Modeling of equilibrium and kinetics of human polyclonal immunoglobulin G adsorption on a tentacle cation exchanger

Adsorption of human immunoglobulin G (IgG) on a commercial cation exchanger with a grafted polymer layer was investigated at pH 4.5 and in the NaCl concentration range of 0–150 mM. Adsorption equilibrium was determined in static batch experiments and verified in batch uptake experiments. Parameters of the Langmuir isotherm were estimated for each salt concentration separately. The batch uptake experiments provided also the estimates of effective pore diffusion coefficients of IgG for individual protein and salt concentrations. The values of the effective pore diffusion coefficient depended strongly on both factors. They increased by about 5–15 times with the NaCl concentration and decreased about three times with the protein concentration. The quality of the estimated parameters was confirmed by frontal experiments described by the general rate model of chromatography.     

Protein adsorption equilibrium and kinetics in multimodal cation exchange resins

Protein adsorption equilibria and kinetics are obtained experimentally for two multimodal cation exchange resins—Nuvia cPrime, which is based on a polymeric matrix, and Capto MMC, which is based on an agarose matrix. In both resins, the ligand contains a phenyl group, a carboxyl group, and a peptide bond but with a different arrangement. Transmission electron microscopy and inverse size exclusion chromatography indicate a bimodal distribution of pores in Nuvia cPrime, including small pores with 10 nm radius and pores larger than 400 nm, and a monodispersed distribution of pores in Capto MMC, averaging 32 nm in radius. Potentiometric titration curves show similar buffering ranges and pK _a values for the ligands in both resins and a slightly higher ligand density for Nuvia cPrime. Equilibrium binding capacities for lysozyme and a monoclonal antibody (mAb) are also similar for both resins at comparable pH and salt concentrations, although Capto MMC shows a weaker dependence on salt concentration as a result of its more hydrophobic character. The main difference is the adsorption kinetics of the mAb, which is the larger of the two proteins studied. For both resins, as shown by means of confocal laser scanning miscopy, the adsorption kinetics is controlled by pore diffusion. Capto MMC with its smaller pores has a slower rate of mass transfer than Nuvia cPrime. As a result, for the mAb, much higher column dynamic binding capacities are obtained for Nuvia cPrime than for Capto MMC.     

Dipole moments of derivatives of glucose,galactose and lactose

Summary The dipole moments of derivatives of D-glucose and D-galactose have been determined in solutions of chloroform, a common polar solvent. These values have been compared with the values obtained previously in solutions of non-polar solvents.

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Zusammenfassimg Die Dipolmomente von Derivaten der D-Glukose und der D-Galaktose wurden in L?sung von Chloroform bestimmt, einem zuweilen verwendeten polaren L?sungsmittel. Die Werte werden mit den früher bestimmten in L?sungen mit unpolaren L?sungsmitteln verglichen.

     

Dipole moments of derivatives of glucose,galactose and lactose part I

Summary The dipole moments of the- and-isomers of 2, 3, 4, 6 tetraacetyl aoetyl D-glucose and 2, 3, 4, 6 tetraacetyl methyl D-glucose have been determined in solutions of benzene, by the application of the method of Halverstadt and Kumler. This is expected to remove from the older data the uncertainties introduced by the extrapolation methods.The moments of the penta-methyl derivatives of D-glucose, of the penta-acetyl derivative of-D-galactose and of the octaacetate of-lactose are also recorded.The effect of temperature on the dipole moments has not been found to be pronounced, in the range 30–40°C.

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Zusammenfassung Dipolmomente einiger Derivate von Glukose, Galaktose und Laktose wurden teilweise erstmals aus benzolischer Lösung ermittelt: Extrapolationsmethode auf unendliche Verdünnung nach Halverstadt und Kumler. Beseitigung einiger Unsicherheiten in früheren Bestimmungen. Es wurde kein wesentlicher Temperatureinfluß im Bereich von 30–40°C gefunden.

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The author wishes to express his gratitude to Dr. S. K. K. Jatkar, and to Dr. B. Sanjiva Rao for his unstinting and valuable help. He is thankful to Dr. R. J. W. Le Fèvre for his kind interest in the work. His thanks are also to the Indian Institute of Science for providing facilities for investigations.     

