Preprint Article Version 1 Preserved in Portico This version is not peer-reviewed

A Remarkable Impact of pH to the Thermoresponsive Properties of Alginate-Based Composite Hydrogels Incorporating P2VP-PEO Micellar Nanoparticles

Version 1 : Received: 1 March 2024 / Approved: 1 March 2024 / Online: 1 March 2024 (12:03:46 CET)

A peer-reviewed article of this Preprint also exists.

Iliopoulou, A.; Iatridi, Z.; Tsitsilianis, C. A Remarkable Impact of pH on the Thermo-Responsive Properties of Alginate-Based Composite Hydrogels Incorporating P2VP-PEO Micellar Nanoparticles. Polymers 2024, 16, 886. Iliopoulou, A.; Iatridi, Z.; Tsitsilianis, C. A Remarkable Impact of pH on the Thermo-Responsive Properties of Alginate-Based Composite Hydrogels Incorporating P2VP-PEO Micellar Nanoparticles. Polymers 2024, 16, 886.

Abstract

A heterograft copolymer with an alginate backbone, hetero-grafted by polymer pendant chains displaying different Lower Critical Solution Temperatures (LCSTs), combined with a pH-responsive Poly(2-vinyl pyridine)-b-poly(ethylene oxide) (P2VP-b-PEO) diblock copolymer forming micellar nanoparticles, was investigated in aqueous media at various pH. Due to its thermoresponsive side chains, the copolymer forms hydrogels with thermo–induced sol–gel transition, above a critical temperature, Tgel (thermo–thickening). However, by lowering pH of the medium in acidic regime, a remarkable increase of the elasticity of the formulation was observed. This effect was more pronounced in low temperatures (below Tgel) suggesting secondary physical crosslinking, which induces significant changes in the hydrogel thermoresponsiveness, transforming the sol–gel transition to soft gel–strong gel. Moreover, the onset of thermothickening shifted to lower temperatures followed by broadening of the transition zone, implying intermolecular interactions between the uncharged alginate backbone with the PNIPAM side chains, likely through H–bonding. The shear–thinning behavior of the soft gel in low temperatures provides injectability, which allows 3D–printing potential applications. Furthermore, the heterograft copolymer/nanoparticles composite hydrogel, encapsulating a model hydrophobic drug in the hydrophobic cores of the nanoparticles, was evaluated as pH-responsive drug delivery system. The presented tunable drug delivery system might be useful for biomedical potential applications.

Keywords

heterograft copolymer; hydrogel; alginate; thermo-responsive; pH-responsive; poly(2- vinyl pyridine)-b-polyethylene oxide; diblock copolymer micelles; drug delivery

Subject

Chemistry and Materials Science, Biomaterials

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