Tannic Acid-Mediated Aggregate Stabilization of Poly(-vinylpyrrolidone)--poly(oligo (ethylene glycol) methyl ether methacrylate) Double Hydrophilic Block Copolymers.

The self-assembly of block copolymers in aqueous solution is an important field in modern polymer science that has been extended to double hydrophilic block copolymers (DHBC) in recent years. In here, a significant improvement of the self-assembly process of DHBC in aqueous solution by utilizing a linear-brush macromolecular architecture is presented. The improved self-assembly behavior of poly(-vinylpyrrolidone)--poly(oligo(ethylene glycol) methyl ether methacrylate) (PVP--P(OEGMA)) and its concentration dependency is investigated via dynamic light scattering (DLS) (apparent hydrodynamic radii ≈ 100-120 nm). Moreover, the DHBC assemblies can be non-covalently crosslinked with tannic acid via hydrogen bonding, which leads to the formation of small aggregates as well (apparent hydrodynamic radius ≈ 15 nm). Non-covalent crosslinking improves the self-assembly and stabilizes the aggregates upon dilution, reducing the concentration dependency of aggregate self-assembly. Additionally, the non-covalent aggregates can be disassembled in basic media. The presence of aggregates was studied via cryogenic scanning electron microscopy (cryo-SEM) and DLS before and after non-covalent crosslinking. Furthermore, analytical ultracentrifugation of the formed aggregate structures was performed, clearly showing the existence of polymer assemblies, particularly after non-covalent crosslinking. In summary, we report on the completely hydrophilic self-assembled structures in solution formed from fully biocompatible building entities in water.