Micelles electrophoretic mobility

For quite some time, there have been indications for a phase-separation in the shell of polyelectrolyte block copolymer micelles. Electrophoretic mobility measurements on PS-PMAc [50] indicated that a part of the shell exhibits a considerable higher ionic strength than the surrounding medium. This had been corroborated by fluorescence studies on PS-PMAc [51-53] and PS-P2VP-heteroarm star polymers [54]. According to the steady-state fluorescence and anisotropy decays of fluorophores attached to the ends of the PMAc-blocks, a certain fraction of the fluorophores (probably those on the blocks that were folded back to the core/shell interface) monitored a lower polarity of the environment. Their mobility was substantially restricted. It thus seemed as if the polyelectrolyte corona was phase separated into a dense interior part and a dilute outer part. Further experimental evidence for the existence of a dense interior corona domain has been found in an NMR/SANS-study on poly(methylmethacrylate-fr-acrylic acid) (PMMA-PAAc) micelles [55]. 

Surface active electrolytes produce charged micelles whose effective charge can be measured by electrophoretic mobility [117,156]. The net charge is lower than the degree of aggregation, however, since some of the counterions remain associated with the micelle, presumably as part of a Stem layer (see Section V-3) [157]. Combination of self-diffusion with electrophoretic mobility measurements indicates that a typical micelle of a univalent surfactant contains about 1(X) monomer units and carries a net charge of 50-70. Additional colloidal characterization techniques are applicable to micelles such as ultrafiltration [158]. 

Anions and uncharged analytes tend to spend more time in the buffered solution and as a result their movement relates to this. While these are useful generalizations, various factors contribute to the migration order of the analytes. These include the anionic or cationic nature of the surfactant, the influence of electroendosmosis, the properties of the buffer, the contributions of electrostatic versus hydrophobic interactions and the electrophoretic mobility of the native analyte. In addition, organic modifiers, e.g. methanol, acetonitrile and tetrahydrofuran are used to enhance separations and these increase the affinity of the more hydrophobic analytes for the liquid rather than the micellar phase. The effect of chirality of the analyte on its interaction with the micelles is utilized to separate enantiomers that either are already present in a sample or have been chemically produced. Such pre-capillary derivatization has been used to produce chiral amino acids for capillary electrophoresis. An alternative approach to chiral separations is the incorporation of additives such as cyclodextrins in the buffer solution. 

In MEKC, mainly anionic surface-active compounds, in particular SDS, are used. SDS and all other anionic surfactants have a net negative charge over a wide range of pH values, and therefore the micelles have a corresponding electrophoretic mobility toward the anode (opposite the direction of electro-osmotic flow). Anionic species do not interact with the negatively charged surface of the capillary, which is favorable in common CZE but especially in ACE. Therefore, SDS is the best-studied tenside in MEKC. Long-chain cationic ammonium species have also been employed for mainly anionic and neutral solutes (16). Bile salts as representatives of anionic surfactants have been used for the analysis of ionic and nonionic compounds and also for the separation of optical isomers (17-19). 

The electrophoretic mobility of sodium dodecyl sulfate micelles was determined by the moving-boundary method after the micelles were made visible by solubilizing dye in them. This quantity was measured at the critical micelle concentration (CMC) in the presence of various concentrations of NaCl. The radius of the micelles was determined by light scatteringj... 

In capillary electrophoresis, components of a mixture are separated according to two main factors electrophoretic mobility and electro-osmotic flow. These terms apply to ions, molecules or micelles. 

The electrical conductance shows a weaker concentration dependence above than below the CMC corresponding to a decrease in the equivalent conductance (Fig. 2.10). The transport number of the surfactant ion rises sharply at the CMC while that of the counterion may become negative. This as well as electrophoretic mobilities may yield information on micellar charge. At high concentrations, conductance anisotropies have been observed for flowing systems. This, as well as flow birefringence, is useful for the demonstration of nonspherical micelle shape. 

When an anionic surfactant such as SDS is used, the micelles migrate toward the anode as a result of electrophoretic mobility. The EOF in uncoated, fused silica capillaries, however, travels toward the cathode at a greater velocity than the micelles travel toward the anode, thereby dragging the micelles slowly toward the detector. When a neutral molecule is injected into the system, it partitions itself between the buffer and the micelle. The more time it spends in the micelle, the longer it will take to reach the detector. In MECC, therefore, the analytes all migrate between a water peak, which is totally unretained, and the micelle peak, which is the most retained. A typical elution order is shown in Figure 5.7, where peak EOF represents a neutral molecule that has no interaction with the micelles and therefore travels at the velocity of the EOF. 

For ionizable solutes, separation mechanisms rely not only on the partitioning of the nonionized forms in the micelles, but also on the electrophoretic mobility of the ionized form of the compounds in the aqueous phase. Electrostatic interactions between the ionic analytes and the charged surface of the micelles are also to be taken into consideration. 

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). 

However, surfactants incorporated into the electrolyte solution at concentrations below their critical micelle concentration (CMC) may act as hydrophobic selectors to modulate the electrophoretic selectivity of hydrophobic peptides and proteins. The binding of ionic or zwitterionic surfactant molecules to peptides and proteins alters both the hydrodynamic (Stokes) radius and the effective charges of these analytes. This causes a variation in the electrophoretic mobility, which is directly proportional to the effective charge and inversely proportional to the Stokes radius. Variations of the charge-to-hydrodynamic radius ratios are also induced by the binding of nonionic surfactants to peptide or protein molecules. The binding of the surfactant molecules to peptides and proteins may vary with the surfactant species and its concentration, and it is influenced by the experimental conditions such as pH, ionic strength, and temperature of the electrolyte solution. Surfactants may bind to samples, either to the... 

When the solute has an electrophoretic mobility Eq. (1) win be more complicated, that is, the migration of the ionic solute includes a portion generated by the micelle when the solute is incorporated into the micelle and also the other portion generated by the electrophoresis of the solute itself. 

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