Micellar electrokinetic chromatography micelle

The elution order for neutral species in MEKC depends on the extent to which they partition into the micelles. Hydrophilic neutrals are insoluble in the micelle s hydrophobic inner environment and elute as a single band as they would in CZE. Neutral solutes that are extremely hydrophobic are completely soluble in the micelle, eluting with the micelles as a single band. Those neutral species that exist in a partition equilibrium between the buffer solution and the micelles elute between the completely hydrophilic and completely hydrophobic neutrals. Those neutral species favoring the buffer solution elute before those favoring the micelles. Micellar electrokinetic chromatography has been used to separate a wide variety of samples, including mixtures of pharmaceutical compounds, vitamins, and explosives. 

R., Khaledi, M. G. Quantitative structure-activity relationships studies with micellar electrokinetic chromatography. Influence of surfactant type and mixed micelles on estimation of hydrophobicity and bioavailability. J. Chromatogr. A 1996, 727, 323-335. 

Micellar electrokinetic chromatography is based on the effects of the interaction of the analyte with surfactant micelles on the electrophoretic process. 

Besides CZE and NACE, micellar electrokinetic chromatography (MEKC) is also widely used, and ionic micelles are used as a pseudo-stationary phase. MEKC can therefore separate both ionic and neutral species (see Chapter 2). Hyphenating MEKC with ESI/MS is problematic due to the non-volatility of micelles, which contaminate the ionization source and the MS detector, resulting in increased baseline noise and reduced sensitivity. However, MEKC—ESI/MS was applied by Mol et al. for identifying drug impurities in galantamine samples. Despite the presence of non-volatile SDS, all impurities were detected with submicrogram per milliliter sensitivity and could be further characterized by MS/MS. 

Micellar electrokinetic chromatography is a hybrid of electrophoresis and chromatography. Introduced by Terabe in 1984 (9), MEKC is one of the most widely used CE modes. Ionic micelles, formed from surfactants added... 

N Chen, Y Zhang, S Terabe, T Nakagawa. Effect of physicochemical properties and molecular structure on the micelle—water partition coefficient in micellar electrokinetic chromatography. J. Chromatogr. A 678 327-332 (1994). 

Figure 26-33 Separation of enantiomers of eight p blocker drugs by micellar electrokinetic chromatography at pH 8.0 in a 120-cm capillary at 30 kV. Micelles were formed by a polymer surfactant containing L-leucinate substituents for chiral recognition. The structure of one compound is shown. [From C. Akbay. S, A. A. Rizvi. and S. A. Shamsi, "Simultaneous Enantiosepcration and Tandem UV-MS Detection of Eight p-Blockers in Micellar Electrokinetic Chromatography Using a Chiral Molecular Micelle Anal. Chem. 2005, 77.1672.]...

Micellar electrokinetic chromatography is a form of chromatography because the micelles behave as a pseudostationary phase. Separation of neutral molecules is based on partitioning between the solution and the pseudostationary phase. The mass transfer term Cux is no longer 0 in the van Deemter equation 26-7, but mass transfer into the micelles is fairly fast and band broadening is modest. 

The water-soluble vitamins niacinamide (a neutral compound), riboflavin (a neutral compound), niacin (an anion), and thiamine (a cation) were separated by micellar electrokinetic chromatography in 15 mM borate buffer (pH 8.0) with 50 mM sodium dodecyl sulfate. The migration times were niacinamide (8.1 min), riboflavin (13.0 min), niacin (14.3 min), and thiamine (21.9 min). What would the order have been in the absence of sodium dodecyl sulfate Which compound is most soluble in the micelles ... 

The Effect of SDS Micelle on the Rate of a Reaction, J. Chem. Ed. 1992, 69, 1024 C. P. Palmer, Demonstrating Chemical and Analytical Concepts Using Electrophoresis and Micellar Electrokinetic Chromatography, J. Chem. Ed 1999, 76, 1542. 

Micellar electrokinetic chromatography (MEKC) is a modality of liquid chromatography having a surfactant molecule in the form of a micelle, which was introduced by Terabe et al. in 1984 [38]. The formation and separation occur in the capillary and, hence, it is also called micellar electrokinetic capillary chromatography (MECC). This modality is useful for some specific molecules having solubilities in micelles and, therefore, utilized for the separation and identification of such compounds with great efficiency, reproducibility, and low levels of detections. The most commonly used compounds for micelle formation are sodium dodecyl sulfate (SDS), sodium tetradecyl sulfate, sodium decanesulfonate, sodium /V-lauryl-/V-mcthyllauratc, sodium... 

