Controlled Delivery and Photopatterning of Mechanical Properties in Polysaccharide Hydrogels Using Vanadium Coordination and Photochemistry.

Incorporation of the transition metal ion V(V) into hydrogels has been used to impart photoresponsive behavior, which was used to tune materials properties during light irradiation. The photoreaction in QHE-cellulose/agarose hydrogels coordinated with vanadium was evidenced by a clear color change of yellow to blue through a green intermediate. This color change was attributed to the reduction of V(V) to V(IV) as described in our previous work. A concomitant oxidative breakdown of the polysaccharide chain was noticeable upon the reduction of V(V) with a decrease in stiffness (G') of the hydrogel material. This reduction of the metal ion and breakdown of polysaccharide chain induced irreversible changes in the microstructure of the hydrogel, enabling the controlled delivery of V(IV) and/or encapsulated cargo. Scanning electron microscopy studies showed an increase in pore sizes and guest cavity formation during irradiation. In addition to the significant drop in mechanical properties like storage and loss modulus in the gel materials, a viscosity drop in the polymer solution was observed through irradiation, indicating breakdown of the polysaccharide chain. A photomask can be used to create discrete patterns on these materials upon irradiation.