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.

We report the electrospinning of mechanically-tunable, cellulose nanocrystal (CNC)-reinforced polyurethanes (PUs). Using high-aspect ratio CNCs from tunicates, the stiffness and strength of electrospun PU/CNC mats are shown to generally increase. Furthermore, by tuning the electrospinning conditions, fibrous PU/CNC mats were created with either aligned or non-aligned fibers, as confirmed by scanning electron microscopy. PU/CNC mats having fibers aligned in the strain direction were stiffer and stronger compared to mats containing non-aligned fibers. Interestingly, fiber alignment was accompanied by an anisotropic orientation of the CNCs, as confirmed by wide-angle X-ray scattering, implying their alignment additionally benefits both stiffness and strength of fibrous PU/CNC nanocomposite mats. These findings suggest that CNC alignment could serve as an additional reinforcement mechanism in the design of stronger fibrous nanocomposite mats.

Inspired by Nature's tunability driven by the modulation of structural organization, we utilize peptide motifs as an approach to tailor not only hierarchical structure, but also thermo-responsive shape memory properties of conventional polymeric materials. Specifically, poly(β-benzyl-L-aspartate)-b-poly(dimethylsiloxane)-b-poly(β-benzyl-L-aspartate) was incorporated as the soft segment in peptide–polyurea hybrids to manipulate hierarchical ordering through peptide secondary structure and a balance of inter- and intra-molecular hydrogen bonding. Employing these bioinspired peptidic polyureas, we investigated the influence of secondary structure on microphase-separated morphology, and shape fixity and recovery via attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), small-angle X-ray scattering (SAXS) and dynamic mechanical analysis (DMA). The β-sheet motifs promoted phase mixing through extensive inter-molecular hydrogen bonding between the hard block and peptide segments and provided an increased chain elasticity, resulting in decreased shape fixity compared to a non-peptidic control. In contrast, intra-molecular hydrogen bonding driven by the α-helical arrangements yielded a microphase-separated and hierarchically ordered morphology, leading to an increase in the shape fixing ratio. These results indicate that peptide secondary structure provides a convenient handle for tuning shape memory properties by regulating hydrogen bonding with the surrounding polyurea hard segment, wherein extent of hydrogen bonding and phase mixing between the peptidic block and hard segment dictate the resulting shape memory behaviour. Furthermore, the ability to shift secondary structure as a function of temperature also was demonstrated as a pathway to influence shape memory response. This research highlights that peptide secondary conformation influences the hierarchical ordering and modulates the shape memory response of peptide–polymer hybrids. We anticipate that these findings will enable the design of smart bio-inspired materials with responsive and tailored function via a balance of hydrogen bonding character, structural organization, and mechanics.

Amphiphilic polymer conetworks were mechanically reinforced with a combination of peptide blocks and cellulose nanocrystals, resulting in transparent, water-swellable and hexane-swellable gels with excellent mechanical properties.

Inspired by spider silk's hierarchical diversity, we leveraged peptide motifs and functional nanofillers to modulate the mechanical properties of a conventional polymer framework via specific matrix–filler interactions.

This paper highlights a bioinspired approach to engineering water-responsive materials via a diverse array of self-assembled nanostructures.