Background: Poly(acrylic acid) (PAA) is a water-soluble synthetic polymer with tissue-adhesive properties. When PAA is mixed with polyvinylpyrrolidone (PVP) in water, it forms a water-insoluble precipitate that neither swells nor adheres to tissues. Methods and Results: We developed a novel solid/solution interface complexation method to obtain a water-swellable PAA/PVP complex. First, PAA solution was dried up in a vessel to form a film. The PAA film was then immersed in an aqueous PVP solution to obtain a highly swollen PAA/PVP hydrogel. Heat drying of the hydrogel yielded a transparent film, while freeze-drying the hydrogel provided a soft sponge. Both the PAA/PVP film and sponge could be re-swelled by water to obtain a bioadhesive gel. A relatively larger specific surface area of the sponge than that of the film led to a more rapid swelling and water absorption behavior and quick adhesion to tissues. The addition of hyaluronic acid (HA) improved the mechanical characteristics of the sponges. PAA/PVP/HA sponges had low cytotoxicity, and they exhibited high hemostatic efficiency in clinical studies after dialysis treatment or tooth extraction, even in patients on antithrombotic drugs. Conclusions: Such bioadhesive materials consisting of low-toxicity polymers have a high potential for use in medical hemostatic devices.

Poly(acrylic acid) (PAA) is a water-soluble synthetic polymer that exhibits bioadhesive properties and has been applied in various novel medical devices, such as drug-delivery carriers and hemostatic agents. PAA forms a water-insoluble complex when mixed with polyvinylpyrrolidone (PVP). If PAA and PVP are mixed in water, they form an aggregated precipitate, which neither swells nor adheres to tissues. The formation of the hydrophobic complex was caused by hydrophobic interactions between the main chains of both polymers aligned the same as a zipper. To hinder the zipper-like alignment of the polymer main chains, hyaluronic acid (HA), a macromolecular viscous polysaccharide, was added to the PVP solution prior to complex formation. When the initial concentration of PAA was lower than 0.05%, HA effectively prevented the aggregation of PAA/PVP complexes and resulted in a slightly clouded suspension. Freeze-drying of the mixture yielded a soft white sponge, which could immediately swell in water to form a highly bioadhesive hydrogel. The PAA/PVP complex prepared with HA exhibited high hemostatic efficiency in clinical studies, even in patients on antithrombotic drugs.