Single drop microextraction using commercial capillary electrophoresis instruments.

Single drop microextraction (SDME), a simple and efficient sample preconcentration method for capillary electrophoresis (CE), was performed using two different commercial CE instruments. With a CE instrument providing adjustable forward and backward pressures, a single drop of an aqueous acceptor phase covered with a thin layer of an organic phase was formed at the capillary tip by programming the sample-handling functions of the instrument to perform 3-phase SDME where the organic film is essentially a membrane. Analytes from an acidic donor phase were concentrated into a basic acceptor phase yielding 190-fold enrichment in 10 min. When the donor phase was agitated using a microstirrer, a 2000-fold enrichment was obtained in 10 min. For a less flexible CE instrument, 2-phase SDME was carried out with a large volume pentanol drop held by a Teflon sleeve, yielding 110-fold enrichments in 30 min. We demonstrate a practical and automated SDME-CE technique with accuracy and reproducibility that is easy to practice to attain matrix isolation and high concentration sensitivity.

In-line coupling of two-phase single drop microextraction and large volume stacking using an electroosmotic flow pump in nonaqueous capillary electrophoresis.

In order to improve the concentration sensitivity of capillary electrophoresis (CE), two sample preconcentration techniques, single drop microextraction (SDME) and large volume stacking using an electroosmotic flow pump (LVSEP), were coupled in-line in a commercial CE instrument. By simple programming of liquid handling sequences, a pentanol drop was prepared at the tip of a fused silica capillary over which a Teflon tube had been sleeved to serve as a hydrophobic support. After extraction of the analytes from an aqueous donor solution into the drop, the entire capillary column was filled with enriched pentanol extract. LVSEP, in which the sample matrix is automatically removed by the EOF, was then carried out using a methanolic run buffer. The overall enrichment factors for the analytes pentachlorophenol (PCP), 3-bromobenzoic acid (3-BBA), and 4-iodobenzoic acid (4-IBA), from a combination of 30min SDME and LVSEP on a 27cm capillary, were about 7000, even without agitation of the donor solution. The resulting limits of detection for PCP, 3-BBA, and 4-IBA were 0.7, 0.3 and 0.7nM, respectively. Since no modification of the existing CE instrument is necessary and a bare capillary is used for LVSEP, this scheme can be adapted quite easily for many CE applications that require high concentration sensitivity.