pH-Sensitive Poly(acrylic acid)-g-poly(L-lysine) Charge-Driven Self-Assembling Hydrogels with 3D-Printability and Self-Healing Properties

We report the rheological behavior of aqueous solutions of a graft copolymer polyampholyte, constituted of polyacrylic acid (PAA) backbone grafted by Poly(L-lysine) (PAA-b-PLL). The graft copolymer self-assembles in aqueous media, forming a three-dimensional (3D) network through polyelectrolyte complexation of the oppositely charged PAA and PLL segments. Rheological investigations showed that the hydrogel exhibits interesting properties, namely, relatively low critical gel concentration, elastic response with slow dynamics, remarkable extended critical strain to flow, shear responsiveness, injectability, 3D printability and self-healing. Due to the weak nature of the involved polyelectrolyte segments, the hydrogel properties display pH-dependency, and they are affected by the presence of salt. Especially upon varying pH, the PLL secondary structure changes from random coil to & alpha;-helix, affecting the crosslinking structural mode and, in turn, the overall network structure as reflected in the rheological properties. Thanks to the biocompatibility of the copolymer constituents and the biodegradability of PLL, the designed gelator seems to exhibit potential for bioapplications.

Automated summary

We investigated the rheological behavior of a graft copolymer polyampholyte composed of polyacrylic acid (PAA) backbone grafted by Poly (L-lysine) (PAA-b-PLL). The hydrogel formed by self-assembly displayed interesting properties such as low critical gel concentration, elastic response, extended critical strain, shear responsiveness, injectability, 3D printability, and self-healing. The properties of the hydrogel were pH-dependent and influenced by the presence of salt due to the changes in PLL secondary structure and crosslinking mode.