Mass transfer kinetics and breakthrough and elution curves for bovine serum albumin using cibacron blue cellulose membranes

The mass transfer of bovine serum albumin onto a stack of cibacron blue cellulose membranes in the loading and elution stages were studied. The breakthrough curves obtained in the loading stage were fitted to the pore and the lumped kinetic (LK) models, respectively. Then experimental data obtained in the elution stage were described by using the LK model in which the kinetic equation, the initial and the boundary conditions were rewritten according to the operation. For the breakthrough curves it was found that the contribution of the sorption kinetics to band broadening was significant whereas that of axial dispersion was negligible. In contrast, both of these contributions were significant to the profile of the elution curve. By studying the mass transfer kinetics in the elution stage, information about the influence of the module geometry on the performance of affinity membrane separations may be obtained.     

Mass transfer model of triethylamine across the n-decane/water interface derived from dynamic interfacial tension experiments

This publication presents a detailed experimental and theoretical study of mass transfer of triethylamine (TEA) across the n-decane/water interface. In preliminary investigations, the partition of TEA between n-decane and water is determined. Based on the experimental finding that the dissociation of TEA takes place in the aqueous and in the organic phase, we assume that the interfacial mass transfer is mainly affected by adsorption and desorption of ionized TEA molecules at the liquid/liquid interface. Due to the amphiphilic structure of the dissociated TEA molecules, a dynamic interfacial tension measurement technique can be used to experimentally determine the interfacial mass transport. A model-based approach, which accounts for diffusive mass transport in the finite liquid bulk phases and for adsorption and desorption of ionized TEA molecules at the interface, is employed to analyze the experimental data. In the equilibrium state, the interfacial tension of dissociated TEA at the n-decane/water interface can be adequately described by the Langmuir isotherm. The comparison between the theoretical and the experimental dynamic interfacial tension data reveals that an additional activation energy barrier for adsorption and desorption at the interface has to be regarded to accurately describe the mass transport of TEA from the n-decane phase into the aqueous phase. Corresponding adsorption rate constants can be obtained by fitting the theoretical predictions to the experimental data. Interfacial tension measurements of mass transfer from the aqueous into the organic phase are characterized by interfacial instabilities caused by Marangoni convection, which result in an enhancement of the transfer rate across the interface.     

Investigation of the concentration dependence of mass transfer coefficients in reversed-phase liquid chromatography

In order to investigate the concentration dependence of mass transfer coefficients in RPLC, experimental breakthrough curves obtained by staircase frontal analysis (FA) were fitted to the simplified models such as multiplate (MP) model, equilibrium dispersive (ED) model, and transport model, and the sophisticated models such as lumped pore diffusion (POR) model and general rate (GR) model. The MP model was used to obtain the initial guesses of the parameters of the ED and the transport models. Then the best values were obtained by minimizing the differences between theoretical and experimental values with a nonlinear fitting procedure. The values of the parameters of the POR and the GR models can be calculated by using the expressions derived from the plate height equations, which was further validated by using the fitting method. It was found that the mass transfer coefficients would depend on the solute concentration. This can be ascribed to the surface diffusivity, which correlates with the concentration and is lumped into the mass transfer coefficients for both simplified and sophisticated models.     

Influence of the particle porosity on chromatographic band profiles

The mass transfer kinetics of butyl benzoate, eluted on a monolithic RPLC column with methanol-water (65:35, v/v) as the mobile phase was investigated, using the perturbation method to acquire isotherm data and the mobile phase velocity dependence of the height equivalent to a theoretical plate of perturbation peaks to acquire kinetics data. The equilibrium isotherm of butyl benzoate is accounted for by the liquid-solid extended multilayer BET isotherm model. The total porosity of the column varies much with the butyl benzoate concentration, influencing strongly the parameters of its mass transfer kinetics and the profiles of the breakthrough curves. Using all these parameters, the general rate model of chromatography predicts band profiles and Van Deemter curves that are in excellent agreement with experimental results provided the influence of concentration on the porosity is properly taken into account. This agreement confirms the validity of the models selected for the isotherm and for the mass transfer kinetics.     

Thermodynamic analysis of the heterogenous binding sites of molecularly imprinted polymers

