Stacking effect via solvent polarity differences in micellar electrokinetic chromatography with aqueous-organic background electrolyte

In this manuscript, a new stacking mode for micellar electrokinetic chromatography with anionic micelles and neutral analytes was investigated. The variation in the velocity of the analytes between the sample and the separation zones, needed for stacking effects, was obtained by using solvents with different polarities, the concentration of salts and micelles being identical between the two zones. Whereas a pure aqueous solvent was used in the injection zone, up to 30% ACN was used in the separation zone. In such conditions, higher interactions between the analyte and the micelles are obtained in the sample zone than in the separation zone, this due to the presence of the organic solvent. As the velocity of neutral analyte depends on its interactions with the moving micelles, its speed will drop when crossing two distinct zones where in the second zone its interactions with the micelles are lower than in the outgoing zone. This will induce a stacking effect. This approach was validated using a background electrolyte in the separation zone made with 10 mM disodium hydrogen phosphate, 15 mM sodium dodecyl sulphate and 15% ACN. The three triazines (simazine, atrazine, and terbuthylazine), used as test analytes, were dissolved in 10 mM disodium hydrogen phosphate, 15 mM sodium dodecyl sulphate and either 15 or 0% ACN. A stacking factor of around 2 was obtained injecting the sample in 0% ACN rather than 15% ACN. This was in accordance with the theoretical values predicted measuring the effective mobilities in both zonesCOMPETE/QREN/UE and PTDC/QUI-QUI/116156/2009 and SFRH / BPD / 30548 / 200