Monoclonal behavior of molecularly imprinted polymer nanoparticles in capillary electrochromatography

A new approach based on miniemulsion polymerization is demonstrated for synthesis of molecularly imprinted nanoparticles (MIP-NP; 30-150 nm) with "monoclonal" binding behavior. The performance of the MIP nanoparticles is characterized with partial filling capillary electrochromatography, for the analysis of rac-propranolol, where (S)-propranolol is used as a template. In contrast to previous HPLC and CEC methods based on the use of MIPs, there is no apparent tailing for the enantiomer peaks, and baseline separation with 25,000-60,000 plate number is achieved. These effects are attributed to reduction of the MIP site heterogeneity by means of peripheral location of the core cross-linked NP and to MIP-binding sites with the same ordered radial orientation. This new MIP approach is based on the substitution of the functional monomers with a surfactant monomer, sodium N-undecenoyl glycinate (SUG) for improved inclusion in the MIP-NP structure and to the use of a miniemulsion in the MIP-NP synthesis. The feasibility of working primarily with aqueous electrolytes (10 mM phosphate with a 20% acetonitrile at pH 7) is attributable to the micellar character of the MIP-NPs, provided by the inclusion of the SUG monomers in the structure. To our knowledge this is the first example of "monoclonal" MIP-NPs incorporated in CEC separations of drug enantiomers.