Polysaccharides are essential in healthcare due to their biocompatibility, versatility, and bioactive properties. Their anti-inflammatory, immunomodulatory, and antibacterial effects make them invaluable for wound healing and tissue engineering. A key innovation of the project lies in formulation of 3D printed polysaccharide wound dressings that can revolutionize the approach to wound healing and personalized medicine. Another novelty is the utilization of bioactive transition-metal cross-links. However, unlocking their full potential requires a comprehensive study of the relationships between formulation, molecular structure, and in vitro/in vivo performance. To achieve this, we employ advanced approaches of structural analysis, providing unprecedented insights into the architecture of these systems, which still remains largely unexplored due to strong paramagnetic effects. By bridging the gap between molecular structure and material performance, this project advances 3D-printed wound dressings, optimizing their physicochemical and biological properties for precision medicine.