Yan, L., A. Harrate, and C. Lee (1997). Online micellar electrokinetic chromatography-electrospray ionization mass spectrometry using anodically-migrating micelles. Anal. Chem., 69(10) 1820-1826. 

Mass distribution ratio in microemulsion electrokinetic chromatography, /cMeekc — Defined analogously to the -> mass distribution ratio (in - micellar electrokinetic chromatography), kMEKC, by replacing terms for micelles with corresponding terms for micro emulsion. 

Conceptually. CE enantioseparations are mainly applied to charged SAs. Micellar electrokinetic chromatography (MEKC) (introduced by Terabe et al. in 1984 488 ), in contrast, permits the separation of electrically neutral compounds. In enantiomer separation by MEKC. ionic pseudo-stationary phases, such as chiral micelles composed of chiral SO moieties, which migrate according to their electrophoretic mobility, may interact stereoselectively with the solutes to be separated. MEKC with synthetic (e.g. A-dodecoxycarbonylvalines, commercialized as SDVal by Waters) 1489.490) or naturally occurring chiral surfactants (e.g. bile salts) 1491-494). and cyclodextrin-moditied MEKC (most often SDS/CD combinations) 1495-498) are the mo.st widely used selector systems in MEKC. The topic of MEKC enantioseparation has been reviewed by Nishi )499). 

Chiral Separations by Micellar Electrokinetic Chromatography with Chiral Micelles... 

Since micellar electrokinetic chromatography (MEKC) was hrst introduced in 1984, it has become one of major separation modes in capillary electrophoresis (CE), especially owing to its applicability to the separation of neutral compounds as well as charged ones. Chiral separation is one of the major objectives of CE, as well as MEKC, and a number of successful reports on enantiomer separations by CE and MEKC has been published. In chiral separations by MEKC, the following two modes are normally employed (a) MEKC using chiral micelles and (b) cyclodextrin (CD)-modilied MEKC (CD-MEKC ... 

S. Terabe, Micellar electrokinetic chromatography, in Capillary Electrophoresis Technology (N. A. Guzman, ed.), Marcel Dekker, Inc., New York, 1993, pp. 65-87. J. N. Israelchvilli, in Physics of Amphiphiles Micelles, Vesicles and Microemulsions (V. Degiorgio and M. Corti, eds.). Proceedings of the International School of Physics Enrico Eermi, CourseXC, North-Holland, Amsterdam, 1985, pp. 24-37. 

The distribution coefficient, K, of a solute for an equilibrium between the aqueous phase and micelle, or the micellar solubilization, depends on temperature generally, the distribution coefficient decreases with an increase in temperature. This means that the migration time of a solute, will be reduced when the temperature is elevated under typical micellar electrokinetic chromatography (MEKC) conditions, where, for example, sodium dodecyl sulfate (SDS) is employed as a pseudo-stationary phase at a neutral condition (i.e., pH 7). Also, the velocity of the electro-osmotic flow (EOF), Meof> and the electrophoretic velocity of the micelle, (me), will be increased by an increase in temperature because of a reduced viscosity of the micellar solution employed in a MEKC system. 

Yang, S.Y., Bumgarner, J.G., Kruk, L.F. and Khaledi, M.G. (1996). Quantitative Structure-Activity Relationships Studies with Micellar Electrokinetic Chromatography Influence of Surfactant Type and Mixed Micelles on Estimation of Hydrophobicity and Bioavailability. J.Chro-mat, 721A, 323-335. 

The technique is therefore particularly suited to water-soluble species which possess a charge, which includes most dyes. Variations from the main technique (often referred to as capillary zone electrophoresis, CZE) do exist and these include the use of surfactants in the buffer to create micelles (often thought of as creating a pseudo-stationary phase inside the capillary) which then improve the separation of neutral species (and frequently charged molecules) owing to hydrophobic interactions. The term micellar electrokinetic chromatography (MECC or MEKC) is often used for CE separations carried out with the aid of a micellar buffer solution. 

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