Reductive Synthesis of Stable, Polysaccharide in Situ-Modified Gold Nanoparticles Using Disulfide Cross-Linked Alginate

Gold nanoparticles (AuNPs) are promising for biomedical applications, but their synthesis often requires toxic reagents. "Green" methods utilizing biopolymers offer a sustainable alternative. This study presents a novel synthesis of stable gold nanoparticles using a disulfide-crosslinked derivative of alginic acid (AA-S-S-AA) as both a reducing agent and stabilizer. The S-S-cross-linked alginate was synthesized with a degree of substitution of ~4.2% and reacted with HAuCl₄ in water at room temperature for just 10 min to give stable and polysaccharide in situ modified gold nanoparticles (AA-AuNPs). The resulting AA-AuNPs were characterized by a surface plasmon resonance peak at 539 nm and exhibited good colloidal stability over 14 days. Electron microscopy revealed spherical nanoparticles with a bimodal size distribution (10 nm and 75-100 nm) and a visible polysaccharide shell (5-9 nm), confirming effective stabilization. X-ray photoelectron spectroscopy confirmed the presence of metallic gold (Au⁰) and Au¹⁺. NMR analysis indicated the oxidation of disulfide groups to sulfonic acid during synthesis. The nanoparticles demonstrated a high negative zeta-potential of -53.9 mV, attributable to the polyanionic alginate corona, ensuring strong electrostatic stabilization. This work establishes sulfur-modified alginic acid as an efficient platform for the rapid synthesis of stable, hybrid nanoparticles for potential use in catalysis and biomedicine.