Capacitively coupled contactless conductivity detection (C⁴D) is a new technique providing high sensitivity in capillary electrophoresis (CE) especially for small ions that can otherwise only be determined with indirect methods. In this work, direct determination and validation of valproic acid (VPA) in biological fluids was achieved using CE with C⁴D. VPA is of pharmacological interest because of its use in epilepsy and bipolar disorder. The running electrolyte solution used consisted of 10 mM 2-(N-morpholino)ethane sulfonic acid (MES)/dl-histidine (His) and 50 μM hexadecyltrimethylammonium bromide (HTAB) at pH 6.0. Caproic acid (CA) was selected as internal standard (IS). Analyses of VPA in serum, plasma and urine samples were performed in less than 3 min. The interference of the sample matrix was reduced by deproteinization of the sample with acetonitrile (ACN). The effect of the solvent type and ratio on interference was investigated. The limits of detection (LOD) and quantitation (LOQ) of VPA in plasma samples were determined as 24 and 80 ng/ml, respectively. The method is linear between the 2 and 150 μg/ml, covering well the therapeutic range of VPA (50–100 μg/ml).

The separation of different ring numbered polyaromatic hydrocarbons (PAHs) was accomplished by using cetyltrimethylammonium bromide (CTAB) in capillary electrokinetic chromatography. In order to increase the solubilities and selectivities of PAHs, acetonitrile (ACN) was used as an organic modifier. Under the optimised conditions, 11 aromatic compounds were separated within 14.5 min in a running electrolyte containing 10 mM phosphate, 30 mM CTAB, and 40% ACN at pH 6.0. The effects of CTAB and ACN concentrations, voltage and pH on the resolution were investigated. Reproducibilities of migration times range between 0.55 and 1.27 R.S.D.% and peak areas between 1.02 and 7.23 R.S.D.%. Limit of detections (LODs) range between 0.09 and 2.24 μg ml^−1. This new and fast separation method of PAHs was applied to cooked oil sample.

The enantioseparation of baclofen (4-amino-3-p-chlorophenylbutyric acid) was achieved by CE-LIF with highly sulfated β-CD (HS-β-CD) as chiral selector. Naphthalene-2,3-dicarboxaldehyde was used for the derivatization of nonfluorescent baclofen. HS-β-CD (2%) containing 50 mM borate buffer at pH 9.5 was chosen as the optimal running electrolyte and applied to the analysis of baclofen enantiomers in human plasma. The linearity of calibration curves (R^ 2 ≥ 0.998) for R-(-) and S-(+)-baclofen was in the 0.1-2.0 μM concentration range. After a simple ACN-protein precipitation, the LOD of baclofen in plasma sample was found as low as 50 nM.

Separation and determination of some common metal ions was achieved with methyl 3-amino-3-(pyridin-3-yl)propanoate dihydrochloride (MAPP) as an ion-pairing reagent and pyridine as a detectable counter-ion for indirect UV detection at 254 nm. The effects of the complexing reagent and chromophore concentrations, applied voltage, and organic solvent content on the separation were investigated. The optimized separation was carried out in a running electrolyte containing 16 mM MAPP and 20 mM pyridine at pH 4.0 and was successfully applied to the qualitative and quantitative analysis of Li⁺, Na⁺, Mg²⁺, Ca²⁺, Ba²⁺, Ni²⁺, and Zn²⁺ in pharmaceutical vitamin preparations and various water samples.

Polycyclic aromatic hydrocarbons (PAHs) including isomeric pairs were separated in capillary electrokinetic chromatography using a cationic surfactant cetylpyridinium bromide (CPBr) as additive. With addition of 2 mM CPBr into the running electrolyte, dynamic coating occurs in the capillary and EOF is reversed. Changes of electroosmotic and electrophoretic mobilities with increasing CPBr concentration were investigated. Under optimum separation conditions, running electrolyte contains 50% MeCN, 20 mM acetate, and 40 mM CPBr at pH = 4.0. Using high concentration of organic solvent, aggregation of surfactants into micelles is prevented. Significant retentions indicate solvophobic, n- and π-electron interactions between CPBr monomers and PAHs.