Field-enhanced sample injection-micelle to solvent stacking in nonaqueous capillary electrophoresis

• Field-enhanced sample injection and micelle to solvent stacking (FESI-MSS) in nonaqueous capillary electrophoresis (NACE).
• FESI-MSS allowed longer sample injection and better sensitivity compared to FESI only in NACE.
• 214–625-fold enhancement and LODs of 0.15–0.7 ng/mL for tamoxifen and metabolites.

The low conductivity of separation electrolytes employed in nonaqueous capillary electrophoresis (NACE) limits the use of on-line sample concentration or stacking by field enhancement. Herein, micelle-to-solvent stacking (MSS) was performed by the simple injection of a micellar solution plug prior to electrokinetic injection of sample prepared under field-enhanced stacking conditions (known as field-enhanced sample injection, FESI). The proposed approach allowed a 214–625-fold improvement in peak signals for targeted anticancer drugs (e.g., tamoxifen) and its major metabolites in NACE using 100% methanol-based separation electrolyte that comprised of 7.5 mM deoxycholic acid sodium salt, 15 mM acetic acid and 1 mM 18-crown-6. These improvements yielded tamoxifen and its metabolites with 2–5 times better stacking efficiency as compared to those obtained without micellar solution injection or FESI only. This is comparable to the results typically achieved when FESI is combined with isotachophoresis (electrokinetic supercharging). The FESI-MSS-NACE was tested for the measuring levels of target drugs in plasma. The analytical figures of merit are also reported.

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