Development of Photoactive -CN/Poly(vinyl alcohol) Composite Hydrogel Films with Antimicrobial and Antibiofilm Activity.

Free-standing, composite hydrogels containing the visible-light responsive metal-free semiconductor graphitic carbon nitride (-CN) as an integral component have been fabricated by direct casting techniques. At 0.67% -CN loading, intermolecular interactions between the semiconductor particles and the PVA polymer chains enhance both the mechanical and photophysical properties of the resulting hydrogels. In contrast, much higher -CN loadings of 3.3 or 6.7% -CN resulted in growth of the average semiconductor particle size and reduction in interactions between the incorporated photocatalyst and the PVA chains. The increased dimensions of the -CN semiconductor particles had the effect of compromising the mechanical properties of the composite system and reducing the lifetime of photogenerated charge carriers. However, the close proximity of -CN particles that is realized at increased semiconductor loading densities improves the absorption cross section of the material, resulting in an overall improvement in the photocatalytic activity of the material. Application of visible radiation caused all of the composite hydrogels to generate hydrogen peroxide (HO) at catalytic rates of 0.9-2.5 M/min, while HO decomposition rates remained similar across the different preparations. In studies to examine antimicrobial performance, irradiation of 6.7% -CN/PVA hydrogel samples with visible radiation (400 ≤ λ ≤ 800 nm) generated sufficient HO to significantly reduce both the viable planktonic cell population and biofilm formation in cultures of .