Alginate Heterografted Copolymer Thermo-Induced Hydrogel Reinforced by PAA-g-P(boc-L-Lysine): Effects on Hydrogel Thermoresponsiveness

In this article, we report on the alginate heterografted by Poly(N-isopropyl acrylamide-co-N-tert-butyl acrylamide) and Poly(N-isopropyl acrylamide) (ALG-g-P(NIPAM86-co-NtBAM14)-g-PNIPAM) copolymer thermoresponsive hydrogel, reinforced by substituting part of the 5 wt% aqueous formulation by small amounts of Poly(acrylic acid)-g-P(boc-L-Lysine) (PAA-g-P(b-LL)) graft copolymer (up to 1 wt%). The resulting complex hydrogels were explored by oscillatory and steady-state shear rheology. The thermoresponsive profile of the formulations were affected remarkably by increasing the PAA-g-P(b-LL) component of the polymer blend. Especially, the sol-gel behavior altered to soft gel-strong gel behavior due to the formation of a semi-interpenetrating network based on the hydrophobic self-organization of the PAA-g-P(b-LL). In addition, the critical characteristics, namely T_{c,thermothickening} (temperature above which the viscosity increases steeply) and ΔT (transition temperature window), shifted and broadened to lower temperatures, respectively, due to the influence of the hydrophobic side chains P(b-LL) on the LCST of the PNIPAM-based grafted chains of the alginate. The effect of ionic strength was also examined, showing that this is another important factor affecting the thermoresponsiveness of the hydrogel. Again, the thermoresponsive profile of the hydrogel was changed significantly by the presence of salt. All the formulations showed self-healing capability and tolerance injectability, suitable for potential bioapplications in living bodies.