Rheology-guided experimental design of dynamically crosslinked keratin/ι-carrageenan hydrogels as potential drug delivery systems.

Authors

Costanza Fratini, Mattia Tiboni, Itxaso Calafel, Mercedes Fernández, Robert Aguirresarobe, Annalisa Aluigi, Luca Casettari

Published in

Carbohydrate polymers. Volume 391. Pages 125842. Nov 01, 2026. Epub Sep 08, 2026.

Abstract

This study establishes a deterministic framework for designing 3D-printable, dynamically crosslinked hydrogel inks for controlled drug delivery via Direct Ink Writing (DIW). By blending cysteine-S-sulfonated keratin with ι-carrageenan through Ca²⁺ ionotropic gelation, shear-responsive networks were created. A Design of Experiments (DoE) approach generated a predictive rheology-to-printability map correlating composition with storage modulus (G^'), flow stress (τ_f), and printability index (P_r). Advanced Large Amplitude Oscillatory Shear (LAOS) profiling revealed a transition from ductile, entanglement-driven networks in keratin-rich blends to brittle yielding via cooperative ionic junction rupture in crosslinked systems. Sequence of Physical Processes (SPP) analysis further identified an intracycle recovery loss factor (tanδ_rec) that dictates post-deposition shape retention. Structural analyses verified that Ca²⁺ drives network compaction and crystalline β-sheet reorganization. Crucially, dexamethasone (Dex) loading acts as a dual-functional modulator via supramolecular hydrogen bonding: behaving as an interfacial sliding agent that reduces interchain friction within densely crosslinked matrices, while acting as a secondary physical crosslinker in weakly crosslinked networks, which amplifies elastic energy storage and induces viscous Lissajous-Bowditch loop expansions. Finally, mathematical modeling confirmed that ionic crosslinking shifts drug transport from anomalous diffusion to a relaxation-controlled Super Case II regime governed by the relaxation rate (k_r).

PMID:
42785881
Bibliographic data and abstract were imported from PubMed on 25 Sep 2026.

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