Application of the Shock Layer Theory to the Determination of the Mass Transfer Rate Coefficient and Its Concentration Dependence for Proteins on Anion Exchange Columns

Sajonz, Peter; Guan-Sajonz, Hong; Zhong, Guoming; Guiochon, Georges

doi:10.1021/bp970002w

Cited by 46 publications

(39 citation statements)

References 16 publications

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“…dependence of both km,L of BSA 17,18 and km of Tröger's base 19 reported previously [8][9][10][11] and derived new information concerning the mass transfer characteristics of the four transport processes described above. In the case of anion exchange separation of BSA, 17,18 it was shown that surface diffusion played a predominant contribution in the kinetic properties of mass transfer and that the linear concentration dependence of km,L probably resulted from that of the surface diffusion coefficient (Ds).…”

supporting

confidence: 61%

“…The extent of the positive concentration dependence of km,L was larger for L-PA than for D-PA. It is expected that a more detailed analysis of the overall mass transfer rate parameter, km,L, could provide new, useful information and allow for a better understanding of the kinetic properties of imprinted stationary phases.A similar positive concentration dependence was also demonstrated for km,L in anion exchange chromatography of bovine serum albumin (BSA), 8,9 and for the mass transfer rate coefficient (km) in the enantiomeric separation of Tröger's base on microcrystalline cellulose triacetate. 10,11 In other previous publications, a concentration dependence was also confirmed for intraparticle diffusivity, 12 for tracer diffusivity, 13 for axial dispersion, 14 for effective diffusivity, 15 and for mutual diffusion coefficients.…”

supporting

confidence: 56%

“…(9). Equations (4) and (9) suggest that the sum of the third and fourth terms in the RHS of Eq. (9), dp 2 /(60De) + (kp/(1 + kp)) 2 /kads, tends toward dp 2 /(60Dp) as K and kp approach zero.…”

Section: Estimation Of Dpmentioning

confidence: 99%

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Kinetic Study of the Concentration Dependence of the Mass Transfer Rate Coefficient in Enantiomeric Separation on a Polymeric Imprinted Stationary Phase

Miyabe

Guiochon

2000

ANAL. SCI.

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Molecular imprinting is a most attractive method of preparation of dedicated stationary phases for chromatography. Its use for enantioseparations is attracting considerable interest. 1,2 Imprinted materials can provide a very high selectivity for the objective compound, i.e., the imprinted molecule. [1][2][3][4][5] Although analytical applications are rapidly developing, the situation on the preparative front is less rosy. 1 Columns packed with imprinted stationary phases exhibit a poor efficiency and elution peaks are often unsymmetrical, especially for the more retained enantiomer. Sellergren et al. 1,2 suggested that the nonlinear behavior of the adsorption isotherm was the main cause of the broad and unsymmetrical bands observed for L-phenylalanine anilide (PA) on an L-PA imprinted chiral stationary phase. Although the possibility of a slow mass transfer kinetics was also pointed out, no detailed study supported this assumption. Yet, information on the mass transfer characteristics of imprinted stationary phases is necessary to clarify strategies for the improvement of these materials.Most kinetic studies in chromatography assume that four mass transfer processes are involved in a column, (1) axial dispersion, (2) fluid-to-particle mass transfer, (3) intraparticle diffusion, and (4) adsorption/desorption. 6 The contributions of these four processes to peak spreading are evaluated separately. Axial dispersion and the fluid-to-particle mass transfer resistance are inherent to flow processes through packed beds. They are well understood, relatively easy to control, and their contributions are often small. By contrast, intraparticle diffusion and adsorption/desorption give often larger contributions to the mass transfer resistance in the column. Their properties are intrinsic to each packing material and they are still often poorly understood. In order to evaluate the actual performance of packing materials, the characteristics of the mass transfer kinetics inside stationary phase particles must be clarified.Sajonz et al. 7 measured the adsorption equilibrium isotherm and the mass transfer kinetics of L-and D-PA on a polymeric stationary phase imprinted with L-PA, using a staircase frontal analysis method. The isotherm was well represented by either the Bi-Langmuir or the Freundlich models, but not by the simple Langmuir isotherm. The equilibrium data suggested that the distribution of the adsorption energy on the surface of the imprinted stationary phase is heterogeneous and showed that this phase has a high selectivity for the imprinted L-enantiomer. The lumped mass transfer rate coefficient (km,L) was calculated from each single breakthrough curve by applying the transport model of chromatography. 6 The values of km,L increased with increasing concentration of the enantiomers. The extent of the positive concentration dependence of km,L was larger for L-PA than for D-PA. It is expected that a more detailed analysis of the overall mass transfer rate parameter, km,L, could provide new, useful information and all...

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supporting

confidence: 61%

supporting

confidence: 56%

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Kinetic Study of the Concentration Dependence of the Mass Transfer Rate Coefficient in Enantiomeric Separation on a Polymeric Imprinted Stationary Phase

Miyabe

Guiochon

2000

ANAL. SCI.

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“…In some cases, however, the use of these models can lead to some considerable model errors [5]. For example, Kaczmarski et al [6] re-evaluated, using the GR and the POR models instead of the transport model previously used [20,21], experimental data on the mass transfer kinetics of BSA in ion-exchange chromatography. They found that all these models could well account for experimental data, but the values of the mass transfer coefficients for the GR and the POR models did not depend on the concentration while those for the transport model did.…”

Section: Introductionmentioning

confidence: 99%

“…The parameters of the MP model were calculated from experimental data by using Eqs. (19) and (20). The values of St9 for the POR model were obtained by using the fitting method and Eq.…”

mentioning

confidence: 99%

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

Wang

Zhang

2006

J. Sep. Sci.

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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.

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Mass transfer and separation criteria for high‐speed countercurrent chromatography

Zhao¹,

He²

2011

AIChE Journal

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in Wiley Online Library (wileyonlinelibrary.com).High-speed countercurrent chromatography (HSCCC) is a versatile technique for preparative separations of a wide variety of solutes. For optimization of operating conditions, prediction of separations, and scale-up study, a model is needed to describe the effluent concentration profile, which determines the separation efficiency (mass transfer, mixing, and partitioning) and the resolution between peaks. A transferdispersive model is proposed to describe the effluent profile based on the assumption that the retention of a peak is caused by partitioning over two phases, and peak broadening is caused by axial dispersion and mass transfer limitation. In this work, mass transfer was investigated by comparing model simulations to experimental data. One generalized correlation of overall mass transfer coefficients was derived. Based on the correlations of axial dispersion coefficients in our previous work and mass transfer coefficients in this study, the model predicts the elution concentration profile well. Furthermore, separation criteria were proposed to predict the separation of two adjacent solutes, and they were verified using literature data.

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Application of the Shock Layer Theory to the Determination of the Mass Transfer Rate Coefficient and Its Concentration Dependence for Proteins on Anion Exchange Columns

Cited by 46 publications

References 16 publications

Kinetic Study of the Concentration Dependence of the Mass Transfer Rate Coefficient in Enantiomeric Separation on a Polymeric Imprinted Stationary Phase

Kinetic Study of the Concentration Dependence of the Mass Transfer Rate Coefficient in Enantiomeric Separation on a Polymeric Imprinted Stationary Phase

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

Mass transfer and separation criteria for high‐speed countercurrent chromatography

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