Dynamic effect of secondary equilibria in reversed-phase chromatography

Melander, Wayne R.; Lin, Hui-Rong; Jacobson, Jana; Horváth, Cs.

doi:10.1021/j150664a017

Cited by 125 publications

(57 citation statements)

References 2 publications

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Section: Discussionmentioning

confidence: 99%

“…[40][41][42][43] However, the contribution of axial dispersion to band broadening is not taken into account in the chromatographic theories. 40,42 Some methods based on CE have also been developed for the kinetic study of intermolecular interactions, 44 e.g., affinity capillary electrophoresis, 45 exponential decay method, 46 and kinetic capillary electrophoresis (KCE). [47][48][49][50][51] In these methods, ka and kd are determined by matching electropherograms or exponential decay curves numerically calculated by changing the rate constants to those experimentally measured.…”

Section: Discussionmentioning

confidence: 99%

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Moment Analysis Theory for Size Exclusion Capillary Electrochromatography with Chemical Reaction of Intermolecular Interaction

Miyabe

Suzuki

2017

ANAL. SCI.

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New moment equations were developed for size exclusion capillary electrochromatography (SECEC), in which intermolecular chemical reactions simultaneously took place. They explain how the first absolute and second central moments of elution peaks are correlated with some fundamental equilibrium and kinetic parameters of mass transfer and chemical reaction in SECEC column. In order to demonstrate the effectiveness of the moment equations, they were used to predict chromatographic behavior under hypothetical SECEC conditions. It was quantitatively studied how the association and dissociation rate constants of intermolecular interaction affected the position and spreading of elution peaks. It was indicated that both the intermolecular reaction kinetics and axial dispersion of solute molecules in a capillary column had a predominant contribution to the band broadening.

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Section: Discussionmentioning

confidence: 99%

Section: Discussionmentioning

confidence: 99%

Moment Analysis Theory for Size Exclusion Capillary Electrochromatography with Chemical Reaction of Intermolecular Interaction

Miyabe

Suzuki

2017

ANAL. SCI.

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“…Kinetic studies of the ligand exchange reaction Melander et al 20 have proposed a model relating the chromatographic profile for the species undergoing equilibrium during the chromatographic process with kinetic parameters. When the relaxation of the chemical reaction in the mobile phase is much shorter than that of the separation, only one peak will be observed.…”

Section: Methodsmentioning

confidence: 99%

Equilibrium and Kinetic Studies on Ligand Exchange Reaction of Aluminum(III)-5-sulfoquinoline-8-ol Complex with Fluoride Ion by Reversed-Phase Ion-Pair Liquid Chromatography

1997

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The reversed-phase ion-pair liquid chromatographic behavior of the complex of aluminum ion with 5-sulfoquinoline-8-ol (HQS) was investigated on the column packed with a polystyrene-divinylbenzene copolymer with the mobile phase containing fluoride ion. It was found that the fluoride ion replaces one or two HQS molecules from the aluminum-HQS complex to form the mixed ligand complexes, which resulted in the appearance of two or more peaks in the chromatograms obtained for aluminum ion. The compositions of the mixed ligand complexes were estimated from the dependence of the areas of the peaks on the mobile phase concentrations of HQS and fluoride ion. The equilibrium and rate constants for the ligand exchange reaction were also evaluated and the reaction mechanism was presented. Aluminum ion could be completely separated from gallium ion by utilizing the ligand exchange reaction. It is now universally recognized that aluminum is toxic to a wide variety of living organisms. This has created the need for rapid and reliable methods for the determination of trace amounts of dissolved aluminum in biological and environmental samples. Various colorimetric and fluorometric methods based on the complexation with chelating agents have been developed for this purpose. '-9 5-Sulfoquinoline-8-ol (HQS) has been well documented on the fluorometric reaction with aluminum10'1' and has been extensively used for the determination of trace amounts of aluminum by fluorometry, flow injection analysis and high-performance liquid chromatography.8"2-15 However, only a few investigations have been carried out on the complexation reaction of aluminum ion with HQS and the mechanism has not yet been clarified. We have recently investigated the reversed-phase ion-pair liquid chromatographic behavior of aluminum complexes with HQS in the phosphate media with a fluorescence detector16'17 and have shown that the reaction between aluminum ion and HQS produced two species of aluminum-HQS complexes. These two species were assigned to the complex of aluminum with HQS and a mixed ligand complex with HQS and phosphate ion. The equilibrium of the interconversion reaction between these two species depended on the column temperature, the concentrations t To whom correspondence should be addressed.of HQS and phosphate ion in the eluent and pH value. Traditionally, spectrophotometric methods have been used to study the equilibrium and kinetics of chemical reactions in solution. However, these methods require that the spectra of the reactant and the product be different from each other, because the progress of the reaction is followed by directly monitoring the entire reaction mixture. A preliminary experiment revealed that the complex of aluminum with HQS and the mixed ligand complex with HQS and phosphate ion have nearly the same fluorometric spectra. Although their UV absorption spectra may be different from each other, the aluminum complex species cannot be distinguished in the presence of an excess amount of HQS, since HQS exhibits the absorption ban...

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“…Because several may exist in the mobile phase, inter-conversion between these species will affect chromatographic performance [17]. Horváth et al studied the effect of secondary equilibria on chromatographic peak shapes in detail [82,83]. Their results showed that, if the rate of inter-conversion is slow, the species will be resolved and multiple peaks will be detected.…”

Section: Hplc Analysis Of Anthocyaninsmentioning

confidence: 99%

“…Therefore the critical region define by 0.1 < Da < 100 is where secondary equilibria will affect chromatographic performance ( Fig. 2.8) [82].…”

Section: Hplc Analysis Of Anthocyaninsmentioning

confidence: 99%

Comprehensive two-dimensional liquid chromatographic analysis of anthocyanins

Willemse¹,

Stander²,

Tredoux³

et al. 2014

Journal of Chromatography A

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Dynamic effect of secondary equilibria in reversed-phase chromatography

Cited by 125 publications

References 2 publications

Moment Analysis Theory for Size Exclusion Capillary Electrochromatography with Chemical Reaction of Intermolecular Interaction

Moment Analysis Theory for Size Exclusion Capillary Electrochromatography with Chemical Reaction of Intermolecular Interaction

Equilibrium and Kinetic Studies on Ligand Exchange Reaction of Aluminum(III)-5-sulfoquinoline-8-ol Complex with Fluoride Ion by Reversed-Phase Ion-Pair Liquid Chromatography

Comprehensive two-dimensional liquid chromatographic analysis of anthocyanins

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