Conformational Behavior and Self-Assembly of Gallol-Containing Block Copolymers in Non-Polar Media

While previous studies have illuminated the behavior of poly(gallol methacrylate)-block-poly(N-phenylmethacrylamide) copolymers (PM-b-PNP) in polar alcoholic mixtures, their performance in non-polar environments remains an uncharted territory. In this study, full-atomistic molecular dynamics (MD) simulations were first employed to investigate the conformational behavior and aggregation of experimentally relevant homo- and block copolymer architectures in heptane. The theoretical findings were subsequently supported through experimental studies using polymers synthesized via controlled reversible addition fragmentation chain transfer (RAFT) polymerization. Our results highlight the critical role of intramolecular hydrogen bonding in stabilizing specific conformations and helix-like structures of PNP homopolymers and the leading role of attractive van der Waals interactions in the aggregation of block copolymers.