Anal. Chem., 80 (8), 2881 -2887, 2008. 10.1021/ac070038v S0003-2700(07)00038-8
Web Release Date: March 13, 2008

Copyright © 2008 American Chemical Society

Monoclonal Behavior of Molecularly Imprinted Polymer Nanoparticles in Capillary Electrochromatography

Feliciano Priego-Capote, Lei Ye, Sadia Shakil, Shahab A. Shamsi, and Staffan Nilsson*

Department of Analytical Chemistry, Córdoba University, Annex C-3 Building, Campus of Rabanales, E-14071 Córdoba, Spain, Department of Chemistry, Center of Biotechnology and Drug Design, Georgia State University, Atlanta, Georgia 30303, and Department of Pure and Applied Biochemistry, Center for Chemistry and Chemical Engineering, Lund University, P.O. Box 124, SE-221 00 Lund, Sweden

Received for review January 8, 2007. Accepted May 14, 2007.

Abstract:

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.


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