly limiting the use of dynamic culture models and ex vivo organ perfusions in pharmacological and toxicological research. The aim of the study was to characterize different materials with respect to their capacity for drug adsorption and to find methods or materials to reduce the loss of substrate by adsorption in order to improve the use of dynamic in vitro systems. The adsorption of different xenobiotics (lidocaine, midazolam, lormetazepam, phenobarbital, testosterone, ethoxyresoroufine) to tubes used in dynamic in vitro systems (polyvinyl-chloride, silicone) were investigated and compared to a new material (silicone-caoutchouc-mixture). In addition, the role of protein deposition onto the tubing was studied and it was investigated whether it was possible to reach saturation of the inner tube surface by pre-loading it with the test compound. We found that silicone tubes provided the highest comfort with respect to handling and reusability, but they also demonstrated the highest capacity for substrate adsorption. Polyvinyl-chloride was the second best in handling but also demonstrated a high complexity in its adsorption behavior. The silicone-caoutchouc-mixture reached acceptable experimental results with respect to its handling and demonstrated a very low capacity for substrate adsorption.

Adsorption↗
PubMed2002

Adsorption and dissolution behavior of human plasma fibronectin on thermally and chemically modified titanium dioxide particles.

Titanium is known for its biocompatibility and is widely used in dental and orthopedic reconstructive surgery. There are reports that osteointegration of these implants is not optimal. The objective of this study was to modify titanium dioxide particles and examine the resultant effects on protein adsorption to these altered surfaces using a model cell binding protein, human plasma fibronectin (HPF). HPF is an important matrix glycoprotein that plays a major role in cell and protein attachment, Titanium dioxide surfaces were modified by heating the titanium dioxide powder at 800 degrees C for 1 h or treating with an oxidizing agent: peroxide in ammonium hydroxide followed by peroxide in hydrochloric acid. Oxidized and control samples were further treated with 9:1 butanol:water for 30 min. Brunauer-Emmett-Teller showed no change in particle surface area as a result of thermal or chemical treatment. Hydrophobicity increased with butanol treatment of titanium dioxide. Diffuse reflectance Fourier transform infrared spectroscopy showed the presence of -CH2 and -CH3 vibrations in the region of 2850-3000 cm(-1) for both the heated, butanol and peroxide/butanol-treated samples. The absence of increased C-O and O-C=O features as determined by electron spectroscopy for chemical analysis indicates that butanol adsorption is not occurring via an esterification mechanism. The interaction between butanol and pre-heated or peroxide-treated titanium dioxide may be one of association (weak electrostatic and/or Van der Waals forces) rather than direct ionic bonding. Maximum HPF adsorption on modified or unmodified titanium dioxide occurred within 30 min, with greater protein adsorption occurring on butanol-treated samples. Desorption was minimal with all modifications. Zeta potential measurements showed that HPF adsorption caused an increase in the negative zeta potential with the greatest change noted for the butanol-treated samples. These findings suggest that wettability and surface charge both play an important role in protein adsorption to titanium dioxide. Thus, by modifying the physico-chemical properties of titanium dioxide surfaces, it may be possible to alter protein adsorption and hence optimize cell attachment.

1-Butanol↗
PubMed2003

Serum protein adsorption and platelet adhesion on pluronic-adsorbed polysulfone membranes.

We examined plasma protein adsorption and platelet adhesion to polysulfone (PSf) flat membranes coated with Pluronic with varying polyethylene oxide (PEO) block length. Adsorption of albumin, globulin and fibrinogen to Pluronic-coated PSf membranes was independent of plasma dilution when concentrations of human blood plasma above 20% were applied. Increasing coating concentrations of aqueous Pluronic solution resulted in decreased protein adsorption by the PSf membranes. Pluronic F68, which was more hydrophilic than Pluronic L62 or L64 and had 80% of PEO content, was the most effective at suppressing the adsorption of plasma proteins and platelet adhesion to PSf membranes. We developed a mixed protein solution containing human albumin, gamma-globulin and fibrinogen to attempt to mimic the competitive and cooperative binding effects found in plasma. Fibrinogen adsorption from plasma could be recapitulated by the mixed protein solution. The number of platelets adhering to the PSf membranes decreased as the coating concentration of Pluronic solution was increased, and platelet adhesion decreased in parallel with fibrinogen adsorption. These results suggest that the bioinert property of PEO segments in the Pluronic, which is ascribed to their high flexibility in aqueous media, suppresses the adsorption of plasma proteins and platelets to the Pluronic-coated PSf membranes.

