Specific ion effects on the aggregation of polysaccharide-based polyelectrolyte complex particles induced by monovalent ions within Hofmeister series

Polysaccharide-based polyelectrolyte complex (PEC) particles have been utilized as carriers for drug delivery systems (DDS) and as building components for material development. Despite their versatility, the aggregation mechanism of PEC particles in the presence of salts remains unclear. To clarify the aggregation mechanism, the specific ion effects of monovalent salts within the Hofmeister series on the aggregation behavior of PEC particles composed of chitosan and chondroitin sulfate C, which are often used as DDS carriers and materials, were studied. Here, we found that weakly hydrated chaotropic anions promoted the aggregation of positively charged PEC particles. The hydrophobicity of the PEC particles was increased by these ions. Strongly hydrated ions such as Cl- are less likely to accumulate in these particles, whereas weakly hydrated chaotropic ions such as SCN- are more likely to accumulate. Molecular dynamics simulations suggested that the hydrophobicity of PECs might be strengthened by ions due to changes in intrinsic and extrinsic ion pairs and hydrophobic interactions. Based on our results, it is expected that the control of surface hydrophilicity or hydrophobicity is an effective approach for controlling the stability of PEC particles in the presence of ions.