Cross-Linking Induced Self-Organization of Polymers into Degradable Assemblies.

Covalently stabilized polymer assemblies are normally fabricated from the self-assembly of polymer chains followed by a cross-linking reaction. In this report, we show that a cross-linking-induced self-assembly approach, in which boronate cross-linking sites are formed by the condensation reaction between boronic and catechol groups, can organize polymer networks into uniform assemblies. Self-assembly of these boronate cross-linked polymer networks adopts two different driving forces in water and methanol solutions. Hydrophobic aggregation of polymer networks in water solution affords spherical assemblies, while B-N dative bond formed between boronate and imine functionalities in methanol solution organizes the polymer networks into bundle-like assemblies. We not only demonstrate the intrinsic stimuli-responsive degradability of these cross-linked assemblies but also show that their degradation can cause a controllable release of guest molecules. Moreover, bundle-like assemblies with rough surface and exposed boronate functionalities exhibit dramatically higher cell penetration capability than the spherical assemblies with smooth surface and embedded boronate functionalities.