A parallel pore and surface diffusion model for predicting the adsorption and elution profiles of lispro insulin and two impurities in gradient-elution reversed phase chromatography

Lispro insulin (LPI), a widely used insulin analog, is produced on tons per year scale. Linear gradient reversed phase chromatography (RPC) is used in the production to separate LPI from two impurities, which differ from LPI by a single amino acid residue. A chromatography model for the ternary separation in this RPC process is unavailable from the literature. In this study, a parallel pore and surface diffusion model is developed and verified for LPI and the two impurities. The LPI can be recovered with high yield (≥95%) and high purity (>99.5%). A new method, which requires a small amount of materials and an order of magnitude fewer experiments, has been developed to estimate the solvent-modulated isotherm parameters. A modified reversed phase modulator model is developed to correlate the adsorption isotherms of LPI and impurities. A strategy has been developed for estimating the intrinsic pore diffusivity and surface diffusivity. Since the adsorption affinities decrease by more than three orders of magnitude as organic fraction (φ) increases from 0.19 to 0.40, the apparent diffusivities based on a pore diffusion model or a surface diffusion model can also vary by several orders of magnitude. For this reason, a pore diffusion model or a surface diffusion model with a constant apparent diffusivity cannot predict closely the chromatograms over the same range of organic fractions, concentrations, and loadings. The parallel pore and surface diffusion model with constant diffusivities can predict closely the frontal and elution profiles over a wide range of organic fractions (0.19-0.40), LPI concentrations (0.05-18 g/L), linear velocities (<10 cm/min), and loading volume (0.0004-13 CV). For large loading stepwise and linear gradient elution, the peaks of LPI and the impurities are strongly focused by self-sharpening and gradient focusing effects as a result of the steep decrease of adsorption affinity from the loading φ (0.19) to elution φ (≥0.27). When the ratio of diffusion rate to convection rate is greater than 10, spreading due to diffusion is largely compensated by the focusing effects. As a result, a pore diffusion model with a constant pore diffusivity can predict closely the elution profiles in stepwise and linear gradient elution. The experimental yield values (≥95%) can be predicted to within ±1% by the model.     

Biosorption of Cr(VI) ions from aqueous solutions: kinetics, equilibrium, thermodynamics and desorption studies

Cr(VI) is a major water pollutant from industrial effluent whose concentration is to be reduced within the permissible limit. Present study reports a systematic evaluation of six different natural adsorbents for the removal of Cr(VI) from aqueous solutions in batch process. The adsorption kinetic data were best described by pseudo-second order model. The values of mass transfer coefficient for Cr(VI) adsorption indicated that the velocity of the adsorbate transport from the bulk to the solid phase was quite fast. The effective diffusivity of Cr(VI) removal for all the adsorbents were of the order of 10(-10) m(2)/s which suggested chemisorption of the process. The adsorption process was jointly controlled by film diffusion and intraparticle diffusion. Maximum monolayer adsorption capacities onto the natural adsorbents used were comparable to the other natural adsorbents used by other researchers. The thermodynamic studies and sorption energy calculation using Dubinin-Radushkevich isotherm model indicated that the adsorption processes were endothermic and chemical in nature. FT-IR studies were carried out to understand the type of functional groups responsible for Cr(VI) binding process. Desorption study was carried out with different concentration of NaOH solutions. Application study was carried out using electroplating industrial wastewater.     

Film-Pore Diffusion Control for the Batch Sorption of Cadmium Ions from Effluent onto Bone Char

The sorption equilibrium and kinetics of cadmium ions from aqueous solution onto bone char have been studied. Equilibrium isotherms for the sorption system were correlated by Langmuir and bi-Langmuir equations. The application of the bi-Langmuir equation was developed because the mechanistic analysis in this research indicated that cadmium removal occurs ion exchange and physical adsorption onto different surface sites. The bi-Langmuir equation provides a better fit to the experimental data. In addition, the removal rates of cadmium ions based on the Langmuir models have been investigated. The effective diffusivity was calculated using the effects of initial metal ion concentration and bone char mass. Two mass-transport models based on film-pore diffusion control have been applied to analyze the concentration decay curves. The film and pore diffusion coefficients using an analytical equation are equal to 1.26x10(-3) cm/s and 5.06x10(-7) cm(2)/s, respectively. The pore diffusion coefficient obtained from the numerical method is 4.89x10(-7) cm(2)/s. A sensitivity analysis showed that the film-pore diffusion model and constant effective diffusivity could be used to describe the mass-transport mechanism of the sorption system with a high degree of correlation. Copyright 2001 Academic Press.     