The thermodynamic interactions of two polymers, one Fmoc-L-Trp-imprinted (MIP), the other one an unimprinted reference (NIP), with the two Fmoc-tryptophan enantiomers were studied by frontal analysis, which allows accurate measurements of the adsorption isotherms. These isotherms were acquired at temperatures of 40, 50, 60, and 70 degrees C, for sample concentrations ranging between 0.005 and 40 mM. The mobile phase used was acetonitrile with one percent acetic acid as an organic modifier. Within the measured concentration ranges, the tri-Langmuir isotherm model accounts best for the isotherm data of both enantiomers on the MIP, the bi-Langmuir model for the isotherm data of Fmoc-L-Trp on the NIP. These isotherm models were selected using three independent processes: statistical tests on the results from regression of the isotherm data to different isotherm models; calculation of the affinity energy distribution from the raw isotherm data; comparison of the experimental and the calculated band profiles. The isotherm parameters obtained from these best selected isotherm models showed that the enantiomeric selectivity does not change significantly with temperature, while the affinity of the substrates for both the MIP and the NIP decrease considerably with increasing temperatures. These temperature effects on the binding performance of the MIP were clarified by considering the thermodynamic functions (i.e., the standard molar Gibbs free energy, the standard molar entropy of adsorption, and the standard molar enthalpy of adsorption) for each identified type of adsorption sites, derived from the Van't Hoff equation. This showed that the entropy of transfer of Fmoc-L-Trp from the mobile to the MIP stationary phase is the dominant driving force for the selective adsorption of Fmoc-L-Trp onto the enantioselective binding sites. This entropy does not change significantly with increasing temperatures from 40 to 70 degrees C.     

两种固定化金属螯合复合亲和膜色谱介质制备

以纤维素滤纸为基质,通过碱处理、环氧活化、偶联亚氨基二乙酸二钠、固定化Ｃｕ＾２＋后制得了大孔纤维素亲和膜。另外,在活化后的膜上通过共价交联覆盖上琼脂糖,制得了具有类似“三明治”结构且性能优于的复合亲和膜,装柱后分别制得固定化金属螯合亲和膜色谱柱。对两种亲和膜进行牛血清白蛋白等温吸附测定显示,两者的最大吸附量分别为１．１７ｍｇ／ｃｍ＾２和１．３０ｍｇ／ｃｍ＾２,与传统的琼脂糖凝胶类介质吸附量相当,表     

Adsorption behavior and prediction of the band profiles of the enantiomers of 3-chloro-1-phenyl-1-propanol. Influence of the mass transfer kinetics

The single-component and competitive adsorption isotherms of the enantiomers of 3-chloro-1-phenyl-1-propanol were measured by frontal analysis. The stationary phase was a cellulose tribenzoate coated on silica, the mobile phase an n-hexane-ethyl acetate (95:5) solution. The adsorption data measured fitted well to the Langmuir isotherm model. The band profiles of single components and of their mixtures were calculated using the equilibrium-dispersive model. These profiles were found to match quite satisfactorily the experimental band profiles. However, the agreement between calculated and experimental band profiles was significantly improved when a more complex model taking into account the mass transfer kinetics was used. The mass transfer rate coefficients, k(f), for both single components were determined by using the transport-dispersive model of chromatography. The coefficients obtained were used to predict the band profiles of mixtures of the two enantiomers to good agreement.     

Oxygenation by a superhydrophobic slip G/L contactor

The compelling need for an efficient supply of gases into liquids or degassing of fluids within confined microchannels triggered our study on membrane assisted microchemical systems. Porous hydrophobic flat/micro-structured polyvinylidene fluoride (PVDF) membranes were fabricated and integrated in a glass G/L contacting microfluidic device with the aid of optical adhesives. The oxygen transport in microchannels, driven by convection and diffusion, was investigated both experimentally and numerically. The effects of intrinsic membrane morphology on the G/L contacting performance of the resultant membranes were studied. The experimental performance of the flat membranes are shown to obey the simulation results with the assumptions of negligible gas phase and membrane mass transfer limitations. Micro-structured membranes revealed apparent slippage and enhanced mass transport rates, and exceeded the experimental performance of the flat membranes.     

Influence of pressure on the chromatographic behavior of insulin variants under nonlinear conditions

The effect of pressure on the chromatographic behavior of two insulin variants in RPLC was investigated on a YMC-ODS C18 column, under nonlinear conditions. The adsorption isotherm data of porcine insulin and Lispro were measured at average column pressures ranging from 52 to 242 bar. These data fit well to the Toth and the bi-Langmuir isotherm models. The saturation capacity increases rapidly with increasing pressure while the affinity (or equilibrium) constant and the parameter characterizing the surface heterogeneity decrease. It is noteworthy that the distribution coefficient of the insulin variants increases with increasing pressure whereas their equilibrium constant b decreases for porcine insulin and increases for Lispro. The association constant b(ds), which characterizes the adsorption and desorption equilibrium of insulin in the system, increases with increasing pressure. The excellent agreement between the experimental overloaded profiles recorded under different pressures and those calculated using the POR model suggests that the chromatographic behavior of insulin is controlled more by equilibrium thermodynamics than by the mass transfer kinetics. The latter seems to be nearly independent of the average column pressure. Thus, increasing the average column pressure is an efficient, albeit costly, way to increase the loading capacity of the column, hence the production rate in preparative chromatography.     