Dextran-grafted cation exchanger based on superporous agarose gel: Adsorption isotherms,uptake kinetics and dynamic protein adsorption performance

A novel chromatographic medium for high-capacity protein adsorption was fabricated by grafting dextran (40 kDa) onto the pore surfaces of superporous agarose (SA) beads. The bead was denoted as D-SA. D-SA, SA and homogeneous agarose (HA) beads were modified with sulfopropyl (SP) group to prepare cation exchangers, and the adsorption and uptake of lysozyme on all three cation-exchange chromatographic beads (SP-HA, SP-SA and SP-D-SA) were investigated at salt concentrations of 6–50 mmol/L. Static adsorption experiments showed that the adsorption capacity of SP-D-SA (2.24 mmol/g) was 78% higher than that of SP-SA (1.26 mmol/g) and 54% higher than that of SP-HA (1.45 mmol/g) at a salt concentration of 6 mmol/L. Moreover, salt concentration had less influence on the adsorption capacity and dissociation constant of SP-D-SA than it did on SP-HA, suggesting that dextran-grafted superporous bead is a more potent architecture for chromatographic beads. In the dynamic uptake of lysozyme to the three cation-exchange beads, the D_e/D₀ (the ratio of effective pore diffusivity to free solution diffusivity) values of 1.6–2.0 were obtained in SA-D-SA, indicating that effective pore diffusivities of SP-D-SA were about two times higher than free solution diffusivity for lysozyme. At 6 mmol/L NaCl, the D_e value in SA-D-SA (22.0 × 10⁻¹¹ m²/s) was 14.4-fold greater than that in SP-HA. Due to the superior uptake kinetics in SA-D-SA, the highest dynamic binding capacity (DBC) and adsorption efficiency (the ratio of DBC to static adsorption capacity) was likewise found in SP-D-SA. It is thus confirmed that SP-D-SA has combined the advantages of superporous matrix structure and drafted ligand chemistry in mass transport and offers a new opportunity for the development of high-performance protein chromatography.     

Two-component protein adsorption to the cation exchanger S Sepharose FF

A model system, consisting of bovine serum albumin, lysozyme and the cation exchanger S Sepharose FF, was used to investigate multicomponent protein adsorption to ion exchangers. Two models, one based on a complete absence of competition between adsorbing molecules and the other a competitive model, based on the assumption that all adsorption sites are available to both proteins, have been compared to experimental results. Evidence for competitive adsorption was seen in experiments in which breakthrough curves and the profiles of adsorbed proteins in packed beds were determined. However, although the results for packed-bed experiments were more closely predicted by the fully competitive model, some discrepancies were found suggesting that when considering multicomponent protein adsorption to ion exchangers it may also be necessary to take account of factors such as the molecular size of the adsorbing proteins and any potential inter-protein interactions, factors which may hinder the development of a general model of multicomponent protein adsorption to ion exchangers.     

Study of kinetics,equilibrium and isotope exchange in ion exchanger systems

An automatic, rapid combustion method has been developed for the determination of tritium and¹⁴C in singly or doubly labelled organic materials by liquid scintillation counting. The sample is burned in a stream of oxygen. The water formed and its tritium content are retained from the gas stream in an absorber containing a small amount of diethyleneglycol monoethyl ether. Radioactive carbon dioxide, if included in the combustion products, is transferred into 3-methoxypropylamine. The final solutions ready for counting are obtained in less than three minutes. Quantitative collection recoveries for both tritium and¹⁴C are achieved and no cross-contamination occurs.     

Hydrogen bonding and cooperativity in isolated and hydrated sugars: mannose, galactose, glucose, and lactose

The conformation of phenyl-substituted monosaccharides (mannose, galactose, and glucose) and their singly hydrated complexes has been investigated in the gas phase by means of a combination of mass selected, conformer specific ultraviolet and infrared double resonance hole burning spectroscopy experiments, and ab initio quantum chemistry calculations. In each case, the water molecule inserts into the carbohydrate at a position where it can replace a weak intramolecular interaction by two stronger intermolecular hydrogen bonds. The insertion can produce significant changes in the conformational preferences of the carbohydrates, and there is a clear preference for structures where cooperative effects enhance the stability of the monosaccharide conformers to which the water molecule chooses to bind. The conclusions drawn from the study of monosaccharide-water complexes are extended to the disaccharide lactose and discussed in the light of the underlying mechanisms that may be involved in the binding of carbohydrate assemblies to proteins and the involvement, or not, of key structural water molecules.     

