Tuning the Properties of Redox-Responsive Chitosan Networks Through Diacid Chain Length and EDC–Carboxylic Acid Molar Ratio

Abstract

In this work, redox-responsive chitosan derivatives were prepared by crosslinking with disulfide-bridged dicarboxylic acids. Taking into account that structural variations in diacids can lead to significant differences in properties, especially swelling capacity, this study aimed to evaluate the impact of increasing alkyl chain length and hydrophobicity. Two dicarboxylic acids of different hydrophobic character and chain length were used: dithiodiglycolic acid (DTGA) and dithiopropionic acid (DTPA). The resulting materials were fully characterized. Despite their structural similarity, the derivatives exhibited distinct behaviors: DTGA derivatives formed stable hydrogels, whereas DTPA ones remained compact upon contact with water. These results were confirmed by swelling measurements and oscillatory rheology. The EDC:COOH molar ratio was also evaluated, revealing a strong effect on the degree of crosslinking. Moreover, DTGA systems prepared at a 1:1 ratio showed significantly higher swelling than those synthesized at 3:1. Regarding redox responsiveness, it was assessed by quantifying thiol content before and after reduction with sodium borohydride, and reversibility was assessed through reduction?oxidation cycles. Finally, preliminary experiments evaluated the materials? ability to incorporate benzalkonium chloride as a model biocide, and their release was tested in the presence of thiosulfate-reducing bacteria, providing initial insight into their behavior in redox-responsive delivery systems.