Adsorption↗
PubMed1997

Effect of C4-, C8- and C18-alkylation of poly(vinyl alcohol) hydrogels on the adsorption of albumin and fibrinogen from buffer and plasma: limited correlation with platelet interactions.

Polyvinyl alcohol (PVA) hydrogel was partially alkylated with short (C4), intermediate (C8) and long (C18) alkyl chains to test the hypothesis that an alkylated surface might promote enhanced interaction with albumin and thus exhibit low platelet thrombogenicity. PVA hydrogel was reacted with alkyl halides (C4, C8 or C18) and coated onto polyethylene. The effect of surface alkylation (extent of alkylation and alkyl chain length) on the adsorption of human serum albumin and fibrinogen to these surfaces was investigated in both buffer and plasma. Platelet interactions were investigated in vitro using flow cytometry methods. The maximum surface concentrations of albumin and fibrinogen adsorbed from buffer onto PVA and alkylated PVA were characteristic of monolayers. At low concentrations differences in adsorption among the surfaces appeared to be related to hydrophobicity as determined by dynamic advancing water contact angle, and to degree of alkylation as determined by angle dependent XPS analysis. Alkyl chain length dependence was not observed. Adsorption from plasma was considerably lower than from buffer, except for albumin on C8-PVA where monolayer adsorption was observed. Fibrinogen adsorption from plasma was similar on PVA, C8-PVA and C18-PVA, but was higher on C4-PVA. For albumin adsorption from plasma, the initial slope of the adsorption-concentration curve was highest for C18-PVA, suggesting higher albumin affinity despite the low degree of substitution of the C18-PVA material. These data suggest possible selectivity of the C18 alkylated PVA for albumin. Platelet studies showed that C4-PVA was the least platelet reactive (microparticle generation and P-selectin expression) of the alkyl derivatized materials.

Adsorption↗
PubMed1999

Irreversible adsorption of human serum albumin to hydrogel contact lenses: a study using electron spin resonance spectroscopy.

Human serum albumin (HSA) was specifically spin labelled with 4-maleimido-tempo (MSL) at its cysteine 34 residue (HSA-MSL). The irreversible adsorption of HSA-MSL to hydrogel contact lenses (etafilcon A, tefilcon and vifilcon A) was investigated using electron spin resonance (ESR) spectroscopy. Changes in ESR spectral characteristics of adsorbed HSA-MSL as compared to HSA-MSL in solution displayed an additional immobilisation of the spin label due to the adsorption. This immobilisation of MSL corresponds to a large conformational alteration of the HSA-MSL near the modified Cys 34 residue. For both etafilcon A and tefilcon, the rate of irreversible adsorption was relatively slow compared with that of vifilcon A where the maximum state of immobilisation and hence conformational change occurred within the first hour of adsorption. Furthermore, tefilcon produced markedly different ESR spectra where a strong conformational change to a less mobile protein was apparent. This supported a model where the direct irreversible adsorption of HSA from solution dominated on tefilcon as opposed to conversion of the adsorbed protein from the reversible to the irreversible state on both etafilcon A and vifilcon A. HSA-MSL adsorption onto hydrophobic poly(methylmethacrylate) (PMMA) and hydrophilic poly(N-ter-butylacrylamide) (PTBAM) latex beads was also investigated. The spin label MSL was found to be less mobile when HSA was adsorbed onto PMMA compared with PTBAM beads. It was also found that the rate of irreversible adsorption of HSA is far higher onto PMMA surfaces than onto PTBAM surfaces.

Adsorption↗
PubMed2002

Use of cellulose-based wastes for adsorption of dyes from aqueous solutions.

Low-cost banana and orange peels were prepared as adsorbents for the adsorption of dyes from aqueous solutions. Dye concentration and pH were varied. The adsorption capacities for both peels decreased in the order methyl orange (MO) > methylene blue (MB) > Rhodamine B (RB) > Congo red (CR) > methyl violet (MV) > amido black 10B (AB). The isotherm data could be well described by the Freundlich and Langmuir equations in the concentration range of 10-120 mg/l. An alkaline pH was favorable for the adsorption of dyes. Based on the adsorption capacity, it was shown that banana peel was more effective than orange peel. Kinetic parameters of adsorption such as the Langergren rate constant and the intraparticle diffusion rate constant were determined. For the present adsorption process intraparticle diffusion of dyes within the particle was identified to be rate limiting. Both peel wastes were shown to be promising materials for adsorption removal of dyes from aqueous solutions.