Experimental and theoretical studies of sodium cation interactions with D-arabinose, xylose, glucose, and galactose

The binding of Na (+) to arabinose (Ara), xylose (Xyl), glucose (Glc), and galactose (Gal) is examined in detail by studying the collision-induced dissociation (CID) of the four sodiated monosaccharide complexes with Xe using a guided ion beam tandem mass spectrometer (GIBMS). Analysis of the energy-dependent CID cross-sections provides 0 K sodium cation affinities for experimental complexes after accounting for unimolecular decay rates, internal energy of reactant ions, and multiple ion-neutral collisions. Quantum chemical calculations for a number of geometric conformations of each Na (+)(L) complex with a comprehensive analysis of the alpha and beta anomeric forms are determined at the B3LYP/6-311+G(d,p) level with single-point energies calculated at MP2(full), B3LYP, and B3P86 levels using a 6-311+G(2d,2p) basis set. This coordinated examination of both experimental work and quantum chemical calculations allows for determination of the bond energy for both the alpha and beta forms of each monosaccharide studied here. An understanding of the energetic contributions of individual structural characteristics as well as the energetic trends in binding among the monosaccharides is developed. Structural characteristics that affect the energetics of binding involve multidentate sodium cation coordination, ring sterics, and hydrogen bonding schemes. The overall trend in sodium binding affinities for the eight ligands follows beta-Ara < alpha-Ara < beta-Xyl < beta-Glc < alpha-Glc < alpha;-Xyl < alpha-Gal < beta-Gal.     

活性炭表面含氧基团对苯酚吸附平衡及动力学的影响

煤基活性炭分别用烧失处理和HNO3氧化处理后得到不同表面性质的活性炭,采用X射线光电子能谱(XPS)、N2吸附、酸碱滴定及零电荷点(pHPZC)对活性炭表面性质及孔结构进行表征,研究了活性炭表面性质对苯酚吸附平衡和吸附动力学影响.经HNO3氧化后,活性炭表面含氧基团显著增加,烧失处理后,表面含氧基团尤其是羧基显著减少.苯酚最大平衡吸附量随活性炭表面含氧基团的增多而减少,吸附速率常数与碳表面含氧基团的量呈正相关,而吸附活化能与活性炭在一定吸附条件下表面所带电荷多少相关.随着活性炭表面含氧基团增多,吸附活化熵增大(负值减小),苯酚在活性炭表面排列的有序性减小.静态吸附与动态吸附实验结果都表明:在含氧基团较少而碱性更强的活性炭上,发生化学吸附的程度更大.     

Effect of pressure and temperature on the adsorption equilibrium in the H2-Ne-zeolite NaA system

The effect of the temperature, pressure, and gas-phase composition on the parameters of the adsorption equilibrium in a zeolite NaA-neon-hydrogen system was studied. From the results obtained optimum conditions for the adsorption separation of a binary neonhydrogen gas mixture were found.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 611–612, March, 1993.     

Thermodynamics and kinetics of adsorption of Cu(II) from aqueous solutions onto a new cation exchanger derived from tamarind fruit shell

