Leveraging peptide-cellulose interactions to tailor the hierarchy and mechanics of peptide-polymer hybrids.

Inspired by spider silk's hierarchical diversity, we leveraged peptide motifs with the capability to tune structural arrangement for controlling the mechanical properties of a conventional polymer framework. The addition of nanofiller with hydrogen bonding sites was used as another pathway towards hierarchical tuning via matrix-filler interactions. Specifically, peptide-polyurea hybrids (PPUs) were combined with cellulose nanocrystals (CNCs) to develop mechanically-tunable nanocomposites via tailored matrix-filler interactions (or peptide-cellulose interactions). In this material platform, we explored the effect of these matrix-filler interactions on the secondary structure, hierarchical ordering, and mechanical properties of the peptide hybrid nanocomposites. Interactions between the peptide matrix and CNCs occur in all of the PPU/CNC nanocomposites, preventing α-helical ordering, but promoting inter-molecular hydrogen bonded ß-sheet formation. Depending on peptide and CNC content, the Young's modulus varies from 10 to 150 MPa. Unlike conventional cellulose-reinforced polymer nanocomposites, the mechanical properties of these composite materials are dictated by a balance of CNC reinforcement, peptidic ordering, and microphase-separated morphology. This research highlights that leveraging peptide-cellulose interactions is a strategy to create materials with targeted mechanical properties for a specific application using a limited selection of building blocks.

Poly (diglycerol adipate) variants as enhanced nanocarrier replacements in drug delivery applications.

Sustainably derived poly(glycerol adipate) (PGA) has been deemed to deliver all the desirable features expected in a polymeric scaffold for drug-delivery, including biodegradability, biocompatibility, self-assembly into nanoparticles (NPs) and a functionalisable pendant group. Despite showing these advantages over commercial alkyl polyesters, PGA suffers from a series of key drawbacks caused by poor amphiphilic balance. This leads to weak drug-polymer interactions and subsequent low drug-loading in NPs, as well as low NPs stability. To overcome this, in the present work, we applied a more significant variation of the polyester backbone while maintaining mild and sustainable polymerisation conditions. We have investigated the effect of the variation of both hydrophilic and hydrophobic segments upon physical properties and drug interactions as well as self-assembly and NPs stability. For the first time we have replaced glycerol with the more hydrophilic diglycerol, as well as adjusting the final amphiphilic balance of the polyester repetitive units by incorporating the more hydrophobic 1,6-n-hexanediol (Hex). The properties of the novel poly(diglycerol adipate) (PDGA) variants have been compared against known polyglycerol-based polyesters. Interestingly, while the bare PDGA showed improved water solubility and diminished self-assembling ability, the Hex variation demonstrated enhanced features as a nanocarrier. In this regard, PDGAHex NPs were tested for their stability in different environments and for their ability to encode enhanced drug loading. Moreover, the novel materials have shown good biocompatibility in both in vitro and in vivo (whole organism) experiments.

Enhancement of the Mechanical Properties of Hydrogels with Continuous Fibrous Reinforcement.

Reinforcing mechanically weak hydrogels with fibers is a promising route to obtain strong and tough materials for biomedical applications while retaining a favorable cell environment. The resulting hierarchical structure recreates structural elements of natural tissues such as articular cartilage, with fiber diameters ranging from the nano- to microscale. Through control of properties such as the fiber diameter, orientation, and porosity, it is possible to design materials which display the nonlinear, synergistic mechanical behavior observed in natural tissues. In order to fully exploit these advantages, it is necessary to understand the structure-property relationships in fiber-reinforced hydrogels. However, there are currently limited models which capture their complex mechanical properties. The majority of reported fiber-reinforced hydrogels contain fibers obtained by electrospinning, which allows for limited spatial control over the fiber scaffold and limits the scope for systematic mechanical testing studies. Nevertheless, new manufacturing techniques such as melt electrowriting and bioprinting have emerged, which allow for increased control over fiber deposition and the potential for future investigations on the effect of specific structural features on mechanical properties. In this review, we therefore explore the mechanics of fiber-reinforced hydrogels, and the evolution of their design and manufacture from replicating specific features of biological tissues to more complex structures, by taking advantage of design principles from both tough hydrogels and fiber-reinforced composites. By highlighting the overlap between these fields, it is possible to identify the remaining challenges and opportunities for the development of effective biomedical devices.