Sequential Assembly of Mutually-Interactive Supramolecular Hydrogels and Fabrication of Multi-Domain Materials

We report a two-component self-sorting hydrogel based on acylhydrazide and carboxylic acid derivatives of 1,3:2,4-dibenzylidene-D-sorbitol (DBS-CONHNH2 and DBS-COOH). A heat-cool cycle induces the self-assembly of DBS-CONHNH2, followed by the self-assembly of DBS-COOH induced by decreasing pH. Although the networks are formed sequentially, there is spectroscopic evidence of interactions between them, which impact on the mechanical properties and significantly enhance the ability of these low-molecular-weight gelators (LMWGs) to form gels when mixed. The DBS-COOH network can be switched ‘off’ and ‘on’ within the two-component gel via a pH change. Using a photoacid generator, the two-component gel can be prepared combining the thermal trigger with photo-irradiation. Photopatterned self-assembly of DBS-COOH within a pre-formed DBS-CONHNH2 gel under a mask yields spatially-controlled multi-domain gels. Different gel domains can have different functions, for example controlling the rate of release of heparin incorporated into the gel, or directing gold nanoparticle assembly. Such photo-patterned multi-component hydrogels have potential applications in regenerative medicine or bio-nano-electronics.