Two-resistance mass transfer model for the adsorption of the pesticide deltamethrin using acid treated oil shale ash

Adsorption characteristics of the pesticides Deltamethrin were studied in aqueous solutions using acid treated Oil Shale Ash (ATOSA) in a series of batch adsorption experiments. The maximum loading capacity of the adsorbent and the rate of adsorption were found to increase with increasing the pesticide initial concentration, mixing speed and were found to decrease with temperature and particle size. Langmuir as well as Freundlich isotherm models fit the adsorption data with R ²>0.97 in all cases. The maximum adsorption capacity for Deltamethrin was 11.4 mg/g. The two-resistance mass transfer model based on the film resistance and homogeneous solid phase diffusion was used to fit the experimental data. A computer program has been developed to estimate the theoretical concentration-time dependent curves and to compare them with the experimental curves by means of the best-fit approach. The model predicts that the external mass transfer coefficient K was affected by varying the initial pesticide concentration, the agitation speed and temperature whereas the diffusion coefficient D was affected by the initial pesticide concentration, and temperature.     

A study of lithium transport in aluminum membranes

We employed the Devanathan–Stachurski experimental methodology for direct measurement of the rate of lithium transport in metals that can be used as negative electrodes in lithium–ion batteries. The measured Li transport rate in aluminum appears to be in relatively good agreement with previously reported results obtained using standard electrochemical techniques. However, Li transport rate measurements in aluminum membranes of different thicknesses reveal anomalies with regard to the standard diffusion controlled mass transfer model. We attribute this effect to a complex Li transport mechanism in Al membranes upon alloying.     

Thermodynamic functions and intra-particle mass transfer kinetics of structural analogues of a template on molecularly imprinted polymers in liquid chromatography

The parameters of the thermodynamics and mass transfer kinetics of the structural analogues (L-enantiomers) of the template were measured on an Fmoc-L-tryptophan (Fmoc-L-Trp) imprinted polymer, at different temperatures. The equilibrium isotherm data and the overloaded band profiles of these compounds were measured at temperatures of 298, 313, 323, and 333 K. The isotherm data were modeled. The thermodynamic functions of the different adsorption sites were derived from the isotherm parameters, using van't Hoff plots. The mass transfer parameters were derived by comparing the experimental peak profiles and profiles calculated using the lumped pore diffusion (POR) model for chromatography. These data show that (1) the strength between the substrate molecules and the MIP increases with increasing number of functional groups on the substrates; (2) enthalpy is the driving force for the affinity of the substrates for the MIP; (3) surface diffusion is the dominant mass transfer mechanism of the substrates through the porous MIP. For those substrate molecules that have the same stereochemistry as the template, the energetic surface heterogeneity needs to be incorporated into the surface diffusion coefficients. Heterogeneous surface diffusivities decrease with increasing affinity of the substrates for the MIP.     

Film and intraparticle mass transfer during the adsorption of metal ions onto bone char

The sorption of three metal ions, namely, copper, cadmium, and zinc, onto bone char has been studied in terms of equilibrium and rate studies. Equilibrium studies have been analyzed using the Langmuir isotherm equation and the maximum sorption capacities for the metals were 0.477, 0.709, and 0.505 mmolg(-1) bone char for cadmium, copper, and zinc ions, respectively. The kinetic experimental data were used to analyze the effect of external film boundary layer and intraparticle mass transfer resistance on the sorption process and its significance. Four methods of determining the external film transport coefficient were developed and tested; three utilized experimental data to obtain the coefficient and the fourth method was completely empirical. The three experimentally based models give very similar results and consequently similar values of the deviation error values, whereas the error values for the empirical correlation were greater than these three values. The results also demonstrated that the methods for determining the film coefficient could be integrated into more complex diffusion-transport models such as film-intraparticle diffusion processes.     

Chromatographic separation simulation of metal‐chelating peptides from surface plasmon resonance binding parameters

Some metal‐chelating peptides have antioxidant properties, with potential nutrition, health, and cosmetics applications. This study aimed to simulate their separation on immobilized metal ion affinity chromatography from their affinity constant for immobilized metal ion determined in surface plasmon resonance, both technics are based on peptide‐metal ion interactions. In our approach, first, the affinity constant of synthetic peptides was determined by surface plasmon resonance and used as input data to numerically simulate the chromatographic separation with a transport‐dispersive model based on Langmuir adsorption isotherm. Then, chromatographic separation was applied on the same peptides to determine their retention time and compare this experimental t_R with the simulated t_R obtained from simulation from surface plasmon resonance data. For the investigated peptides, the relative values of t_R were comparable. Hence, our study demonstrated the pertinence of such numerical simulation correlating immobilized metal ion affinity chromatography and surface plasmon resonance.     

