Polysaccharide-based materials created by physical processes have received considerable attention for biomedical applications. These structures are often made by associating charged polyelectrolytes in aqueous solutions, avoiding toxic chemistries (crosslinking agents). We review the principal polysaccharides (glycosaminoglycans, marine polysaccharides, and derivatives) containing ionizable groups in their structures and cellulose (neutral polysaccharide). Physical materials with high stability in aqueous media can be developed depending on the selected strategy. We review strategies, including coacervation, ionotropic gelation, electrospinning, layer-by-layer coating, gelation of polymer blends, solvent evaporation, and freezing–thawing methods, that create polysaccharide-based assemblies via in situ (one-step) methods for biomedical applications. We focus on materials used for growth factor (GFs) delivery, scaffolds, antimicrobial coatings, and wound dressings.

Pectin and chitosan films containing glycerol (Gly) at 5, 10, 15, 20, 30, and 40 wt % were prepared in an aqueous HCl solution (0.10 M) by the solvent evaporation method. The unwashed film (UF) containing 40 wt % Gly (UF40) had elongation at break (ε, %) of 19%. Washed films (WFs) had high tensile strength (σ > 46 MPa) and low elongation at break (ε, <5.0%), enabling their use in food packaging applications. The polymers’ self-assembling occurred during the washing, increasing the stiffness. The XPS analysis suggests that some HCl is lost during the drying process, resulting in a low acid content on the UF surfaces. The UF40 (at 5.0 mg/mL) exhibits cytocompatibility toward mammalian cells and antimicrobial and anti-adhesive properties against Escherichia coli. The remaining HCl in the UF40 can be a disadvantage for food packaging applications; the UF40 (∅ = 8.5 mm; 55 μm thickness) releases H₃O⁺/HCl, reducing the pH to approximately 3.0 when kept in 200 mL distilled water for approximately 30 min. Therefore, we propose the use of UF40 to coat commercial food packaging. The UF40 has low permeability to water vapor and oxygen and works as a barrier against ultraviolet light. The UF40 is also colorless and completely transparent. The UF40 maintained tomatoes’ structural integrity for 18 days at room temperature with no oxidation or microorganism contamination. This paper presents a critical viewpoint concerning chitosan-based films with antimicrobial activities.