Solvent effect on adsorption phenomena in reversed‐phase liquid chromatography

Miyabe, Kanji; Suzuki, Motoyuki

doi:10.1002/aic.690410312

Cited by 27 publications

(36 citation statements)

References 28 publications

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“…Clearly, there is no argument that eluite interactions with the hydrocarbonaceous bonded phases under conditions of gas chromatography are quite strong. This finding of the Gedanken experiment was later confirmed by Miyabe and Suzuki [48,143] who investigated the effect of solvent on adsorption characteristics in liquid-phase chromatography by comparing experimental adsorption data for several organics in both gas-and liquid-phase systems using octadecylsilyl silica gel columns. Even Horváth and Melander [12] recognized this phenomenon when adapting the solvophobic treatment to describe retention in RPC.…”

Section: Criticisms Of the Solvophobic Theorymentioning

confidence: 60%

“…Miyabe and Suzuki [48] measured the equilibrium constants for the adsorption of several organic compounds on C 18 bonded phase in RPC employing methanol/water mobile phase systems as well as in gas chromatography. [48] Compound convenience of calculations. The correlation between experimentally observed and theoretically calculated DG solv o values was reasonable for small eluites like toluene, pentane and cyclohexane, but poor for eluites with long alkyl chains, such as n-hexane, n-heptane and n-octane.…”

Section: Prediction Of Retention Factormentioning

confidence: 99%

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Fundamentals of Reversed Phase Chromatography: Thermodynamic and Exothermodynamic Treatment

Vailaya

2005

Journal of Liquid Chromatography & Related Technologies

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Reversed phase chromatography (RPC) is the most popular branch of HPLC for the analysis and purification of a wide variety of substances. Despite significant advances in both our knowledge and understanding of the fundamental principles governing the retention behavior in RPC, there is considerable debate in the literature regarding the mechanism of retention. This review addresses the theoretical foundation of the chromatographic technique, with an emphasis on thermodynamic and exothermodynamic treatment of retention equilibrium, as well as their implication on the mechanistic aspects of RPC retention. A unified and rigorous treatment based on the solvophobic theory is reviewed in terms of its ability to shed light on the physicochemical underpinnings of the retention in RPC, and to quantitatively predict the retention behavior of nonpolar compounds, acids and bases, and peptides and proteins. Also highlighted are areas of future challenges in the theory and practice of RPC, potentially leading to a better quantitative understanding and use of the popular technique. It is undoubtedly the unsung champion of the modern biological sciences, enabling the intricacies of cellular biology to be at last discriminated in detail. [2] Without the recent advances in HPLC, modern biology, functional genomics, and proteomics would not exist. The incredible power of HPLC to discern the molecular diversity of biological phenomena is largely attributed to its ability to distinguish mass differences as little as 1 Da in a macromolecule, such as proteins when coupled with mass spectrometry, [3,4] to separate proteins that differ by only a single amino acid, [5] to separate conformational isomers of a long chain polypeptide, [6] and to resolve the different tertiary conformational structures of DNA fragments. [7] The exquisite sensitivity, the speed, and the impressive resolving power of modern HPLC find application in various fields, such as pharmaceutical, food and clinical analysis, pollution control, downstream processing, measurement of physicochemical properties of drugs as well as the separation of peptides, proteins, and nucleic acids. At the heart of the HPLC revolution is the mode of separation that we are all familiar with-reversed phase chromatography (RPC). The seminal works of Horváth and co-workers [8 -11] have contributed significantly to the theory and practice of RPC, resulting in its wide acceptance by the scientific community as a high resolution separation technique of choice. It is estimated that approximately 80% of HPLC analysis is conducted in this mode. [12] The success of this technique is attributed to the employment of microparticulate alkyl-silica monomeric bonded phases, such as octadecylated silica, which offers high separation efficiency combined with unparalleled convenience, versatility and reproducibility. The use of bonded hydrocarbonaceous stationary phases having a variety of functional groups and a wide choice of hydroorganic eluents to modulate retention offer a broad range of operating con...

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Section: Criticisms Of the Solvophobic Theorymentioning

confidence: 60%

Section: Prediction Of Retention Factormentioning

confidence: 99%

Fundamentals of Reversed Phase Chromatography: Thermodynamic and Exothermodynamic Treatment

Vailaya

2005

Journal of Liquid Chromatography & Related Technologies

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“…Determination of Column Void Volumes. Interparticle and intraparticle voids were determined respectively from the tracer retention times of blue dextran and sodium nitrate (Miyabe and Suzuki, 1995a). Different experiments at various flow rates and at two different concentrations of ethanol were tried to ensure that the void volumes—the porosities derived from these retention times—were free of any artifacts due to slow diffusion of nitrate or weak adsorption of blue dextran.…”

Section: Methodsmentioning

confidence: 99%

“…For low‐affinity solutes, isocratic pulse elution can be used for parameter estimation (Miyabe and Suzuki, 1995a,b; Snyder et al, 1979) when the sample concentration is low and the isotherm is in the linear range. For high‐affinity biochemicals, however, the retention is long, and peak broadening due to mass transfer can be so severe that peaks from isocratic elution are too diluted to be detected even by the most sensitive detectors available.…”

