Efficient one-pot synthesis of hydrophilic and fluorescent molecularly imprinted polymer nanoparticles for direct drug quantification in real biological samples

Efficient one-pot synthesis of hydrophilic and fluorescent molecularly imprinted polymer (MIP) nanoparticles and their application as optical chemosensor for direct drug quantification in real, undiluted biological samples are described. The general principle was demonstrated by preparing tetracycline (Tc, a broad-spectrum antibiotic)-imprinted fluorescent polymer nanoparticles bearing hydrophilic polymer brushes via poly(2-hydroxyethyl methacrylate) (PHEMA) macromolecular chain transfer agent-mediated reversible addition-fragmentation chain transfer (RAFT) precipitation polymerization in the presence of a fluorescent monomer. The introduction of hydrophilic PHEMA brushes and fluorescence labeling onto/into the MIP nanoparticles proved to not only significantly improve their surface hydrophilicity and lead to their obvious specific binding and high selectivity toward Tc in the undiluted bovine serum, but also impart them with strong fluorescent properties. In particular, significant fluorescence quenching was observed upon their binding with Tc in such complex biological milieu, which makes these Tc-MIP nanoparticles useful optical chemosensor with a detection limit of 0.26 μM. Furthermore, such advanced functional MIP nanoparticles-based chemosensor was also successfully utilized for the direct, sensitive, and accurate determination of Tc in another biological medium (i.e., the undiluted pig serum) with average recoveries ranging from 98% to 102%, even in the presence of several interfering drugs.