Effective intraparticle diffusion coefficients of CoCl2 in mesoporous functionalized silica adsorbents

The scope of this work is to determine the effective intraparticle diffusion coefficient of CoCl₂ over mesoporous functionalized silica. Silica is selected as a carrier of the functionalized groups for its rigid structure which excludes troublesome swelling, often found in polymeric adsorbents. 2-(2-pyridyl)ethyl-functionalized silica is selected as a promising affinity adsorbent for the reversible adsorption of CoCl₂. The adsorption kinetics is investigated with the Zero Length Column (ZLC) method. Initially, experiments were performed at different flow rates to eliminate the effect of external mass transfer. The effect of pore size (60 Å and 90 Å), particle size (40?10^?6 m–1000?10^?6 m) and initial CoCl₂ concentration (1 mol/m³–2.0 mol/m³) on the mass transfer was investigated. A model was developed to determine the pore diffusion coefficient of CoCl₂ by fitting the experimental data to the model. The pore diffusion coefficients determined for two different pore sizes of silica are D _p (60 Å) =1.95?10^?10 [m²/s] and D _p (90 Å) =5.8?10^?10 [m²/s]. The particle size and the initial CoCl₂ concentration do not have an influence on the value of diffusion coefficient. However, particle size has an influence on the diffusion time constant. In comparison with polymer adsorbents, silica based adsorbents have higher values of diffusion coefficients, as well as a more uniform and stable pore structure.     

Hydrophobic interaction chromatography of proteins III. Transport and kinetic parameters in isocratic elution

The effective pore diffusivities, D(e), of five model proteins (ribonuclease A, lysozyme, alpha-lactalbumin, ovalbumin, and BSA) in eight commercial phenyl hydrophobic interaction chromatography (HIC) media were determined by analyzing the plate height data from isocratic elution using the first two moments of the general linear rate model. The adsorbents represent a diverse set of HIC media that are widely used for protein purification. The estimated pore diffusivities were used to calculate the elution profiles of proteins in these adsorbents and were compared with the elution profiles obtained experimentally. High protein loading and sample protein concentration led to the underestimation of the pore diffusivity by the linear rate model. Comparisons between the calculated and the experimental profiles suggest that the pore diffusivities obtained from the linear rate model are generally accurate for proteins with low structural flexibility but not for more flexible ones, presumably because conformational change effects contribute significantly to the overall HETP. The general linear rate model was modified to account for the protein folding/unfolding kinetics, and parameter values could be estimated by fitting the experimental elution profiles to the modified model. In addition to conformational change, adsorbent type also had a significant effect on the accuracies of the pore diffusivities estimated by the linear rate model. The results also show that pore diffusion was the rate-limiting step in all absorbents for rigid proteins such as ribonuclease A and lysozyme. For structurally flexible proteins, conformational change contributed significantly to the overall reduced plate heights of the isocratic elution peaks. The physical properties of adsorbents, such as protein accessible porosity, pore size distribution, pore radius and pore connectivity, play important roles in determining the effective protein pore diffusivities.     

树脂填充聚醚砜纤维吸附剂对牛血清蛋白吸附性能的研究

重点研究树脂填充聚醚砜(PES)纤维吸附剂与模型蛋白质牛血清蛋白(BSA)之间的吸附与脱附行为.结果表明,蛋白质BSA在树脂填充PES纤维吸附剂中的平衡吸附过程较好地符合朗格缪尔吸附模型,树脂Lewatit CNP80ws填充PES吸附剂的最大吸附容量约为139mg BSA/g吸附剂.表面具有开孔结构的树脂填充PES纤维吸附剂的吸附速率较快,在不同结构纤维吸附剂中BSA的扩散系数在1·82×10-14~8·7×10-14m2/s范围内变化.另外,考察了BSA溶液的pH与洗脱剂等因素对吸附剂吸附与脱附性能的影响,研究结果对蛋白质的实际分离纯化具有重要的参考价值.     

