The separation of a series of aromatic carboxylic acids, sulfonates and opiates using electrokinetic chromatography employing a mixture of the soluble cationic polymer poly(diallydimethylammonium chloride) (PDDAC) and the amphiphilic anion hexanesulfonate as pseudostationary phases is described. In this system, the PDDAC pseudostationary phase interacts with the anionic analytes, whereas the hexanesulfonate pseudostationary phase interacts with the cationic analytes. A migration model has been derived which takes into account the ion-exchange (IE) interactions between the anions and the cationic PDDAC as well as the ion-pair (IP) interactions between the opiates and the hexanesulfonate. A further interaction between the combined PDDAC-hexanesulfonate complex and the more hydrophobic analytes is also evident and is accounted for in the model. Constants obtained by applying the model agreed well with the expected trends in IE affinities of the anions for PDDAC and also corresponded with the hydrophobic natures of the analytes. Optimization of the PDDAC and hexanesulfonate concentrations was performed using the normalized resolution product and minimum resolution product criteria. The minimum resolution product criterion proved to be most successful. An advantage of the described system is the improvement in peak shapes obtained after addition of hexanesulfonate to the electrolyte, resulting in increased plate numbers and better resolution. The system was very robust with mobilities varying by less than 2% over a period of days and on using different capillaries.

Cationic polymerization

Micellar electrokinetic chromatography

Ammonium chloride

10.1002/1522-2683(200209)23:17<2821::aid-elps2821>3.0.co;2-l

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Investigation of Properties of a PTFE Capillary Used as the Separation Capillary in Capillary Electrophoresis

Mirek Macka Philip Zakaria Emily F. Hilder Pavel N. Nesterenko Paul R. Haddad

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Latex-Coated Polymeric Monolithic Ion-Exchange Stationary Phases. 1. Anion-Exchange Capillary Electrochromatography and In-Line Sample Preconcentration in Capillary Electrophoresis

Analytical Chemistry (2004)

Joseph P. Hutchinson Philip Zakaria Andrew R. Bowie Mirek Macka Nebojša Avdalović

A sulfonated methacrylate monolithic polymer has been synthesized inside fused-silica capillaries of diameters 50-533-microm i.d. and coated with 65-nm-diameter fully functionalized quaternary ammonium latex particles (AS18, Dionex Corp.) to form an anion-exchange stationary phase. This stationary phase was used for ion-exchange capillary electrochromatography of inorganic anions in a 75-microm-i.d. capillary with Tris/perchlorate electrolyte and direct UV detection at 195 nm. Seven inorganic anions (bromide, nitrate, iodide, iodate, bromate, thiocyanate, chromate) could be separated over a period of 90 s, and the elution order indicated that both ion exchange and electrophoresis contributed to the separation mechanism. Separation efficiencies of up to 1.66 x 10(5) plates m(-1) were achieved, and the monoliths were stable under pressures of up to 62 MPa. Another latex-coated monolith in a 250-microm-i.d. capillary was used for in-line preconcentration by coupling it to a separation capillary in which the EOF had been reversed using a coating of either a cationic polymer or cationic latex particles. Several capillary volumes of sample were loaded onto the preconcentration monolith, and the analytes (inorganic anions) were then eluted from the monolith with a transient isotachophoretic gradient before being separated by electrophoresis in the separation capillary. Linear calibration curves were obtained for aqueous mixtures of bromide, nitrite, nitrate, and iodide. Recoveries of all analytes except iodide were reduced significantly when the sample matrix contained high levels of chloride. The preconcentration method was applied to the determination of iodide in open ocean water and provided a limit of detection of 75 pM (9.5 ng/L) calculated at a signal-to-noise ratio of 3. The relative standard deviation for migration time and peak area for iodide were 1.1 and 2.7%, respectively (n = 6). Iodide was eluted as an efficient peak, yielding a separation efficiency of 5.13 x 10(7) plates m(-1). This focusing was reproducible for repeated analyses of seawater.

Iodate

Monolith

Isotachophoresis

Electrochromatography

Ion chromatography

Ammonium iodide

10.1021/ac048748d

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Citations (117)