Self-Healing Multiblock Copolypeptide Hydrogels via Polyion Complexation

Abstract

Diblock, triblock and pentablock copolypeptides were designed and prepared for formation of polyion complex hydrogels in aqueous media. Increasing the number of block segments was found to allow formation of hydrogels with substantially enhanced stiffness at equivalent concentrations. Use of similar length ionic segments also allowed mixing of different block architectures to fine tune hydrogel properties. The pentablock hydrogels possess a promising combination of high stiffness, rapid self-healing properties, and cell compatible surface chemistry that makes them promising candidates for applications requiring injectable or printable hydrogel scaffolds. Polyion complex (PIC) assembly of dual hydrophilic block copolymers containing non-ionic and oppositely charged ionic segments has been developed as a facile method to prepare a diverse array of micelles, vesicles, and hydrogels in aqueous media. 1-3 Due to the high water solubility of precursors, PIC formation allows the preparation of supramolecular assemblies at high concentrations via simple mixing, and does not require the use of either heating or cosolvents. These assemblies are experiencing extensive development in applications, including as carriers for therapeutic molecules and as scaffolds for cell culture and tissue repair. 1-5 We recently reported the design of PIC diblock copolypeptide hydrogels

Repairing Creep-Resistant and Kinetically Inert Hydrogels via Yeast Activity-Regulated Energy Dissipation

“…The hydrogels after the post-soaking (pH 7.4) with a swelling ratio of ∼14% (Figure S1) possess satisfying kinetic stability/inertness but lack spontaneous healing ability. The bioinspired self-healing is an advanced function to enhance synthetic materials with longevity and reliability. − We design the following method to realize the healing of damaged yeast-containing polymer hydrogels with high kinetic stability. The broken hydrogels are treated with sucrose on the fracture surfaces.…”

Advances in Synthesis and Applications of Self-Healing Hydrogels

“…When hydrophobic chains are exposed to water, they tend to aggregate in order for their hydrophobic parts to avoid contact with water as much as possible. In many recent cases, hydrophobic interaction has been used along with other types of cross-linkages to synthesize self-healing hydrogels, such as metal-ligand coordination ( Tang et al, 2018 ), ionic interaction ( Sun and Deming, 2019 ), or even through multiple ones ( Deng et al, 2019 ). Liu P. et al (2019) studied a thermo-responsive hydrogel made from poly(lactic-co-glycolic acid)-PLGA-PEG-PLGA copolymer, which is widely used in drug delivery ( Joo et al, 2009 ), and was the first to discover the self-healing property of this polymer.…”

Cascade synthesis of architecture-transformable thermo-labile multisite multiblock copolymers

“…Meanwhile, tremendous efforts have been devoted to block copolymers since they can hold great promise as promising soft materials. 7,8,[27][28][29][30][31][32] With increasing block number, multiblock copolymers involving (AB) n and (ABA) n -type copolymers are liable to exhibit more intriguing physical properties involving single-chain folding, 14,15,33 aggregation behaviors, [34][35][36][37] tensile strength, 29,38,39 and bioproperties. [40][41][42][43] As reactive linkers and side groups are incorporated into multiblock copolymers, the resultant multisite multiblock copolymers (MMBPs) may exhibit more flexible topological transformations among linear, cyclic, branched and single-chain folding architectures.…”