Adsorption↗
PubMed2002

Equilibrium and kinetic modeling of adsorption of reactive dye on cross-linked chitosan beads.

The adsorption of reactive dye (Reactive Red 189) from aqueous solutions on cross-linked chitosan beads was studied in a batch system. The equilibrium isotherms at different particle sizes (2.3-2.5, 2.5-2.7 and 3.5-3.8mm) and the kinetics of adsorption with respect to the initial dye concentration (4320, 5760 and 7286 g/m(3)), temperature (30, 40 and 50 degrees C), pH (1.0, 3.0, 6.0 and 9.0), and cross-linking ratio (cross-linking agent/chitosan weight ratio: 0.2, 0.5, 0.7 and 1.0) were investigated. Langmuir and Freundlich adsorption models were applied to describe the experimental isotherms and isotherm constants. Equilibrium data fitted very well to the Langmuir model in the entire saturation concentration range (0-1800 g/m(3)). The maximum monolayer adsorption capacities obtained from the Langmuir model are very large, which are 1936, 1686 and 1642 g/kg for small, mediumand large particle sizes, respectively, at pH 3.0, 30 degrees C, and the cross-linking ratio of 0.2. The pseudo first- and second-order kinetic models were used to describe the kinetic data, and the rate constants were evaluated. The experimental data fitted well to the second-order kinetic model, which indicates that the chemical sorption is the rate-limiting step, instead of mass transfer. The initial dye concentration and the solution pH both significantly affect the adsorption capacity, but the temperature and the cross-linking ratio are relatively minor factors. An increase in initial dye concentration results in the increase of adsorption capacity, which also increases with decreasing pH. The activation energy is 43.0 kJ/mol for the adsorption of the dye on the cross-linked chitosan beads at pH 3.0 and initial dye concentration 3768 g/m(3).

Adsorption↗
PubMed2003

Adsorption of cadmium by sulphur dioxide treated activated carbon.

Merck carbon (1.5 mm) was treated in three ways: heating from ambient temperature to 900 degrees C in SO(2); treatment at ambient temperature in SO(2); or successive treatments in SO(2) and H(2)S at ambient temperature. All samples were then characterised and tested as adsorbents of Cd(2+) from aqueous solution. The characterisation was in terms of composition by effecting ultimate and proximate analyses and also of textural properties by N(2) adsorption at -196 degrees C. Kinetics and extent of the adsorption process of Cd(2+) were studied at 25 and 45 degrees C at pH of the Cd(2+) solution (i.e., 6.2) and at 25 degrees C also at pH 2.0. The various treatments of the starting carbon had no significant effect on the kinetics of the adsorption of Cd(2+), but increased its adsorption capacity. The most effective treatment was heating to 900 degrees C, the adsorption in this case being 70.3% more than that of the starting carbon. The adsorption increased at 45 degrees C but decreased at pH 2.0 when compared to adsorption at 25 degrees C and pH 6.2, respectively.

Adsorption↗
PubMed2001

Adsorption of IgG onto hydrophobic teflon. Differences between the F(ab) and F(c) domains.

The effect of differences in the degree of hydrophobicity of protein patches/fragments on the adsorption behaviour of the protein is investigated. The adsorption isotherm of a monoclonal mouse anti-human immunoglobulin G (isotype 2b) onto hydrophobic Teflon particles is measured using a depletion method. The adsorption-induced denaturation of the immunoglobulin as a function of the adsorbed amount is studied by differential scanning calorimetry, and the corresponding rearrangements in the secondary structure of the whole IgG molecule and its F(ab) and F(c) fragments are determined by circular dichroism spectroscopy. The effects of adsorption on the F(ab) and F(c) fragments in the intact IgG molecule occur independently. Adsorption of the whole IgG molecule leads to denaturation of the F(ab) fragments, whereas the F(c) fragment remains unperturbed; adsorption of the isolated fragments results in structural changes in both F(ab) and F(c). The surface hydrophobicity of the isolated fragments was studied by HPLC. These experiments support the hypothesis that differences in the degree of denaturation between F(ab) and F(c) are due to the higher degree of hydrophobicity of the F(ab) fragment. The adsorption-induced changes in the secondary structure are more prominent for the isolated fragments as compared to intact IgG. This is ascribed to the higher flexibility of the isolated fragment, as compared to the fragment in the whole molecule.

Adsorption↗
PubMed2001

The role of plasma proteins in brain targeting: species dependent protein adsorption patterns on brain-specific lipid drug conjugate (LDC) nanoparticles.

