Evaluation of critical packing parameter in the series of polytyrosine-PEG amphiphilic copolymers

Here, we report on the evaluation of critical packing parameters, PC, of L-tyrosine and ethylene glycol (PEG) amphiphilic block copolymers. The copolymers were synthesized via L-tyrosine-N-carboxyanhydride ring-opening polymerization using different amino-terminated PEGs as macroinitiators. The size and shape of their associates formed in water were investigated by transmission electron microscopy and dynamic and static light scatterings. The copolymers containing 20–30 wt. % of Tyr formed rod-like micelles. The copolymers with 30–50 wt. % of Tyr formed spherical vesicles, while those with 50–80 wt. % Tyr formed irregularly shaped polymeric nanoparticles. PC of the copolymers was estimated as the ratio of the van der Waals volume of the hydrophobic block (V) to its length (L) and the cross-sectional area of the polar block (SH). The values of SH for each copolymer were calculated according to the equation obtained from the correlation analysis of the published data. The hydrophobic block length L was calculated in three ways, i.e., assuming that polytyrosine adopts (1) stretched, (2) amyloid hairpin, or (3) Gaussian coil conformation. In the latter case, the best match of the calculated PC values with the morphology of the copolymer assemblies was observed.