Polyelectrolyte complex scaffoldings for photocrosslinked hydrogels

• Published in: Molecular systems design & engineering 2023-05, Vol.8 (5), p.611-623
• Main Authors: Li, Defu, Ghovvati, Mahsa, Annabi, Nasim, Srivastava, Samanvaya
• Format: Article
• Language: English
• Subjects: Additives; Biomedical materials; Chemistry; Covalence; Crosslinking; Dilution; Engineering; Hydrogels; Inks; Interpenetrating networks; Materials Science; Polyelectrolytes; Prepolymers; Science & Technology - Other Topics; Secondary flow; Self-assembly; Shear modulus; Shear strength; Tensile strength; Viscosity
• ISSN: 2058-9689; 2058-9689
• DOI: 10.1039/d2me00171c

Photocrosslinkable precursors (small molecules or polymers) undergo rapid crosslinking upon photoirradiation, forming covalently crosslinked hydrogels. The spatiotemporally controlled crosslinking, which can be achieved in situ , encourages the utility of photocrosslinked hydrogels in biomedicine as bioadhesives, bioprinting inks, and extracellular matrix mimics. However, the low viscosity of the precursor solutions results in unwanted flows and dilution, leading to handling difficulties and compromised strength of the photocrosslinked hydrogels. Here, we introduce oppositely charged triblock polyelectrolytes as additives for precursor solutions that transform them into self-assembled polyelectrolyte complex (PEC) hydrogels with enhanced shear strength and viscosity, providing interim protection against precursor dilution and mitigating secondary flows. The PEC network also augments the properties of the photocrosslinked hydrogels. Crosslinking of the precursors upon photoirradiation results in the formation of interpenetrating polymer network hydrogels with PEC and covalently-linked networks that exhibit shear moduli exceeding the linear combination of the moduli of the constituent networks and overcome the tensile strength-extensibility tradeoff that restricts the performance of covalently-linked hydrogels. The reinforcement approach is shown to be compatible with four types of photocrosslinkable precursors, does not require any modification of the precursors, and introduces minimal processing steps, paving the way for a broader translation of photocrosslinkable materials for biomedical applications. Self-assembled polyelectrolyte complex-based scaffoldings to address the limitations and enrich the microstructure and the mechanical properties of photocrosslinked hydrogels.