Peptide‐Reinforced Amphiphilic Polymer Conetworks

Abstract

Amphiphilic polymer conetworks (APCNs) are polymer networks composed of hydrophilic and hydrophobic chain segments. Their applications range from soft contact lenses to membranes and biomaterials. APCNs based on polydimethylsiloxane (PDMS) and poly(2‐hydroxyethyl acrylate) are flexible and elastic in the dry and swollen state. However, they are not good at resisting deformation under load, i.e., their toughness is low. A bio‐inspired approach to reinforce APCNs is presented based on the incorporation of poly(β‐benzyl‐L‐aspartate) (PBLA) blocks between cross‐linking points and PDMS chain segments. The mechanical properties of the resulting peptide‐reinforced APCNs can be tailored by the secondary structure of the peptide chains (β‐sheets or a mixture of α‐helices and β‐sheets). Compared to non‐reinforced APCNs, the peptide‐reinforced networks have higher extensibility (53 vs. up to 341%), strength (0.71 ± 0.16 vs. 22.28 ± 2.81 MPa), and toughness (0.10 ± 0.04 vs. up to 4.85 ± 1.32 MJ m−3), as measured in their dry state. The PBLA peptides reversibly toughen and reinforce the APCNs, while other key material properties of APCNs are retained, such as optical transparency and swellability in water and organic solvents. This paves the way for applications of APCNs that benefit from significantly increased mechanical properties.

Mechanically Robust Hemostatic Hydrogel Membranes with Programmable Strain-Adaptive Microdomain Entanglement for Wound Treatment in Dynamic Tissues

“…(G) Toughness of PU/OC and PU/OC/QCS with and without whole blood treatment. (H) Radar plot of tensile-related properties in dynamic hydrogel membranes and the other same kinds of materials. − (I–L) Elastic moduli, tensile moduli, fracture strengths, and maximum elongations of PU/OC/QCS with Glu, BSA, Na + , Ca 2+ , Mg 2+ , Fe 3+ , PRP, and RBC treatments, respectively. (M) Toughness of PU/OC/QCS with Glu, BSA, Na + , Ca 2+ , Mg 2+ , Fe 3+ , PRP, and RBC treatments.…”

“…The tensile stresses, tensile strains, and tensile moduli of various hydrogels are summarized in a radar plot − (Figure H) for comparison with those of PU/OC and PU/OC/QCS in the present study. Notably, the above-mentioned parameters of PU/OC/QCS outperformed most of the tough hydrogels in recent reports, − which was attributed to (1) dynamic nature of Schiff base bonds for elastic energy dissipation and (2) metal-Schiff base coordination for introducing crystalline microdomains. However, it is also notable that the elongation at break of PU/OC and PU/OC/QCS declined to 178.64 and 249.80% after whole blood treatment, and the decrease in ductility was attributed to the metal–Schiff base coordination-augmented cross-linking of the OC and QCS segments.…”

Trendbericht: Makromolekulare Chemie 2023

“…Bruns und Mitarbeitende fügten in einem bioinspirierten Ansatz Poly(β-benzyl-L-aspartat)-Blöcke zwischen Vernetzungspunkten und Kettensegmenten von Polydimethylsiloxan (PDMS) ein; es entstanden peptidverstärkte Netzwerke mit hoher Dehnbarkeit, Bruchstärke und Zähigkeit. 10) Shastri und Mitarbeitende stellten nanostrukturierte Doppelnetzwerke aus Polysacchariden marinen Ursprungs dar, mit vergleichbaren Eigenschaften wie synthetische Polymere. 11) Ein biobasiertes, recycelbares Vitrimer entwickelten Besenius und Mitarbeitende; 12) Rieger und Team wiederum nutzten die Ringöffnungspolymerisation von Norcampher.…”

Model dynamic covalent thermoresponsive amphiphilic polymer co-networks based on acylhydrazone end-linked Tetronic T904 star block copolymers

“…The non-polar pockets can host sizeable quantities of hydrophobic solutes, either to be delivered, e.g., hydrophobic drug delivery, 3 or, conversely, to be transported from the external aqueous milieu into the APCNs, e.g., sequestration of hydrophobic environmental pollutants. 4 Finally, the formed hydrophobic domains mechanically reinforce [5][6][7] the APCNs, as their reversible deformation provides another energy dissipation mechanism. These enhanced mechanical properties and the internal selfassembly of APCNs are important for their applications, which, in addition to the above-mentioned drug delivery, also include the fabrication of soft contact lenses (the most successful APCN application with global annual sales of 10 billion US dollars), 8 and emerging applications in energy [9][10][11][12][13] and analytical science.…”