Post-Self-Assembly Cross-Linking to Integrate Molecular Nanofibers with Copolymers in Oscillatory Hydrogels

Abstract

We study the use of post-self-assembly cross-linking to combine molecular nanofibers of hydrogelators with copolymers to generate oscillatory materials using the Belousov-Zhabotinsky reaction. The formation of nanofibers from designed hydrogelators provides multiple polymerizable sites for copolymerizing with N-isopropylacrylamide and for attaching a catalytic ruthenium bipyridine complex on the copolymer. The combination of supramolecular self-assembly with copolymerization offers a versatile and facile approach for generating soft materials that have large pores in the gel network and robust mechanical integrity. These larger pores facilitate the diffusion of the reactants and accelerate the chemical oscillation by about a factor of 4 relative to a poly(NIPAAm-Ru) gel that contains no molecular nanofibers.

Printable hybrid hydrogel by dual enzymatic polymerization with superactivity

“…Recently, our group developed polymer enhanced hybrid self-recovering hydrogels via glucose oxidase mediated polymerization 24. Another post-self-assembly cross-linking approach was reported by Xu et al , who demonstrated that in situ photo-polymerization of acrylic modified oligopeptide hydrogelators with copolymers can achieve a tough hydrogel 25,26. Moreover, these hydrogels have been utilized in multiple applications such as the immobilization of enzymes, controlled release of drugs, controlled cell adhesion and biomimetic materials 21–24,27–29…”

“…Therefore, we report herein a dual enzyme-mediated redox initiation to achieve post-self-assembly cross-linking of acrylic modified hydrogelators (NapFFK-acrylic acid, Scheme S1a†)25,26 with monomers for hybrid hydrogel generation. The injectable supramolecular hydrogel is printed into a 3D structure due to the sol–gel transition and quick recovery during the pressure-driven prototyping.…”

Supramolecular biofunctional materials

“…[90, 179–182] The simplicity of this approach has result in the subsequent design and development of a large group of self-assembling, peptidic hydrogelators capped by Nap motif. [22, 106, 183–185]…”

Supramolecular Design of Unsymmetric Reverse Bolaamphiphiles for Cell‐Sensitive Hydrogel Degradation and Drug Release

“…One way to overcome this issue is through post-assembly crosslinking, where the cleavage sites are chemically conjugated onto the peptide nanostructures, ensuring surface degradation. [20] However, this method suffers from the complicated procedure of crosslinking chemistry and subsequent removal of the potentially toxic initiators. Another method is to incorporate MMP degradable sequences into the main peptide design such as RADA peptides, [21] multi-domain peptides, [22] and bhairpin peptides [23] to form enzyme-responsive hydrogel systems.…”