Tailoring Writability and Performance of Star Block Copolypeptides Hydrogels through Side‐Chain Design

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.

Polypeptide-Based Systems: From Synthesis to Application in Drug Delivery

“…Polypeptide hydrogels, along with hydro- More information on the various factors that play an important role in the polypeptide gelation process, properties, and applications of polypeptide hydrogels can be found in some relevant reviews [16,382,392]. Polypeptide hydrogels, along with hydrogels based on other polymers, are characterized by properties that make them suitable for additive manufacturing of 3D materials, and these properties can be tunable through molecular design [16,395,420,421]. The development of polypeptide-based hydrogels using covalent and non-covalent cross-linking for various 3D printing strategies has recently received special attention.…”

Self-assembled branched polypeptides as amelogenin mimics for enamel repair

“…Thus, we aimed to develop a more biocompatible and readily accessible integrated polypeptide, capable of tuning its self-assembled architecture through a polymerization strategy and imitating the self-assembling behavior of Ame to a greater extent. 45–47…”

“…Thus, we aimed to develop a more biocompatible and readily accessible integrated polypeptide, capable of tuning its self-assembled architecture through a polymerization strategy and imitating the self-assembling behavior of Ame to a greater extent. [45][46][47] In recent years, branched poly(amido amine) derivatives have been reported to exhibit self-assembly behavior similar to Ame and effectively mediate the crystallization process of HAP, which demonstrates that the branched polymer chain can enhance the complexity and diversity of self-assembly, making it become a promising biomimetic structure of a threedimensional protein. [48][49][50][51][52][53][54] Accordingly, we chose branched poly(g-benzyl-L-glutamate) (PBLG) as the mimic of the Ame's N-terminal domain, a hydrophobic poly(amino acid) with excellent self-assembling capability, great degradability and superior biocompatibility, [55][56][57][58][59][60][61][62][63][64] which was coupled with the hydrophilic C-Ame segment to form a complete Ame mimic (Fig.…”