Estimation of Solute-Stationary Phase and Solute-Mobile Phase Interactions in the Presence of Ionic Liquids

The presence of free silanols on alkyl-bonded reversed-phase stationary phases is responsible for broad and asymmetrical peaks when basic drugs are chromatographed with conventional octadecylsilane (C18) columns due to ionic interactions. In the last few years, ionic liquids (ILs) have attracted att...

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Main Author: María José Ruiz-Ángel
Format: Article
Language:English
Published: MDPI AG 2019-08-01
Series:Separations
Subjects:
Online Access:https://www.mdpi.com/2297-8739/6/3/40
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author María José Ruiz-Ángel
author_facet María José Ruiz-Ángel
author_sort María José Ruiz-Ángel
collection DOAJ
description The presence of free silanols on alkyl-bonded reversed-phase stationary phases is responsible for broad and asymmetrical peaks when basic drugs are chromatographed with conventional octadecylsilane (C18) columns due to ionic interactions. In the last few years, ionic liquids (ILs) have attracted attention to reduce this undesirable silanol activity. ILs should be considered as dual modifiers (with a cationic and anionic character), which means that both cations and anions are able to adsorb on the stationary phase, creating a positively or negatively charged layer, depending on the relative adsorption. The accessibility of basic compounds to the silanols is prevented by both the IL cation and anion, improving the peak profiles. A comparative study of the performance of six imidazolium-based ILs, differing in their cation/anions, as modifiers of the chromatographic behavior of a group of ten β-adrenoceptor antagonists, is addressed. Mobile phases containing cationic amines (triethylamine and dimethyloctylamine) were used as a reference for the interpretation of the results. Using a mathematical model based on two chemical equilibria, the association constants between the solutes and modified stationary phase as well as those between solutes and the additive in the mobile phase were estimated. These values, together with the changes in retention and peak shape, were used to obtain conclusions about the retention mechanism, changes in the nature of the chromatographic system, and silanol suppression effect.
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spelling doaj.art-5dffe63323b04a8e83636388e0ddddbd2022-12-22T04:01:28ZengMDPI AGSeparations2297-87392019-08-01634010.3390/separations6030040separations6030040Estimation of Solute-Stationary Phase and Solute-Mobile Phase Interactions in the Presence of Ionic LiquidsMaría José Ruiz-Ángel0Departament de Química Analítica, Universitat de València, 46010 València, SpainThe presence of free silanols on alkyl-bonded reversed-phase stationary phases is responsible for broad and asymmetrical peaks when basic drugs are chromatographed with conventional octadecylsilane (C18) columns due to ionic interactions. In the last few years, ionic liquids (ILs) have attracted attention to reduce this undesirable silanol activity. ILs should be considered as dual modifiers (with a cationic and anionic character), which means that both cations and anions are able to adsorb on the stationary phase, creating a positively or negatively charged layer, depending on the relative adsorption. The accessibility of basic compounds to the silanols is prevented by both the IL cation and anion, improving the peak profiles. A comparative study of the performance of six imidazolium-based ILs, differing in their cation/anions, as modifiers of the chromatographic behavior of a group of ten β-adrenoceptor antagonists, is addressed. Mobile phases containing cationic amines (triethylamine and dimethyloctylamine) were used as a reference for the interpretation of the results. Using a mathematical model based on two chemical equilibria, the association constants between the solutes and modified stationary phase as well as those between solutes and the additive in the mobile phase were estimated. These values, together with the changes in retention and peak shape, were used to obtain conclusions about the retention mechanism, changes in the nature of the chromatographic system, and silanol suppression effect.https://www.mdpi.com/2297-8739/6/3/40ionic liquidsbasic drugsRPLCpeak shapechemical equilibria
spellingShingle María José Ruiz-Ángel
Estimation of Solute-Stationary Phase and Solute-Mobile Phase Interactions in the Presence of Ionic Liquids
Separations
ionic liquids
basic drugs
RPLC
peak shape
chemical equilibria
title Estimation of Solute-Stationary Phase and Solute-Mobile Phase Interactions in the Presence of Ionic Liquids
title_full Estimation of Solute-Stationary Phase and Solute-Mobile Phase Interactions in the Presence of Ionic Liquids
title_fullStr Estimation of Solute-Stationary Phase and Solute-Mobile Phase Interactions in the Presence of Ionic Liquids
title_full_unstemmed Estimation of Solute-Stationary Phase and Solute-Mobile Phase Interactions in the Presence of Ionic Liquids
title_short Estimation of Solute-Stationary Phase and Solute-Mobile Phase Interactions in the Presence of Ionic Liquids
title_sort estimation of solute stationary phase and solute mobile phase interactions in the presence of ionic liquids
topic ionic liquids
basic drugs
RPLC
peak shape
chemical equilibria
url https://www.mdpi.com/2297-8739/6/3/40
work_keys_str_mv AT mariajoseruizangel estimationofsolutestationaryphaseandsolutemobilephaseinteractionsinthepresenceofionicliquids