Adsorption equilibrium and kinetics of copper ions and phenol onto modified adsorbents

The adsorption equilibrium and kinetics of single and binary component copper ions and phenol onto powdered activated carbon (PAC), alginate beads and alginate-activated carbon beads (AAC) were studied. Adsorption equilibrium data for single component copper ions and phenol onto the adsorbents could be represented by the Langmuir equation. Multicomponent equilibrium data were correlated by the extended Langmuir and ideal adsorbed solution theory (IAST). The IAST gave the best fit to our data. The amount of copper ions adsorbed onto the AAC beads in the binary component was greater than that of phenol. The internal diffusion coefficients were determined by comparing the experimental concentration curves with those predicted from surface diffusion and pore diffusion model.     

改性碳纳米管常温下吸附分离低浓度CO2

采用浸渍法将四乙烯五胺(TEPA)和三乙烯四胺(TETA)负载至碳纳米管(CNTs)上,得到一种固态胺吸附剂CNTs-TEPA和CNTs-TETA,用以吸附低浓度下的CO2.利用扫描电镜(SEM)、透射电镜(TEM)、傅里叶红外(FTIR)光谱、N2物理吸附脱附、元素分析和热重分析(TGA)等方法表征样品.结果表明:CNTs-TEPA和CNTs-TETA形态并未发生变化,仍保留CNTs规整有序的孔道结构,但样品的比表面积和孔容都显著减小.在常温条件下,CNTs-TEPA和CNTs-TETA的CO2吸附量与CNTs相比有显著提高,同时,在胺浸渍质量相同的情况下,改性后的CNTs-TEPA效果优于CNTs-TETA.温度从20℃升至30℃,CNTs-TEPA和CNTs-TETA的CO2吸附量分别从126.7、101.2mg·g-1升至139.3、110.4mg·g-1.CNTs的吸附量随着温度的增加变化不明显.最后,采用Suyadal和Yasyerli两种模型对CO2的动态吸附穿透曲线进行拟合,结果说明Yasyerli模型对CNTs、CNTs-TEPA和CNTs-TETA的CO2吸附过程的拟合程度更高.     

Adsorption of hydrogen isotopes on micro- and mesoporous adsorbents with orderly structure

The equilibrium and dynamic adsorption data of H(2) and D(2) on different micro- and mesoporous adsorbents with orderly structure including 3A, 4A, 5A, Y, and 10X zeolites; carbon CMK-3; silica SBA-15; and so forth were collected. Critical effect of the nanodimension of adsorbents on the adsorption behavior of hydrogen and its isotopes is shown. The highest adsorption capacity was observed at pore size 0.7 nm, but equal or even larger isotope difference in the equilibrium adsorption was observed at larger pore sizes, whereas the largest isotope difference in the dynamic adsorption was observed at 0.5 nm. The adsorption rate of D(2) is larger than that of H(2) in microporous adsorbents, but the sequence could be switched over in mesoporous materials. Linear relationship was observed between the adsorption capacity for hydrogen and the specific surface area of adsorbents although the adsorbents are made of different material, which provides a convincing proof of the monolayer mechanism of hydrogen adsorption. The linear plot for microporous adsorbents has a larger slope than that for mesoporous adsorbents, which is attributed to the stronger adsorption potential in micropores.     

Effects of ligand density and pore size on the adsorption of bovine IgG with DEAE ion-exchange resins

Immunoglobulin G is an important plasma protein with many applications in therapeutics and diagnostics, which can be purified effectively by ion exchange chromatography. The ligand densities and pore properties of ion-exchange resins have significant effects on the separation behaviors of protein, however, the understandings are quite limited. In this work, with bovine immunoglobulin as the model IgG, the adsorption isotherms and adsorption kinetics were investigated systematically with series of diethylaminoethyl ion-exchange resins with different ligand densities and pore sizes. The Langmuir equation and pore diffusion model were used to fit the experimental data. The influences of ligand density and pore size on the saturated adsorption capacity, the dissociation constant and the effective diffusivity were discussed. The adsorption capacities increased with the increase of ligand density and the decrease of pore size, and an integrative parameter was proposed to describe the combined effects of ligand density and pore size. It was also found that the effective pore diffusion coefficient of the adsorption kinetics was influenced by pore sizes of resins, but was relatively independent on the ligand densities of resins. For a given protein, the ligand density and pore size should be optimized for improving the protein adsorption.     

