Self-Assembly of PEG-b-PTMC Copolymers: Micelles and Polymersomes Size Control

Poly(ethylene glycol)₄₅-b-poly(trimethylene carbonate) PEG₄₅-b-PTMC diblock copolymers were synthesized with five different PTMC degrees of polymerization (n = 38, 96, 144, 170, 332) and their self-assembly properties in water were studied using a manual nanoprecipitation procedure. We confirmed that the copolymer's hydrophilic weight fraction (f_PEG) is controlling nanoparticles morphology. We determined that the PEG₄₅-b-PTMC₉₆ with f_PEG ≈ 17% is the optimal hydrophilic fraction for the stabilization of well-defined unilamellar vesicles with a membrane thickness of δ ≈ 14.6 nm. Maintaining this fraction constant and modulating the overall molar mass of the block copolymers allowed the establishment of a power law of [Formula: see text] which provides a robust correlation between the molar mass of PTMC and vesicles' membrane thickness. Finally, we proved that controlling nanoprecipitation's conditions by microfluidics allowed fine-tuning and control of the nanoparticles size and polydispersity index while maintaining their shape with a perfect batch-to-batch reproducibility.