A toolbox of oligopeptide-modified polymers for tailored elastomers

Abstract

Biomaterials are constructed from limited sets of building blocks but exhibit extraordinary and versatile properties, because hierarchical structure formation lets them employ identical supramolecular motifs for different purposes. Here we exert a similar degree of structural control in synthetic supramolecular elastomers and thus tailor them for a broad range of thermomechanical properties. We show that oligopeptide-terminated polymers selectively self-assemble into small aggregates or nanofibrils, depending on the length of the oligopeptides. This process is self-sorting if differently long oligopeptides are combined so that different nanostructures coexist in bulk mixtures. Blends of polymers with oligopeptides matching in length furnish reinforced elastomers that exhibit shear moduli one order of magnitude higher than the parent polymers. By contrast, novel interpenetrating supramolecular networks that display excellent vibration damping properties are obtained from blends comprising non-matching oligopeptides or unmodified polymers. Hence, blends of oligopeptide-modified polymers constitute a toolbox for tailored elastomers with versatile properties.

Dynamic cross-links to facilitate recyclable polybutadiene elastomer with excellent toughness and stretchability

“…The phenomenon can be attributed to the reversible break and reformation of ionic hydrogen bonds at high temperature that causes large energy dissipation. The dynamically cross‐linked PB‐TAAs show higher tan δ peak values in the glass‐transition region and a new broad tan δ peak in the rubbery region, indicating dynamic noncovalent cross‐linking may be a promising way than chemically cross‐linking for the preparation of high‐performance damping materials …”

Development of New Smart Materials and Spinning Systems Inspired by Natural Silks and Their Applications

“…As the length of the peptide domain increased, single β-sheet tapes and stacked nanofibrils formed. Mixing M and D together gave rise to inherently reinforced thermoplastic elastomers and interpenetrating supramolecular networks (Croisier et al, 2014).…”

“…The thiophene blocks further stabilized the supramolecule through the formation of π-π stacks, which conveyed conductivity to the supramolecular structures (Gus'kova et al, 2008). Croisier et al (2014) synthesized a series of peptide/ poly(isobutylene) hybrid elastomers. In these hybrids, silk peptides were conjugated to one terminus or both termini of an poly(isobutylene) unit to form a diblock hybrid (monofunctional hybrid M) or a triblock hybrid (difunctional hybrid D).…”

Supramolecular thermoplastics and thermoplastic elastomer materials with self-healing ability based on oligomeric charged triblock copolymers

“…The crosslinks can for example be formed by multiple hydrogen bonds, [4][5][6][7][8][9][10][11][12][13][14][15] π-π stacking interactions, 16,17 ionic interaction [18][19][20][21] or metal-ligand interaction. [22][23][24][25] Supramolecular materials based on self-assembly of oligopeptides 26 and nucleobases 27 have also been reported. Even relatively weak hydrogen bonds in combination with phase segregation can form a rather strong network from low-molecular-weight components.…”