Fritless particle-loaded monoliths for chiral capillary electrochromatographic (CEC) separation were prepared. Silica particles containing a chiral selector are suspended in a monomer solution, which is drawn into the capillary followed by in situ polymerization. Thereby the silica-based particles containing the chiral selector are embedded in a nonchiral continuous bed. This kind of chiral stationary phase is inexpensive, easy, and reproducible to prepare and circumvents the preparation of frits. As a model, teicoplanin aglycone as chiral selector bonded to 3 microm silica particles was used. The applicability of this approach is demonstrated by means of the chiral separation of aliphatic and aromatic amino acids and dipeptides. As a further application, the chiral selector ristocetin A bonded to 3 microm silica particles was used for the enantiomeric separation of chiral alpha-hydroxy acids. Since alpha-hydroxy acids migrate toward the anode, a cationic charge-providing agent was copolymerized with the matrix. This served to reverse the direction of the electroosmatic flow (EOF).

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Perfluorinated carboxylic acids (PFCAs) represent an important group of persistent perfluorinated organic compounds commonly determined in environmental and biological samples. A reversed-phase HPLC method was developed based on derivatization of the PFCAs with the commercially available fluorescent reagent 3-bromoacetyl coumarin. The method was optimized and this resulted in the efficient separation of PFCAs containing from 3 to 12 carbon atoms in molecule in 25 min run. To improve sensitivity, the preconcentration step has been optimized using Oasis-WAX and C18 sorbents for SPE. A 100-fold preconcentration is achieved by solid-phase extraction with the sorbent C18 Sep-PAK to result in limits of detection in the range from 43 to 75 ppt for the analytes examined, and in the application of the method of water analysis.FigureChromatogram of mixture of perfluorinated carboxylic acids C3-PFCA – C12-PFCA with fluorescence detection after derivatization with 3-bromoacetyl coumarin (b), and blank (a)

A capillary electrophoretic method with UV detection for separation and quantitation of perfluorocarboxylic acids (PFCAs) from C6-PFCA to C12-PFCA has been developed. The optimization of measurement conditions included the choice of the most appropriate type and concentration of buffer in the background electrolyte (BGE), as well as the type and the content of an organic modifier. The optimal separation of investigated PFCAs was achieved with 50 mM phosphate buffer and 40% isopropanol in the BGE using direct UV detection. The optimum wavelength for direct UV detection was optimized at 190 nm. For indirect detection, several chromophores were studied. Five mM 3,5-Dinitrobenzoic acid (3,5-DNBA) in 20 mM phosphate buffer BGE and indirect UV detection at 280 nm gave the optimal detection and separation performance for the investigated PFCAs. The possibility of on-line preconcentration of solutes by stacking has been examined for indirect detection. The detection limits (LODs) determined for direct UV detection ranged from 2 microg/mL for C6-PFCA to 33 microg/mL for C12-PFCA. The LODs obtained for indirect UV detection were comparable to those obtained for direct UV detection.

Perfluorinated carboxylic acids (PFCAs), amphiphiles of anthropogenic origin, are spread worldwide throughout the environment. This work deals with their zone electrophoresis (ZE) separation on a chip with coupled columns and integrated conductivity detection. Analogies with the electrophoretic behavior of PFCAs and fatty acids were employed in a search for electrolyte conditions suitable for their separation. ZE separations in the water-ethanol electrolyte systems, based on differences in the ionic mobilities of the anions of PFCAs, provided favorable resolution and detection conditions of the homologues containing up to 10 carbon atoms in the alkyl chain. Concentration limits of detection of 0.3-6.5 micromol/L were attained for PFCAs (loaded by a 900 nL volume sample injection channel of the chip) under these separation conditions. The material of which the chip was made [poly(methylmethacrylate)] restricted its use in investigations of the separations of higher PFCA homologues as it was damaged by ethanolic and/or methanolic background electrolyte solutions required in experiments with these amphiphilic compounds.