Reversible self-assembly of superstructured networks

Abstract

Soft structures in nature such as protein assemblies can organize reversibly into functional and often hierarchical architectures through noncovalent interactions. Molecularly encoding this dynamic capability in synthetic materials has remained an elusive goal. We report on hydrogels of peptide-DNA conjugates and peptides that organize into superstructures of intertwined filaments that disassemble upon the addition of molecules or changes in charge density. Experiments and simulations demonstrate that this response requires large scale spatial redistribution of molecules directed by strong noncovalent interactions among them. Simulations also suggest that the chemically reversible structures can only occur within a limited range of supramolecular cohesive energies. Storage moduli of the hydrogels change reversibly as superstructures form and disappear, as does the phenotype of neural cells in contact with these materials.

The Power of Confocal Laser Scanning Microscopy in Supramolecular Chemistry: In situ Real‐time Imaging of Stimuli‐Responsive Multicomponent Supramolecular Hydrogels

“…Furthermore, these techniques cannot discriminate chemical species in multicomponent systems. Recently, confocal laser scanning microscopy (CLSM) has emerged as a powerful tool for structural analysis of multicomponent supramolecular hydrogel systems (Figure ) . CLSM not only allows observation of supramolecular nanofibers and hydrogels without the need for a drying process but can also distinguish between chemical species through the use of appropriately designed fluorescent probes.…”

Polymer Networks: From Plastics and Gels to Porous Frameworks

“…Stupp, Luijten, and co‐workers recently reported a peptide‐based network that experiences topology switching on large length scales in response to added chemical stimuli (Figure B) . The co‐assembly of three peptide amphiphiles, two possessing complementary oligonucleotide terminal segments, resulted in a hydrogel formed from twisted bundles and single fibers with diameters on the micrometer and nanometer scale, respectively.…”

Polymernetzwerke: Von Kunststoffen und Gelen zu porösen Gerüsten

“…Stupp, Luijten und Mitarbeiter beschrieben kürzlich ein Netzwerk auf Peptidbasis, bei dem das Schalten der Topologie als Reaktion auf chemische Stimuli auf großen Längenskalen erfolgt (Abbildung B) . Die Assemblierung von drei Peptid‐Amphiphilen, von denen zwei endständige komplementäre Oligonucleotidsegmente aufwiesen, ergab ein Hydrogel aus verdrillten Bündeln und einzelnen Fasern mit Durchmessern auf der Mikro‐ bzw.…”