Efficient adsorbents of nanoporous aluminosilicate monoliths for organic dyes from aqueous solution

Growing public awareness on the potential risk to humans of toxic chemicals in the environment has generated demand for new and improved methods for toxicity assessment and removal, rational means for health risk estimation. With the aim of controlling nanoscale adsorbents for functionality in molecular sieving of organic pollutants, we fabricated cubic Im3m mesocages with uniform entrance and large cavity pores of aluminosilicates as highly promising candidates for the colorimetric monitoring of organic dyes in an aqueous solution. However, a feasible control over engineering of three-dimensional (3D) mesopore cage structures with uniform entrance (~5 nm) and large cavity (~10 nm) allowed the development of nanoadsorbent membranes as a powerful tool for large-quantity and high-speed (in minutes) adsorption/removal of bulk molecules such as organic dyes. Incorporation of high aluminum contents (Si/Al=1) into 3D cubic Im3m cage mesoporous silica monoliths resulted in small, easy-to-use optical adsorbent strips. In such adsorption systems, natural surfaces of active acid sites of aluminosilicate strips strongly induced both physical adsorption of chemically responsive dyes and intraparticle diffusion into cubic Im3m mesocage monoliths. Results likewise indicated that although aluminosilicate strips with low Si/Al ratios exhibit distortion in pore ordering and decrease in surface area and pore volume, enhancement of both molecular converges and intraparticle diffusion onto the network surfaces and into the pore architectures of adsorbent membranes was achieved. Moreover, 3D mesopore cage adsorbents are reversible, offering potential for multiple adsorption assays.     

Fundamental characteristics of synthetic adsorbents intended for industrial chromatographic separations

With the aim of obtaining comprehensive information on the selection of synthetic adsorbents for industrial applications, effect of pore and chemical structure of industrial-grade synthetic adsorbents on adsorption capacity of several pharmaceutical compounds was investigated. For relatively low molecular mass compounds, such as cephalexin, berberine chloride and tetracycline hydrochloride, surface area per unit volume of polystyrenic adsorbents dominated the equilibrium adsorption capacity. On the contrary, effect of pore size of the polystyrenic adsorbents on the equilibrium adsorption capacity was observed for relatively high molecular mass compounds, such as rifampicin, Vitamin B12 and insulin. Polystyrenic adsorbent with high surface area and small pore size showed small adsorption capacity for relatively high molecular mass compounds, whereas polystyrenic adsorbent with relatively small surface area but with large pore size showed large adsorption capacity. Effect of chemical structure on the equilibrium adsorption capacity of several pharmaceutical compounds was also studied among polystyrenic, modified polystyrenic and polymethacrylic adsorbents. The modified polystyrenic adsorbent showed larger adsorption capacity for all compounds tested in this study due to enhanced hydrophobicity. The polymethacrylic adsorbent possessed high adsorption capacity for rifampicin and insulin, but it showed lower adsorption capacity for the other compounds studied. This result may be attributed to hydrogen bonding playing major role for the adsorption of compounds on polymethacrylic adsorbent. Furthermore, column adsorption experiments were operated to estimate the effect of pore characteristics of the polystyrenic adsorbents on dynamic adsorption behavior, and it is found that both surface area and pore size of the polystyrenic adsorbents significantly affect the dynamic adsorption capacity as well as flow rate.     

