Coassembly of Linear Diblock Copolymer Chains and Homopolymer Brushes on Silica Particles: A Combined Computer Simulation and Experimental Study

A combined computer simulation and experimental study on coassembly of poly­(2-(dimethylamino)­ethyl methacrylate)-<i>block</i>-polystyrene (PDMAEMA-<i>b</i>-PS) block copolymers and PS brushes on silica particles was performed. PS brushes on silica particles at two different grafting densities were prepared by the “grafting to” approach, and PDMAEMA-<i>b</i>-PS block copolymers with different molecular weights and compositions were synthesized by reversible addition–fragmentation chain transfer polymerization. In THF/methanol mixtures, block copolymer chains and PS brushes coassemble into surface micelles (s-micelles), with collapsed PS cores and PDMAEMA coronae. Meanwhile, block copolymer chains are able to self-assemble into block copolymer micelles (b-micelles). Computer simulation results and experimental results indicate that block copolymer concentration, PS and PDMAEMA block lengths, and PS grafting density exert significant influences on the coassembly process. In low BCP concentration regime, the average size of s-micelles increases with BCP concentration and keeps unchanged at high concentration. The PS block length has a significant influence on the size of s-micelles. The average size increases with an increase in PS block length. For a BCP with long solvophilic PDMAEMA block, it is energy favorable to self-assemble into b-micelles, but to coassemble into s-micelles. With an increase in PDMAEMA block length, the morphology of the s-micelles changes from wormlike/spherical structures to spherical structures and to smaller spherical structures. The average size of the s-micelles coassembled by PS brushes at a lower grafting density is smaller than those coassembled by PS brushes at a higher grafting density

Protein-Cross-Linked Triple-Responsive Polymer Networks Based on Molecular Recognition

Hydrogels containing protein components are a type of promising biomaterial. In this paper, we designed triple-responsive polymer–protein networks based on molecular recognition. Reduced bovine serum albumin (BSA) was modified with multiple β-cyclodextrin (βCD) by thiol–disulfide exchange reaction. The βCD-modified BSA was added into the aqueous solution of acrylamide copolymer with pendant adamantyl groups, resulting in the formation of polymer–protein network structures. The assembled polymer networks show triple-responsive behaviors upon treatment with trypsin, reduced glutathione, or native βCD. The network structures may find applications in tissue engineering and drug controlled release