Affinity Capillary Electrophoresis as a Tool to Characterize Intermolecular Interactions

Kiessig, Steffen; Stettler, Alexandra R.; Fuhrimann, Samuel; Schwarz, Maria A.

doi:10.1002/9780470661345.smc035

Cited by 4 publications

(2 citation statements)

References 91 publications

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“…High-performance liquid phase separation techniques, such as capillary electrophoresis (CE) and high-performance liquid chromatography (HPLC), have also been used for the analysis of intermolecular interactions. For example, CE has been widely used for measuring K A , k a , and k d . − However, the values of k a and k d are usually estimated by a curve fitting approach between numerical calculation results and experimental data, which is not an analytical determination method of k a and k d from electropherograms experimentally measured.…”

Section: Introductionmentioning

confidence: 99%

Moment Theory of Chromatography for the Analysis of Reaction Kinetics of Intermolecular Interactions

2021

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Moment theory was applied to the kinetic study of intermolecular interactions. The association equilibrium constant (K A ) and association (k a ) and dissociation (k d ) rate constants of chemical reactions were analytically determined on the basis of the moment theory from elution peak profiles measured by highperformance liquid chromatography (HPLC). The HPLC data were measured under the conditions that neither immobilization nor fluorescence labeling of solute and ligand molecules is required. These are the advantages of the moment analysis method for determining accurate values of K A , k a , and k d . Moment equations were developed on the basis of the Einstein equation for diffusion, the random walk model, and the general rate model of chromatography. The moment analysis method was applied to the inclusion complex formation system between dibenzo-18-crown-6 or dibenzo-15-crown-5 and alkali metal cations. It was demonstrated that the values of K A , k a , and k d can be determined on the assumption that the stoichiometry between crown ethers and cations is 1:1 or 2:1. The influence of the difference in the size between the inner cavity of crown ethers and cations on the association and dissociation of the inclusion complex was considered. The moment analysis method using HPLC is effective for analyzing intermolecular interactions from various perspectives because it is based on the separation technique and has different characteristics from other methods such as spectroscopy. The results of this study contribute to the dissemination of an opportunity for studying intermolecular interactions from equilibrium and kinetic points of view to many researchers because HPLC is widespread.

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Section: Introductionmentioning

confidence: 99%

Moment Theory of Chromatography for the Analysis of Reaction Kinetics of Intermolecular Interactions

2021

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“…Capillary electrophoresis (CE) can be used as an alternative. − Association equilibrium constant ( K A ) and association ( k a ) and dissociation ( k d ) rate constants of intermolecular interactions are determined by using CE under the conditions that neither immobilization nor chemical modification of solute or ligand molecules is usually required. However, in some cases, the values of k a and k d are estimated by a curve-fitting approach so that the electropherograms numerically simulated agree with experimental data.…”

Section: Introductionmentioning

confidence: 99%

Moment Analysis Method for Measurement of Reaction Equilibrium and Rate Constants by Using High-Performance Liquid Chromatography

Miyabe,

Ishitobi,

Hiyama

et al. 2024

Anal. Chem.

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The moment analysis method was developed for the determination of association equilibrium constant (K A ) and association (k a ) and dissociation (k d ) rate constants of intermolecular interactions between solute and ligand molecules. They are accurately determined by using moment equations from elution peak profiles because they are measured by using high-performance liquid chromatography (HPLC) under preferable conditions that neither immobilization nor chemical modification (i.e., fluorescence labeling) of solute and ligand molecules is required. To demonstrate the effectiveness of the method, it was applied to the inclusion complex formation system between dibenzo-18-crown-6 (DB18C6) and alkaline earth metal cations, i.e., Mg 2+ , Ca 2+ , and Sr 2+ , as a concrete example. Because the diameter of the three metal cations is smaller than that of the inner cavity of DB18C6, the values of K A , k a , and k d were analytically determined by assuming the stoichiometry of 1:1 between DB18C6 and the metal cation. They reflected the influence of the difference in the size between the inner cavity of DB18C6 and the metal cations on the inclusion complex formation. It seems that the moment analysis method based on HPLC separation is effective for the multifaceted analysis of chemical reactions because some characteristics of the method are different from those of other conventional methods. It must contribute to the dissemination of an opportunity for the study of chemical reactions to many researchers because of the versatility of HPLC.

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Kinetic Study of Solute Permeation across Surfactant Micelle/Bulk Solvent Interface by Moment Analysis - Chromatographic Capillary Electrophoresis (MA-CCE)

Miyabe¹,

Suzuki²

2016

Bulletin of the Chemical Society of Japan

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We applied moment analysis (MA) with chromatographic capillary electrophoresis (CCE) to the analytical determination of rate constants (kin and kout) of solute permeation at the interface between a bulk solvent and surfactant micelles. CE experiments were carried out in the MEKC system using thymol and sodium dodecylsulfate (SDS) as the solute and surfactant, respectively, under CCE conditions. In CCE mode, experimental conditions are controlled so that the migration of micelles, which dissolve single or plural solute molecules, is stopped in the axial direction of a capillary. Only solute molecules migrate in the capillary and are detected to record elution peak profiles. The mass-transfer kinetics of solute molecules in the capillary are determined from the elution peak profiles by the MA theory. The values of kin and kout were respectively determined as 1.5 × 10−6 and 2.6 × 10−9 m s−1 for the permeation of thymol molecules at the interfacial boundary of SDS micelle. It was demonstrated that MA-CCE was effective for the kinetic study of solute permeation across the interface between a bulk solvent and spherical molecular aggregates, e.g., surfactant micelles.

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Affinity Capillary Electrophoresis as a Tool to Characterize Intermolecular Interactions

Cited by 4 publications

References 91 publications

Moment Theory of Chromatography for the Analysis of Reaction Kinetics of Intermolecular Interactions

Moment Theory of Chromatography for the Analysis of Reaction Kinetics of Intermolecular Interactions

Moment Analysis Method for Measurement of Reaction Equilibrium and Rate Constants by Using High-Performance Liquid Chromatography

Kinetic Study of Solute Permeation across Surfactant Micelle/Bulk Solvent Interface by Moment Analysis - Chromatographic Capillary Electrophoresis (MA-CCE)

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