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Modelling the pH dependent retention and competitive adsorption of charged and ionizable solutes in mixed-mode and reversed-phase liquid chromatography
Karlstad University, Faculty of Health, Science and Technology (starting 2013), Department of Engineering and Chemical Sciences (from 2013).
Karlstad University, Faculty of Health, Science and Technology (starting 2013), Department of Engineering and Chemical Sciences (from 2013).ORCID iD: 0000-0002-1840-616X
Karlstad University, Faculty of Health, Science and Technology (starting 2013), Department of Engineering and Chemical Sciences (from 2013).ORCID iD: 0000-0003-1819-1709
2024 (English)In: Journal of Chromatography A, ISSN 0021-9673, E-ISSN 1873-3778, Vol. 1730, article id 465058Article in journal (Refereed) Published
Abstract [en]

This study investigated the influence of pH on the retention of solutes using a mixed-mode column with carboxyl (-COOH) groups acting as weak cation exchanger bonded to the terminal of C18 ligands (C18-WCX column) and a traditional reversed-phase C18 column. First, a model based on electrostatic theory was derived and successfully used to predict the retention of charged solutes (charged, and ionizable) as a function of mobile phase pH on a C18-WCX column. While the Horváth model predicts the pH-dependent retention of ionizable solutes in reversed-phase liquid chromatography (RPLC) solely based on solute ionization, the developed model incorporates the concept of surface potential generated on the surface of the stationary phase and its variation with pH. To comprehensively understand the adsorption process, adsorption isotherms for these solutes were individually acquired on the C18-WCX and reversed-phase C18 columns. The adsorption isotherms followed the Langmuir model for the uncharged solute and the electrostatically modified Langmuir model for charged solutes. The elution profiles for the single components were calculated from these isotherms using the equilibrium dispersion column model and were found to be in close agreement with the experimental elution profiles. To enable modelling of two-component cases involving charged solute(s), a competitive adsorption isotherm model based on electrostatic theory was derived. This model was later successfully used to calculate the elution profiles of two components for scenarios involving (a) a C18 Column: two charged solutes, (b) a C18 Column: one charged and one uncharged solute, and (c) a C18-WCX Column: two charged solutes. The strong alignment between the experimental and calculated elution profiles in all three scenarios validated the developed competitive adsorption model. 

Place, publisher, year, edition, pages
Elsevier, 2024. Vol. 1730, article id 465058
Keywords [en]
Adsorption, Adsorption isotherms, Column chromatography, Ionization of liquids, Ionization potential, Liquid chromatography, electrolyte, polypropylene, Adsorption modeling, Charged solutes, Competitive adsorption, Competitive adsorption model, Electrostatic retention model, Elution profiles, Mixed mode, Mixed-mode liquid chromatography, Retention mechanism, Retention modeling, adsorption, algorithm, anion exchange, Article, chromatography, chromatography by stationary phase, column chromatography, elution, equilibrium constant, flow rate, high performance liquid chromatography, ionization, isotherm, pH, retention time (chromatography), reversed phase liquid chromatography, static electricity, ultraviolet irradiation, Electrostatics
National Category
Analytical Chemistry
Research subject
Chemistry
Identifiers
URN: urn:nbn:se:kau:diva-100711DOI: 10.1016/j.chroma.2024.465058ISI: 001254982900001Scopus ID: 2-s2.0-85195665282OAI: oai:DiVA.org:kau-100711DiVA, id: diva2:1878130
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Karlstad UniversityAvailable from: 2024-06-26 Created: 2024-06-26 Last updated: 2024-07-05Bibliographically approved

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Haseeb, AbdulFernandes, Miguel XavierSamuelsson, Jörgen

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