A novel cation exchanger (TFS-CE) having carboxylate functionality was prepared through graft copolymerization of hydroxyethylmethacrylate onto tamarind fruit shell (TFS) in the presence of N,N′-methylenebisacrylamide as a cross-linking agent using K₂S₂O₈/Na₂S₂O₃ initiator system, followed by functionalisation. The TFS-CE was used for the removal of Cu(II) from aqueous solutions. At fixed solid/solution ratio the various factors affecting adsorption such as pH, initial concentration, contact time, and temperature were investigated. Kinetic experiments showed that the amount of Cu(II) adsorbed increased with increase in Cu(II) concentration and equilibrium was attained at 1 h. The kinetics of adsorption follows pseudo-second-order model and the rate constant increases with increase in temperature indicating endothermic nature of adsorption. The Arrhenius and Eyring equations were used to obtain the kinetic parameters such as activation energy (E_a) and enthalpy (ΔH^#), entropy (ΔS^#) and free energy (ΔG^#) of activation for the adsorption process. The value of E_a for adsorption was found to be 10.84 kJ · mol^?1 and the adsorption involves diffusion controlled process. The equilibrium data were well fitted to the Langmuir isotherm. The maximum adsorption capacity for Cu(II) was 64 · 10 mg · g^?1 at T = 303 K. The thermodynamic parameters such as changes in free energy (ΔG^°), enthalpy (ΔH^°), and entropy (ΔS^°) were derived to predict the nature of adsorption process. The isosteric heat of adsorption increases with increase in surface loading indicating some lateral interactions between the adsorbed metal ions.     

The influence of cation, anion and temperature on the liquid-liquid equilibrium of some pentanols-water system

Liquid-liquid equilibrium (LLE) measurements for aqueous systems containing some pentanols and sodium, or potassium nitrate have been performed experimentally at 25 °C and atmospheric pressure. The pentanols are: 1-pentanol (1P), 2-pentanol (2P), 3-pentanol (3P), 2-methyl-1-butanol (3M1B) and 2-methyl-2-butanol (2M2B). The obtained data have been modeled using an extended UNIQUAC activity coefficient model. The influence of the cation, the anion and the temperature on the liquid-liquid equilibrium, are illustrated by applying the Setschenow equation on the studied systems and on other systems from literature. The results show that the influence of sodium salts is higher than that of potassium salts with the same anion and the same alcohol. On the other hand, the influence of the nitrate and bromide salts is lower than that of chloride salts with the same cation and the same alcohol. Linearity of Setschenow relation indicates that the influence of the given salts on the liquid-liquid equilibrium in the systems under study, are additive. The effect of temperature on the phase behavior is that the mutual solubilities of both liquids, in the presence of salt, decrease with temperature.     

Novel glucose non-interference biosensor for lactose detection based on galactose oxidase-peroxidase with and without co-immobilised beta-galactosidase

Two types of amperometric biosensors for lactose detection based either on co-immobilisation of two enzymes (galactose oxidase with peroxidase) or co-immobilisation of three enzymes (beta-galactosidase, galactose oxidase and peroxidase) were constructed. A graphite rod with pre-adsorbed ferrocene was used as a working electrode. The use of galactose oxidase instead of the frequently used glucose oxidase resulted in the construction of a glucose-non-interfering lactose sensor. Co-immobilisation of peroxidase with galactose oxidase allowed the effect of borate on the extension of the linear range and the effect of the working potential on galactose oxidase activation to be studied. The presence of beta-galactosidase greatly enhances the sensor's sensitivity, but its linear range is narrower than that of the sensor without beta-galactosidase. Addition of DEAE-dextran and inositol to the enzyme layer improved the half-life more than 16-fold compared with the sensor without stabilisers. A response time between 60 and 75 s (90% of the steady-state value) and a detection limit for lactose determination from 44 to 339 microM (signal-to-noise ratio = 3) were observed depending on the conditions. The precision of measurements of standard lactose solution for the trienzymatic and bienzymatic sensors was 2.19 and 2.02%, respectively. The precision of analysis of dairy products varied from 0.24 to 5.24%. Analyses of real samples showed good correlation with HPLC analysis; eight samples and 10 standard lactose solutions without pre-treatment were analysed in 1 h.     

Effects of site occupancy, cation relocation, and pore geometry on adsorption kinetics in ETS-4

Strontium-exchanged titanium silicate, Sr-ETS-4, is a new molecular sieve with promises for exciting applications in gas separation. The literature mentions poor thermal stability and low adsorption capacity as the drawbacks of the as-synthesized Na-ETS-4 and therefore the need for cation exchange. Upon ion exchange, Sr-ETS-4 shows appreciable kinetic selectivity between methane and nitrogen, which can be improved further by controlled dehydration. In this study, we trace the changes at the molecular level behind this improvement. By combining distributed information in the literature, it is shown that the governing factors are changes in pore geometry with progressive dehydration, changes in ion occupancy, and relocation of cations due to Sr exchange.     

