Molecularly Imprinted Sites Translate into Macroscopic Shape-Memory Properties of Hydrogels.

The polymerization of acrylamide, dopamine methacrylamide, and bis-acrylamide in the presence of one of the electron acceptors, N,N'-dimethyl-4,4'-bipyridinium, (1), N,N'-dimethylbipyridinium-4,4'-ethylene, (2), or bipyridinium dithienylethene, (3), yields hydrogel matrices of high stiffness that are cooperatively cross-linked by bis-acrylamide and electron donor (dopamine)-acceptor complexes. Washing off the diffusional electron acceptor units yields molecularly imprinted matrices of lower stiffness, stabilized only by the bis-acrylamide bridges that include specific binding sites for the selective association of the electron acceptor (1), (2), or (3). These imprinted hydrogel matrices show selective recovery of the stiff properties upon binding the respective electron acceptor units to the imprinted sites. The control over the stiffness properties enables the development of shape-memory, molecularly imprinted hydrogels and stiffness-based sensors. The results show how molecularly imprinted sites translate into macroscopic shape-memory properties of hydrogels.