Synthesis and micellar characterization of amphiphilic diblock copolymers based on poly(2-ethyl-2-oxazoline) and aliphatic polyesters

Amphiphilic diblock copolymers were synthesized based on poly(2-ethyl-2-oxazoline) (PEtOz) as a hydrophilic block and aliphatic polyesters such as poly(L-lactide) (PLA) or poly(ε-caprolactone) (PCL) as a hydrophobic block. Their micellar characteristics in an aqueous phase were investigated by using dynamic light scattering and fluorescence techniques. The block copolymers formed micelles in the aqueous phase with critical micelle concentrations (cmcs) in the range of 1.0-8.1 mg/L. The cmc values become lower upon increasing the length of the hydrophobic block. The mean diameter of the micelles were in the range of 108-192 nm, with a narrow distribution. In general, the micelle size increased as the hydrophobic PLA or PCL block became larger. The partition equilibrium constants, K_v, of pyrene in the micellar solutions of the block copolymers were from 1.79 × 10⁵ to 5.88 × 10⁵. For each block copolymer system of PEtOz-PLA or PEtOz-PCL, the K_v value increased as the length of the hydrophobic block increased. The steady-state fluorescence anisotropy values (r) of 1,6-diphenyl-1,3,5-hexatriene (DPH) were 0.265-0.284 in PEtOz-PLA solution and 0.189-0.196 in PEtOz-PCL solution. The anisotropy values of PEtOz-PLAs were higher than those of PEtOz-PCLs. The anisotropy values were independent of the length of the hydrophobic block when the chemical structures of the hydrophobic blocks were identical. The micelles underwent hydrogen bonding at pH <3.5 with poly(acrylic acid), which produced polymer complex precipitates that could be reversibly dispersed as micelles at pH >3.8.