Star-Shaped Copolymers Based on Poly(N-vinylcaprolactam) and their Use as Nanocarriers of Methotrexate

Star-shaped poly(N-vinylcaprolactam)-block-poly(ethylhexylacrylate)-block-polyethylene glycol (PNVCL-b-PEHA-b-PEG) triblock copolymers and star-shaped poly(N-vinylcaprolactam)-block-polyethylene glycol (PNVCL-b-PEG) diblock copolymers were synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization. The resulting star block copolymers were characterized using 1H NMR and UV-vis spectroscopy, gel permeation chromatography, and dynamic light scattering. The star-shaped PNVCL-b-PEG and PNVCL-b-PEHA-b-PEG block copolymers self-assemble spontaneously into aggregates in water. The aggregates formed ranged from ~17 to 135 nm in diameter and were used to encapsulate methotrexate (MTX). It was observed that the aggregates from PNVCL-b-PEHA-b-PEG copolymers exhibited a higher drug loading and a lower release of MTX (19 wt-% and 54 %) as compared with star copolymers without PEHA (5 wt-% and 81 %) after 24 h at a temperature below their lower critical solution temperature values.