Exchange of polymer molecules between block copolymer micelles studied by emission spectroscopy. A method for the quantification of unimer exchange rates

Amphiphilic block copolymers, composed of poly(sodium methacrylate) (PMANa) as the water soluble sequence and poly((dimethylamino)ethyl methacrylate) (PDMAEMA) as the hydrophobic sequence, were anionically synthesized. Due to their amphiphilic character, these polymers aggregate into micelles in aqueous solutions. Of particular interest is the possibility of exchange of free chains, called unimers, between micelles and the bulk and the quantification of the exchange rate. The exchange of unimers between the micellar aggregates was determined spectroscopically. A donor molecule, naphthalene, was covalently bound to the hydrophobic blocks of the copolymers, while the acceptor, pyrene, was dissolved in aggregates built up from an identical, but unlabeled, copolymer. The energy transfer from an excited donor to a ground-state acceptor, with subsequent emission from the acceptor, was used to follow the migration of donor-labeled chains into micelles containing the dissolved acceptor. These data were analyzed according to a kinetic model, and the respective kinetic parameters could be determined. The influence of the relative composition of the block copolymer on the exchange rate was investigated to illustrate the usability of the kinetic model. While keeping the relative amount of comonomers as well as the molecular weights constant, the molecular architecture was also studied: hence the diblock (PDMAEMA-b-PMANa) and the corresponding triblocks (PDMAEMA-b-PMANa-b-PDMAEMA) and (PMANa-b-PDMAEMA-b-PMANa) were investigated.