Nonlinear FR-ZLC method for investigation of adsorption equilibrium and kinetics

A new method for investigation of adsorption equilibrium and kinetics, named Nonlinear Frequency Response-Zero Length Column (NFR-ZLC) method, is introduced. It combines the advantages of the Nonlinear FR method (the potential to identify a model corresponding to the most probable kinetic mechanism and to estimate the equilibrium and kinetic parameters of the identified model) and of the ZLC method (the potential to derive direct information about the processes on the particle level, by eliminating the influence of the adsorber). The frequency response functions of a ZLC system, up to the third order, and for three simple kinetic mechanisms (film resistance control, micropore diffusion control and pore-surface diffusion control) are derived and simulated. The procedure for estimation of the equilibrium and kinetic parameters is defined and illustrated based on numerical simulations.     

Preparation of novel heterogeneous catalysts by adsorption of a cationic tetrapyrrole on to bentonite: equilibrium, kinetics, and thermodynamics

Abstract  

Adsorption of an octacationic tetrapyrrole, octakis(2-trimethylammoniumethylsulfanyl)porphyrazinatocobalt octaiodide (QCoPz), from aqueous solutions on to negatively charged bentonite was investigated. Effects of temperature, dye concentration, solid concentration, and contact time on adsorption were determined. Zeta potential and ion-release measurements were also used as supporting experiments. Experimental data were analyzed using four adsorption kinetic models; a pseudo second-order kinetic model resulted in better correlation with experimental results than the others. Experimental equilibrium data were analyzed by non-linear regression using five adsorption isotherm models with two, three, or four terms. Free energies, enthalpies, and entropies for the adsorption process were determined. The results indicated that adsorption of QCoPz on bentonite was exothermic and spontaneous in nature. FT-IR spectroscopy of the composite and its desorptive behavior were also investigated to identify the mechanism of adsorption. The novel QCoPz–bentonite composites obtained are likely to be used in “green chemistry” and in a wide range of optical and/or catalytic applications, especially those crucially important in the petroleum and pulp/paper industries for waste water cleaning (destruction of mercaptans, sulfides, phenol, and halogenated aromatics, etc.) and removal of bad odor.     

Sorption,acid, and catalytic properties of a sulfonic cation exchanger supported on the carbon fiber

Distribution in strength of the acid centers in sulfonic cation in the form of exchanger granules and fibers was studied by the novel modification of the thermal desorption method.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 11, 2004, pp. 1779–1782.Original Russian Text Copyright © 2004 by Egiazarov, Shachenkova, Radkevich, Cherches, Gorbatsevich, Ermolenko.     

Effect of the synthesis temperature of sodium nonatitanate on batch kinetics of strontium-ion adsorption from aqueous solution

Sodium titanate materials are promising inorganic ion exchangers for the adsorption of strontium from aqueous solutions. Sodium nonatitanate exhibits a layered structure consisting of titanate layers and exchangeable sodium ions between the layers. The materials used in this study include samples synthesized by a hydrothermal method at temperatures between 60 °C and 200 °C. Their structure, composition, and morphology were investigated with X-Ray diffraction measurements; thermogravimetric, compositional and surface area analyses, and scanning electron microscopy. The structure, composition, and morphology depended on the synthesis temperature. Batch kinetics experiments for the removal of strontium from aqueous solutions were performed, and the data were fitted by a pseudo-second-order reaction model and a diffusive model. The strontium extraction capacity also depended on the synthesis temperature and exhibited a maximum for samples synthesized at 100 °C. The sorption process occurs in one or two diffusion-controlled steps that also depend on the synthesis temperature. These diffusion-limited steps are the boundary-layer diffusion and intra-particle diffusion in the case of pure nonatitanate synthesized at temperatures lower than 170 °C, and only intra-particle diffusion in the case of nonatitanate synthesized at 200 °C.