Capillary organic cations

MEKC is also performed using cationic, nonionic, and zwitterionic surfactants. Widely employed are cationic surfactant consisting of a long chain tetralkylammonium salt, such as cetyltrimeth-ylammonium bromide, which causes the reversal of the direction of the EOE, due to the adsorption of the organic cation on the capillary wall. Other interesting options include the use of mixed micelles resulting from the simultaneous incorporation into the BGE of ionic and nonionic or ionic and zwitterionic surfactants. Chiral surfactants, either natural as bile salts [207] or synthetic [208] are employed for enantiomer separations. 

Miller, J. L., Khaledi, M. G., and Shea, D., Separation of polycyclic aromatic hydrocarbons by nonaqueous capillary electrophoresis using charge-transfer complexation with planar organic cations, Anal. Chem., 69,1223-1229,1997. 

Capillary zone electrophoresis provides effective separations of any charged species, including inorganic anions and cations, organic acids and amines, and large biomolecules such as proteins. For example, CZE has been used to separate a mixture of 36 inorganic and organic ions in less than 3 minutes.Neutral species, of course, cannot be separated. 

Beck, W. and Engelhardt, H., Capillary electrophoresis of organic and inorganic cations with indirect UV detection, Chromatographia, 33, 313, 1992. 

The selectivity of separation is mainly affected by parameters of the bulk electrolyte in the capillary. These include type of anion and cation, pH, ionic strength, concentration, addition of modifiers such as com-plexing agents, organic solvents, surfactants, etc. It is expressed in terms of mobility differences (A/i) or the mobility ratio s (a) ... 

The main difficulties in CE analysis of cationic surfactants arise from their strong adsorption to the capillary wall and their ability to form micelles at low concentrations. The addition of organic modifiers in high amounts or separation in absolutely non-aqueous media disrupt micelle formation within the sample and also effectiveness of the organic modifier to disrupt micelles of alkylbenzyl dimethyl ammonium... 

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. 

Ions are highly charged species by nature and lend themselves well to analysis by capillary electrophoresis (CE). In pharmaceutical analyses, we usually deal with small organic and inorganic anions and small cations or aliphatic amines. 

Ion exchange chromatography (Chapter 12) is a well-established technique applicable to the determination of particular types of organic and organometallic compounds and anions and cations as has capillary column coupling isotachoelectrophoresis (Chapter 13). 

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