Section: Introductionmentioning

confidence: 99%

Estimation of Solvent‐Modulated Linear Adsorption Parameters of Taxanes from Dilute Plant Tissue Culture Broth

Tanzil

et al. 1996

Biotechnology Progress

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A stepwise elution technique is developed to estimate the linear solvent-modulated isotherm parameters of taxanes from dilute plant tissue culture broth. The technique is proven to be robust under various experimental conditions because mass transfer effects are decoupled from isotherm effects on elution bands. Simple algebraic equations are derived to relate isotherm parameters to the retention times at different solvent compositions in stepwise elution under volume overload conditions. A minimum loading volume, which is a function of mass transfer parameters, column geometries, and adsorption affinities, is estimated from moment analysis to ensure that band spreading due to mass transfer does not affect the accuracy of this method. The isotherms of a low-cost solute, phenylalanine, under different ethanol concentrations are measured by a standard multiple frontal chromatography method. The results serve as benchmarks for the parameters that are estimated over the same ethanol concentration range using the stepwise elution technique. The parameters determined from these two independent methods are in close agreement. For paclitaxel and cephalomannine, the retention times and peak shapes from plant tissue culture broth experiments are well predicted from rate model simulations using the parameters estimated from single-component elution data.

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“…5,7,8,[20][21][22][23] Under such conditions, it is energetically advantageous for adsorbed molecules to be desorbed from a surface to a bulk phase than to migrate on the surface, suggesting that surface diffusion phenomena are absent. In previous papers 5,20 the authors attempted to quantitatively explain the situation by applying solvophobic theory, that the results were partially attributed to the influence of a solvent on the liquid phase adsorption. The correlations between E s and Q st listed in Table 2 are connected with the thermodynamic properties of the surface diffusion.…”

Section: Second Moment Analysismentioning

confidence: 99%

Effect of the Type of Organic Modifiers on Mass Transfer in Reversed-Phase Liquid Chromatography

Miyabe

Takeuchi

1998

ANAL. SCI.

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Methanol/water and acetonitrile/water mixtures have generally been used as a mobile phase in reversedphase liquid chromatography (RP-LC). Chromatographic separations are significantly affected by the mobile-phase conditions, such as the type and composition of the organic modifiers. A number of studies have been made on the influence of the mobile-phase conditions on the retention behavior in RP-LC in connection with the specification of the separation mechanism and with the establishment of optimization strategies for chromatographic conditions.It is also essential to analyze the chromatographic processes from the viewpoints of mass-transfer kinetics and the thermodynamic properties as well as the retention behavior in order to understand the separation mechanism in RP-LC. However, there have not been very many kinetic studies on mass-transfer phenomena in RP packing materials [1][2][3][4] , in contrast to the extremely extensive studies on chromatographic retention. The authors have studied mass-transfer phenomena in RP-LC using mainly methanol/water and octadecylsilyl (ODS)-silica gel as mobile and stationary phases. 5-8Pulse-response experiments were made under various conditions of the solutes as well as the stationary and mobile phases. Their type, composition, and concentration were changed. Some items of information about the retention behavior, mass-transfer rates, and thermodynamic properties in RP-LC were obtained.This paper is concerned with the influence of the type of organic modifiers in the mobile phases on the chromatographic properties in RP-LC. The information about the retention behavior, mass-transfer rates, and thermodynamic properties were determined by using a mixture of acetonitrile and water (70/30, v/v) and an ODS-silica gel as a mobile and stationary phase. In a previous paper 9 , the authors reported on results of a similar study using alkylbenzenes and p-alkylphenols as solutes. In this study, the characteristics of the RP-LC system were analyzed in more detail using more solutes than before. In particular, it was attempted to correlate the surface diffusion coefficient (D s ) with various physical parameters of the solutes. The results in 70 vol% acetonitrile were compared with those in 70 vol% methanol. On the basis of the results, a few estimation procedures of D s have been proposed. In this paper, the mass-transfer and concentration phenomena of solutes from a bulk mobile phase to the surface of ODS-silica gel is represented by the word "adsorption" in a wide sense. The mechanism of the mass transfer, i.e., "partition or adsorption", is not defined. Experimental Column and reagentsSeveral properties of an ODS column (YMC) and the experimental conditions are given in Table 1. An ODS column packed with relatively large ODS-silica gel particles was used in order to make it easy to quantitatively analyze the influence of the mass-transfer rates on the peak spreading. The volumetric composition of acetonitrile was 70%, which was selected as a typical value of mobile-phase compositio...

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Solvent effect on adsorption phenomena in reversed‐phase liquid chromatography

Cited by 27 publications

References 28 publications

Fundamentals of Reversed Phase Chromatography: Thermodynamic and Exothermodynamic Treatment

Fundamentals of Reversed Phase Chromatography: Thermodynamic and Exothermodynamic Treatment

Estimation of Solvent‐Modulated Linear Adsorption Parameters of Taxanes from Dilute Plant Tissue Culture Broth

Effect of the Type of Organic Modifiers on Mass Transfer in Reversed-Phase Liquid Chromatography

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