Copolymer Micelles with Polyelectrolyte Shell in Aqueous Media. A Mean-Field Study

The multimolecular micelles formed by polystyrene- block -poly(methacrylic acid) (PS-PMA) copolymer and by hydrophobically modified PS-PMA copolymer with naphthalene and anthracene (PS-N-PMA-A) were studied by self-consistent field (SCF) calculations in aqueous media. The labeling with covalently bonded naphthalene between PS and PMA blocks and with anthracene at the free end of PMA blocks, which is suitable for experimental nonradiative excitation energy transfer (NRET) studies of PS-N-PMA-A micelles, modifies the structure of micellar shell. The study was aimed at understanding structure and behavior of micelles at different pH and ionic strength. The results show that the presence of hydrophobic tags has only a small influence on the overall structure of micelles but it strongly affects the distribution of PMA free ends. The hydrophobic labels (anthracenes) try to return into the shell and their certain fraction is localized close to the core/shell interface, which causes a fairly high NRET efficiency. The calculated and experimentally measured NRET efficiency were compared; their trends are reasonable at the semiquantitative level.