Association behavior of biotinylated and non-biotinylated poly(ethylene oxide)-b-poly(2-(diethylamino)ethyl methacrylate)

Biotinylated and non-biotinylated copolymers of poly(ethylene oxide) (PEO) and poly(2-(diethylamino)ethyl methacrylate) (PDEAEMA) were synthesized by the atom transfer radical polymerization technique. The chemical compositions of the copolymers as determined by NMR are represented by PEO(113)PDEAEMA(70) and biotin-PEO(104)PDEAEMA(93), respectively. The aggregation behavior of these polymers in aqueous solutions at different pHs and ionic strengths was studied using a combination of potentiometric titration, dynamic light scattering, static light scattering, and transmission electron microscopy. Both PEO-b-PDEAEMA and biotin-PEO-b-PDEAEMA diblock copolymers form micelles at high pH with hydrodynamic radii (Rh) of about 19 and 23 nm, respectively. At low pH, the copolymers are dispersed as unimers in solution with R-h values of about 6-7 nm. However, at a physiological salt concentration (c(s)) of about 0.16 M NaCl and a pH of 7-8, the copolymers form large loosely packed Gaussian chains, which were not present at the low c(s) of 0.001 M NaCl. The critical micelle concentrations (cmc's) and the cytotoxicities of the copolymers were investigated to determine a suitable polymer concentration range for future biological applications. Both PEO-b-PDEAEMA and biotin-PEO-b-PDEAEMA diblock copolymers possess identical cmc values of about 0.0023 mg/g, while the cytotoxicity test indicated that the copolymers are not toxic up to 0.05 mg/g (>83% cell survival at this concentration).