The in vivo organ distribution of particulate drug carriers is decisively influenced by the interaction with plasma proteins after i.v. administration. Serum protein adsorption on lipid drug conjugate nanoparticles, a new carrier system for i.v. application, was investigated by 2-dimensional electrophoresis (2-DE). The particles were surface-modified to target them to the brain. To assess the protein adsorption pattern after i.v. injection in mice prior to in vivo studies, the particles were incubated in mouse serum. Incubation in human serum was carried out in parallel to investigate similarities or differences in the protein patterns obtained from men and mice. Distinct differences were found. Particles incubated in human serum showed preferential adsorption of apolipoproteins A-I, A-IV and E. Previously, preferential adsorption of ApoE was reported as one important factor for targeting of Tween(R)80 modified polybutylcyanoacrylate nanoparticles to the brain. Preferential adsorption of ApoA-I and A-IV took place after incubation in mouse serum, adsorption of ApoE could not be clearly confirmed. In vivo localization of the LDC nanoparticles at the blood-brain barrier and diffusion of the marker Nile Red into the brain could be shown by confocal laser-scanning microscopy. Differences of the obtained adsorption patterns are discussed with regard to their relevance for correlations of in vitro and in vivo data obtained from different species.

Adsorption↗
PubMed2001

In vitro study on fluoxetine adsorption onto charcoal using potentiometry.

This in vitro investigation was performed to study the adsorption rate constant as well as the adsorption characteristics of fluoxetine (F) to activated charcoal and its commercial formulation Carbomix powder in simulated gastric (pH 1.2) fluid environment. Ion-selective electrode (ISE) potentiometry, based on the selective, direct and continuous monitoring of F with an F-ISE constructed in our laboratory was used. The method used in the kinetic experiments consists of the rapid addition of a slurry containing the charcoal into the drug solution under stirring and continuous recording of the F-ISE potential until the establishment of equilibrium. The free ionized drug concentration at appropriate time intervals was calculated from the recorded adsorption curve and the apparent adsorption rate constant was estimated assuming pseudo first order kinetics. Within run R.S.D. of the estimates ranged from 0.24 to 11.5%, while between run R.S.D. (n=3-4) ranged from 0.90 to 13.8%. A linear relationship was found between the apparent adsorption rate constants and the amount of charcoal used with slopes (+/-S.D.) for activated charcoal and Carbomix equal to 1.14(+/-0.21) and 0.146(+/-0.009) s(-1)g(-1), respectively. Successive additions of microvolumes of F solution were made into a charcoal slurry with measurement of the F-ISE potential at equilibrium. The maximum adsorption capacity values (+/-S.D.) of activated charcoal and Carbomix were 254.8+/-1.8 and 405+/-41 mg/g, respectively while the affinity constant values (+/-S.D.) were 45.6+/-2.2 and 55.5+/-2.9 l/g, respectively. The adsorption of F to charcoals was rapid and for amounts of charcoal 10 times greater than the amount of the drug, 95% of F was adsorbed within the first 5 min. Relative to the toxic and lethal doses in cases of F intoxications, both types of charcoals tested adsorbed effectively F at gastric pH. Carbomix can be considered as appropriate charcoal formulation for medical treatment in cases of F poisoning.

Adsorption↗
PubMed2002

Arsenic adsorption from aqueous solutions by activated red mud.

Heat treatment and acid treatment methods have been tested on red mud to increase its arsenic adsorption capability. The results indicate that the adsorptive capacity of red mud can be increased by acid treatment. This treatment causes sodalite compounds to leach out. As(III) and As(V) adsorption characteristics of activated red mud have similar tendencies with raw red mud. Batch adsorption studies have shown that activated red mud in dosages ranging from 20 to 100 g l(-1) can be used effectively to remove arsenic from aqueous solutions. The process is pH dependent, the optimum range being 5.8-7.5 for As(III) and 1.8-3.5 for As(V). The maximum removals are 96.52% for As(V) and 87.54% for As(III) for solutions with a final pH of 7.25 and 3.50, respectively, for the initial arsenic concentration of 133.5 micromol l(-1) (10 mg l(-1)), activated red mud dosage of 20 g l(-1), contact time of 60 min and temperature of 25 degrees C. The adsorption data obtained follow a first-order rate expression and fit the Langmuir isotherm well. Isotherms have been used to obtain the thermodynamic parameters. It was found that the adsorption of As(III) was exothermic, whereas As(V) adsorption was endothermic.

Adsorption↗