Adsorption rate of Reactive Black 5 on chitosan based materials: geometry and swelling effects

The overall adsorption rate of Reactive Black 5 dye (RB5) on chitosan based materials was elucidated using diffusional models. Fundamental aspects, such as, geometry of the adsorbents and swelling effects were considered. Chitosan based materials (powder and film) were prepared from shrimp wastes and characterized regarding to the fundamental features for adsorption. Experimental decay curves were obtained under different conditions of stirring rate and initial dye concentration. The data were modeled according to the external mass transfer and diffusional models. The k_L (external mass transfer coefficient), D_ep (effective pore diffusion coefficient) and D_s (surface diffusion coefficient) values were estimated. For both adsorbents, it was found that the surface diffusion was the intraparticle diffusion mechanism governing the adsorption rate of RB5, since its contribution was higher than 92 % regardless the position and time. The D_s values ranged from 2.85 × 10^?11 to 5.78 × 10^?11 for chitosan powder and from 4.15 × 10^?11 to 12.12 × 10^?11 cm² s^?1 for chitosan films. The RB5 adsorption was faster when chitosan powder was used, mainly at higher stirring rates and initial dye concentrations. The swelling effect was most pronounced for the chitosan films, where, provided an increase of about 65 times in the D_s value.     

Adsorption Studies of Nonionic Surfactants onto Polyvinyltoluene Microlatexes in Aqueous Medium

Negatively charged polyvinyltoluene (PVT) microlatexes of various dimensions were prepared by polymerization of the corresponding vinyltoluene-in-water microemulsion precursors containing sodium dodecyl sulfate and n-pentanol. PVT microlatexes were used as adsorbents for adsorption of nonionic surfactants such as Tween 80, Tween 20, and Triton X-100. The extents of adsorption were known from the differences in the diffusion coefficient of the PVT microlatexes containing a solubilized suitable electro active probe. The surface excess (Gamma), equilibrium constant of adsorption (K(ads)), molecular cross-sectional surface area (sigma), intercalation ratio (kappa), etc., were determined for sodium dodecyl sulfate composition variation and ionic strength effects. A surface reconstruction model was proposed to rationalize the results. Copyright 2000 Academic Press.     

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.     

乙酸乙酯水溶液中水在3A分子筛上的吸附平衡与动力学

乙酸乙酯水溶液中水在3A分子筛上的吸附平衡与动力学;乙酸乙酯;水;吸附平衡与动力学;表面扩散系数;3A分子筛     

Preparation and performance evaluation of resin-derived carbon spheres for desulfurization of fuels

A polystyrene-based ion-exchange resin was employed as the precursor for preparation of resin-derived carbon spheres(RCSs) through KOH activation with various impregnation ratios.Pore structure,yield and hardness,surface functional groups of the samples and their adsorption performance towards dibenzothiophene(DBT) were investigated.The RCSs with large surface areas(up to 2696m2/g) and total pore volumes(up to 1.46 cm3/g) exhibited larger adsorption capacities than a commercial activated carbon,F400.Polanyi-Dubinin-Mane(PDM) model was applied to fit the adsorption data,which proved that micropore filling was involved during the adsorption process.Moreover,a good linear relationship was observed between the extra-micropore volume and adsorption capacity.Intra-particle diffusion(IPD) model was used to describe the kinetic data of DBT onto the adsorbents.The adsorption processes were divided into three stages according to the different diffusion parameter.The selective adsorption towards DBT in the presence of competing compounds was also investigated and the high selectivity of the RSCs towards DBT may be attributed to the large quantity of acidic oxygen-containing groups.     

Effect of particle size of activated clay on the adsorption of paraquat from aqueous solution

This paper describes the effect of particle size on the process of paraquat adsorption from aqueous solution onto an activated clay surface at 25 degrees C and initial pH 11.0. Measurements of the pore properties of the clay adsorbents with three different particle sizes (0.053-0.074 mm, 0.037-0.053 mm, and <0.037 mm) were carried out. The rates and isotherms of adsorption have been also investigated by batch methods under the controlled conditions. From the experimental results obtained, the adsorption process can be well described with the pseudo-second order model and Freundlich model for adsorption kinetics and adsorption isotherm, respectively. In addition, the effect of the particle size of the clay adsorbent on the adsorption kinetics was found to be of considerable significance; namely, the rate constant (k) of paraquat adsorption by the clay adsorbent decreased with increasing particle size. It was concluded that the pore properties (i.e., surface area and total pore volume) and particle size of the clay adsorbent played a significant role in determining adsorption capacity and adsorption rate, respectively.