One-pot/simultaneous synthesis of PHPMA-g-PLA copolymers via metal-free ROP/RAFT polymerization and their self-assembly from micelles to thermoresponsive vesicles

0579131 - ÚMCH 2024 RIV US eng J - Článek v odborném periodiku
Lukáš Petrova, Svetlana - Sincari, Vladimir - Konefal, Rafal - Pavlova, Ewa - Lobaz, Volodymyr - Kočková, Olga - Hrubý, Martin
One-pot/simultaneous synthesis of PHPMA-g-PLA copolymers via metal-free ROP/RAFT polymerization and their self-assembly from micelles to thermoresponsive vesicles.
Macromolecular Chemistry and Physics. Roč. 224, č. 23 (2023), č. článku 2300271. ISSN 1022-1352. E-ISSN 1521-3935
Grant CEP: GA ČR(CZ) GA21-01090S; GA MŠMT(CZ) LM2018133
Institucionální podpora: RVO:61389013
Klíčová slova: graft copolymers * nanoparticles * one-pot/one-step RAFT/ROP synthesis
Obor OECD: Polymer science
Impakt faktor: 2.5, rok: 2022
Způsob publikování: Open access
https://onlinelibrary.wiley.com/doi/10.1002/macp.202300271

The present article reports a simple and straightforward approach to access thermoresponsive graft copolymers based on lactide (LA) and a methacrylic monomer, 2-hydroxypropyl methacrylate (HPMA), using a synthesized carboxy-functionalized trithiocarbonate-based chain transfer agent. One protocol involves a metal-free simultaneous synthesis through a combination of reversible addition-fragmentation chain transfer polymerization and organic acid-catalyzed ring-opening polymerization, which follows first-order kinetics. The resulting copolymers with a controlled structure exhibit remarkably narrow molecular weight distributions (Ð < 1.10). Within this framework, the self-assembly of PHPMA-g-PLA graft copolymers (GCs) into nanoparticles (NPs) is demonstrated at concentrations of 0.2 and 0.5 wt.%, respectively. The displacement method, based on the rapid injection of the organic solvent (acetone) into an aqueous medium under vigorous stirring, produces spherical NPs such as micelles, vesicles, or non-spherical “lumpy rods”. The presence of a pseudo-thermoresponsive segment (PHPMA) in GCs facilitates stimulus-responsive self-assembly behavior. Well-defined spherical NPs—primarily vesicles of substantial size—develop upon heating above the glass transition temperature (Tg ≈35–36 °C) of the GCs in an acetone–water (80/20 wt.%) mixture. Last, specific interactions between the obtained PHPMA-g-PLA nano-objects and blood proteins in human plasma are studied using isothermal calorimetry.
Trvalý link: https://hdl.handle.net/11104/0348233