Generalized model of the linear theory of electromigration and its application to electrokinetic chromatography: Capillary zone electrophoretic systems with complex-forming equilibria
| Autor: | Pavel Dubský, Michal Malý, Gabriel S. Gerlero, Magda Dovhunová, Pablo A. Kler |
|---|---|
| Rok vydání: | 2019 |
| Předmět: |
Electrophoresis
Work (thermodynamics) Capillary action LINEAR THEORY OF ELECTROMIGRATION Electrolyte Buffers 010402 general chemistry 01 natural sciences Biochemistry Electromigration Analytical Chemistry Electrokinetic phenomena Electrolytes Cyclodextrins Chromatography TISELIUS’ EQUATION Chemistry 010401 analytical chemistry Organic Chemistry Linear system Ciencias Químicas Electrophoresis Capillary Charge (physics) Stereoisomerism General Medicine PEAKMASTER CYCLODEXTRIN 0104 chemical sciences Nonlinear system Linear Models ELEKTROKINETIC CHROMATOGRAPHY Química Analítica CIENCIAS NATURALES Y EXACTAS Software |
| Zdroj: | Journal of chromatography. A. 1610 |
| ISSN: | 1873-3778 |
| Popis: | We discuss several possible phenomena in electrophoretic systems with complexing agents present in the background electrolyte. In our previous work, we extended the linear theory of electromigration with the first-order nonlinear term, which originally applied to acid-base equilibria only, by generalizing it to any fast chemical equilibria. This extension provides us with a fresh insight into the well-established technique of elecktrokinetic chromatography (EKC). We combine mathematical analysis of the generalized model with its solution by means of the new version of our software PeakMaster 6, and experimental data. We re-examine the fundamental equations by Wren and Rowe and Tiselius in the frame of the generalized linear theory of electromigration. Besides, we show that selector concentration can increase inside the interacting-analyte zone due to its complexation with the analyte, which contradicts the generally accepted idea of a consumption of a portion of the selector inside the zone. Next, we focus our discussion on interacting buffers (i.e., buffer constituents that form a complex with the selector). We demonstrate how such side-interaction of the selector with another buffer constituent can influence measuring analyte-selector interactions. Finally, we describe occurrence and mobilities of system peaks in these EKC systems. We investigate systems with fully charged analytes and neutral cyclodextrins as selectors. Although the theory is not limited in terms of the charge and/or the degree of (de)protonation of any constituent, this setup allows us to find analytical solutions to generalized model under approximate, yet realistic, conditions and to demonstrate all important phenomena that may occur in EKC systems. An occurrence of system peaks in a system with fully charged selector is also investigated. Fil: Dovhunová, Magda. Charles University; República Checa Fil: Malý, Michal. Charles University; República Checa Fil: Dubský, Pavel. Charles University; República Checa Fil: Gerlero, Gabriel Santiago. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Centro de Investigaciones en Métodos Computacionales. Universidad Nacional del Litoral. Centro de Investigaciones en Métodos Computacionales; Argentina Fil: Kler, Pablo Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Centro de Investigaciones en Métodos Computacionales. Universidad Nacional del Litoral. Centro de Investigaciones en Métodos Computacionales; Argentina |
| Databáze: | OpenAIRE |
| Externí odkaz: |
|
Full Text from ScienceDirect