Bioactive Polysaccharide-Phytochemical Supramolecular Co-Assemblies for Carrier-Free and Carrier-Minimized...

Carrier-free and carrier-minimized supramolecular nanomedicines seek to reduce inert excipient burden while improving the delivery of poorly soluble therapeutics. This narrative review examines co-assembled systems that combine bioactive polysaccharides with phytochemicals. Natural-product-derived chemotherapeutics are included where relevant. We distinguish true molecular co-assembly from polysaccharide coating, encapsulation, and simple physical mixing. The field is organized around structure-property-assembly-function relationships. We evaluate how hydrophobic interactions, π-π stacking, hydrogen bonding, electrostatic attraction, and metal coordination contribute to assembly, while separating experimentally demonstrated interactions from mechanistic proposals. We then compare structural stabilization, receptor-mediated targeting, mucosal-barrier modulation, and stimulus-responsive disassembly across cancer, inflammatory bowel disease, wound repair, and other chronic inflammatory settings. Particular attention is given to evidence level, quantitative formulation attributes, biological-fluid stability, negative or inconsistent outcomes, reproducible manufacturing, and clinical translation. This review contributes an evidence-qualified design framework that links polysaccharide and phytochemical features to assembly behavior, therapeutic synergy, and administration route. Its green active-excipient perspective may support more sustainable nanomedicine development, provided that safety, reproducibility, and clinical-evidence gaps are resolved.