Injectable and Self-Healing Boronic-Acid-Modified Succinoglycan Hydrogels: Dual-Stimuli-Responsive Platforms for Controlled Tannic Acid Release

In this study, succinoglycan (SG), an anionic exopolysaccharide derived from <i>Sinorhizobium meliloti</i> Rm1021, was chemically modified to introduce boronic acid groups, creating a boronic-acid-functionalized polysaccharide (SG-APBA). The degree of substitution varied from 4.24% to 24.3%, depending on APBA concentration, with SG-APBA 2 identified as the optimal formulation. The properties of SG-APBA were characterized using ¹H NMR, FTIR, TGA, and XRD, along with rheological analysis to assess changes in the polymer's behavior. The hydrogel, referred to as SAT, was formed through dynamic boronate-ester bonds and hydrogen bonds between SG-APBA and tannic acid (TA). This hydrogel demonstrated excellent injectability, self-healing capacity, and biocompatibility. Incorporation of boronic acid groups allowed the hydrogel to respond to variations in glucose levels and pH, enabling controlled TA release and enhancing its stimulus-responsive antioxidant and antibacterial activities. Antioxidant performance was confirmed through DPPH and ABTS radical scavenging assays, achieving respective activities of 89.8% and 96.4%. Antibacterial effectiveness was validated via inhibition zone tests. Additionally, the SAT hydrogel exhibited dual responsiveness to pH and glucose, with TA release percentages of 55.4% at pH 9.0, 62.7% at pH 7.4, and 69.9% at pH 5.0; and 62.7% at 0 mM glucose, 68.9% at 5 mM, and 72.5% at 25 mM glucose after 120 h. Moreover, combined alterations in pH and glucose triggered a synergistic double-shock effect, markedly accelerating TA release relative to individual stimuli. Overall, these results indicate that the SG-APBA/TA hydrogel has strong potential as a stimuli-responsive platform for drug delivery and biomedical applications.