Batch and continuous fixed-bed column biosorption of thorium(IV) from aqueous solutions: equilibrium and dynamic modeling

Biosorption of thorium(IV) from aqueous solution by Cystoseira indica alga was investigated in batch and fixed-bed column experiments. In the batch study the effects of pH and initial concentration were investigated. The optimum pH for Th(IV) biosorption was found to be 3.5. The experimental isotherms obtained at different pH conditions were analyzed using three two-parameter models and three three-parameter models. Among the two-parameter models the Langmuir model and among the three-parameter models the Redlich–Peterson model vividly described the equilibrium data. The results showed that C. indica alga is a homogeneous biosorbent and Th(IV) biosorption is a favorable and physical process. The maximum biosorption capacity from the Langmuir model was 151.3, 195.7 and 120.6 mg/g at pH 2.5, 3.5 and 4.5, respectively. The continuous isotherm obtained from the column data was modeled by the Langmuir model and the maximum biosorption capacity was 283.8 mg/g. The experimental data were fitted by the use of an analytical and a numerical model, namely Clark and mass transfer models. The results showed that the mass transfer model adequately described the experimental data. Sensitivity analysis revealed that the value of k _in has more effect than the axial dispersion coefficient (D _z) on the shape of breakthrough curve.     

Equilibrium, kinetics, mechanism, and process design for the sorption of methylene blue onto rice husk

Batch experiments were carried out for the sorption of methylene blue onto rice husk particles. The operating variables studied were initial solution pH, initial dye concentration, adsorbent concentration, and contact time. Equilibrium data were fitted to the Freundlich and Langmuir isotherm equations and the equilibrium data were found to be well represented by the Langmuir isotherm equation. The monolayer sorption capacity of rice husks for methylene blue sorption was found to be 40.5833 mg/g at room temperature (32 degrees C). The sorption was analyzed using pseudo-first-order and pseudo-second-order kinetic models and the sorption kinetics was found to follow a pseudo-second-order kinetic model. Also the applicability of pseudo second order in modeling the kinetic data was also discussed. The sorption process was found to be controlled by both surface and pore diffusion with surface diffusion at the earlier stages followed by pore diffusion at the later stages. The average external mass transfer coefficient and intraparticle diffusion coefficient was found to be 0.01133 min(-1) and 0.695358 mg/g min0.5. Analysis of sorption data using a Boyd plot confirms that external mass transfer is the rate limiting step in the sorption process. The effective diffusion coefficient, Di was calculated using the Boyd constant and was found to be 5.05 x 10(-04) cm2/s for an initial dye concentration of 50 mg/L. A single-stage batch-adsorber design of the adsorption of methylene blue onto rice husk has been studied based on the Langmuir isotherm equation.     

Effect of agitation on removal of acetic acid from pretreated hydrolysate by activated carbon

The effect of agitation on the adsorption of acetic acid by activated carbon was tested utilizing an external mass transfer-diffusion model. Simulated pretreated biomass was contacted with activated carbon under prescribed conditions of temperature and agitation. Adsorption isotherm studies are presented as well as batch kinetic rate studies. Use of these data enabled the determination of isotherm constants, an external mass transfer coefficient, and an effective diffusivity for each agitation rate studied. The external film coefficient results ranged from 33.62 μm/s to a complete absence of external mass transfer resistance, and the diffusivity results ranged from 0.8625 to 10.70 μm²/s. The optimum combination of no external film resistance, and highest diffusivity, 10.70 μm²/s, occurred at 250 rpm and 25°C. The results of these models and the experimental parameters suggested an efficacious method and conditions for the removal of this undesirable chemical.     

Analysis of diffusion models for protein adsorption to porous anion-exchange adsorbent

The ion-exchange adsorption kinetics of bovine serum albumin (BSA) and gamma-globulin to an anion exchanger, DEAE Spherodex M, has been studied by batch adsorption experiments. Various diffusion models, that is, pore diffusion, surface diffusion, homogeneous diffusion and parallel diffusion models, are analyzed for their suitabilities to depict the adsorption kinetics. Protein diffusivities are estimated by matching the models with the experimental data. The dependence of the diffusivities on initial protein concentration is observed and discussed. The adsorption isotherm of BSA is nearly rectangular, so there is little surface diffusion. As a result, the surface and homogeneous diffusion models do not fit to the kinetic data of BSA adsorption. The adsorption isotherm of gamma-globulin is less favorable, and the surface diffusion contributes greatly to the mass transport. Consequently, both the surface and homogeneous diffusion models fit to the kinetic data of gamma-globulin well. The adsorption kinetics of BSA and gamma-globulin can be very well fitted by parallel diffusion model, because the model reflects correctly the intraparticle mass transfer mechanism. In addition, for both the favorably bound proteins, the pore diffusion model fits the adsorption kinetics reasonably well. The results here indicate that the pore diffusion model can be used as a good approximate to depict protein adsorption kinetics for protein adsorption systems from rectangular to linear isotherms.