Core-block engineering enables control of ice recrystallisation inhibition in polymer nanoparticles

Abstract

Ice-binding proteins (IBPs) are potent ice recrystallisation inhibitors (IRIs) that have inspired the development of synthetic cryoprotectants, spanning small molecules to polymers, but there are only a few soft nanomaterial IRI's reported. Polymerisation-induced self-assembly (PISA) derived nanoparticles are an appealing biomaterial scaffold due to their tuneability and synthetic scalability. Here we demonstrate for the first time that the internal hydrophobic core of PISA-derived nanoparticles controls the observable IRI activity, rather than the expected solvent-exposed hydrophilic corona. We systematically map the chemical and compositional design space of spherical PISA nanoparticles to parameterise the key features for this activity. Switching from glassy to soft nanoparticle cores leads to significantly enhanced IRI activity, whereas crosslinking the same soft cores eliminated all activity. These results establish a new framework for precision-tuneable IRI-active colloids and unlock opportunities to control IRI through modulation of the internal structure of nanoparticles without adapting the surface.