The Valence-Dependent Activity of Colloidal Molecules as Ice Recrystallization Inhibitors

Inspired by advances in cryopreservation techniques, which are essential for modern biomedical applications, there is a special interest in the ice recrystallization inhibition (IRI) of the antifreeze protein (AFPs) mimics. There are in-depth studies on synthetic materials mimicking AFPs, from simple molecular structure levels to complex self-assemblies. Herein, we report the valence-dependent IRI activity of colloidal organic molecules (CMs). The CMs were prepared through polymerization-induced particle-assembly (PIPA) of the ABC-type triblock terpolymer of poly(acryloxyethyl trimethylammonium chloride)-b-poly(benzyl acrylate)-b-poly(diacetone acrylamide) (PATAC-b-PBzA-b-PDAAM) at high monomer conversions. Stabilized by the cationic block of PATAC, the strong intermolecular H-bonding and incompatibility of the PDAAM block with PBzA contributed to the in situ formation of Janus particles (AX₁) beyond the initial spherical seed particles (AX₀), as well as the high valency clusters of linear AX₂ and trigonal AX₃. Their distribution was controlled mainly by the polymerization degrees (DPs) of PATAC and PDAAM blocks. IRI activity results of the CMs suggest that the higher fraction of AX₁ results in the better IRI activity. Increasing the fraction of AX₁ from 27% to 65% led to a decrease of the mean grain size from 39.8% to 10.9% and a depressed growth rate of ice crystals by 58%. Moreover, by replacing the PDAAM block with the temperature-responsive one of poly(N-isopropylacrylamide) (PNIPAM), temperature-adjustable IRI activity was observed, which is well related to the reversible transition of AX₀ to AX₁, providing a new idea for the molecular design of amphiphilic polymer nanoparticle-based IRI activity materials.