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Abstract Shear‐recoverable hydrogels based on block copolypeptides with rapid self‐recovery hold potential in extrudable and injectable 3D‐printing applications. In this work, a series of 3‐arm star‐shaped block copolypeptides composed of an inner hydrophilic poly(l‐glutamate) domain and an outer β‐sheet forming domain is synthesized with varying side chains and block lengths. By changing the β‐sheet forming domains, hydrogels with diverse microstructures and mechanical properties are prepared and structure–function relationships are determined using scattering and rheological techniques. Differences in the properties of these materials are amplified during direct‐ink writing with a strong correlation observed between printability and material chemistry. Significantly, it is observed that non‐canonical β‐sheet blocks based on phenyl glycine form more stable networks with superior mechanical properties and writability compared to widely used natural amino acid counterparts. The versatile design available through block copolypeptide materials provides a robust platform to access tunable material properties based solely on molecular design. These systems can be exploited in extrusion‐based applications such as 3D‐printing without the need for additives.
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Tailored Polypeptide Star Copolymers for 3D Printing of Bacterial Composites Via Direct Ink Writing
Abstract Hydrogels hold much promise for 3D printing of functional living materials; however, challenges remain in tailoring mechanical robustness as well as biological performance. In addressing this challenge, the modular synthesis of functional hydrogels from 3‐arm diblock copolypeptide stars composed of an inner poly(l‐glutamate) domain and outer poly(l‐tyrosine) or poly(l‐valine) blocks is described. Physical crosslinking due to ß‐sheet assembly of these star block copolymers gives mechanical stability during extrusion printing and the selective incorporation of methacrylate units allows for subsequent photocrosslinking to occur under biocompatible conditions. This permits direct ink writing (DIW) printing of bacteria‐based mixtures leading to 3D objects with high fidelity and excellent bacterial viability. The tunable stiffness of different copolypeptide networks enables control over proliferation and colony formation for embeddedEscherichia colibacteria as demonstrated via isopropyl ß‐d‐1‐thiogalactopyranoside (IPTG) induction of green fluorescent protein (GFP) expression. This translation of molecular structure to network properties highlights the versatility of these polypeptide hydrogel systems with the combination of writable structures and biological activity illustrating the future potential of these 3D‐printed biocomposites.
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- Award ID(s):
- 1933487
- PAR ID:
- 10385019
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Advanced Materials
- Volume:
- 35
- Issue:
- 3
- ISSN:
- 0935-9648
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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