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.

ABA-type triblock copolymer micellar system with lower critical solution temperature-type sol-gel transition.

A temperature sensitive sol-gel transition induced by the self-assembly of amphiphilic copolymers and its application in industry have been the objects of increasing study. We demonstrate here a two-step, reversible addition-fragmentation chain transfer (RAFT) polymerization of an ABA-type copolymer consisting of poly(N,N-dimethylacrylamide)-b-poly(diacetone acrylamide)-b-poly(N,N-dimethylacrylamide) (PDMAA-b-PDAAM-b-PDMAA). This copolymer can be easily dispersed in water, and this dispersion is critical for its lower critical solution temperature (LCST)-type sol-gel transition, which was monitored using dynamic light scattering (DLS), transmission electron microscopy (TEM), and rheology analysis, in addition to temperature-dependent 1H nuclear magnetic resonance (1H NMR) and Fourier transform infrared spectroscopy (FTIR). Results revealed an abnormal sphere-to-worm micellar transition of this ABA copolymer at the LCST point, which could be affected by the length of the PDAAM block (B-block), the length as well as the distribution of the PDMAA block (A-block), and the concentration of the copolymer dispersion. Thus, copolymer dispersion could be feasibly used for drug loading at a low temperature, which could then be transformed into a gel at an elevated temperature. The loading and controllable release of the model drug of paracetamol into and out of a copolymer gel was further determined. The sustained release behavior was also studied using the Rigter-Peppas model.