A series of Zn/Mn binary oxides with different molar ratios were synthesized via co-precipitation from a solution obtained through the leaching of a black mass originating from the mechanical recycling of spent alkaline and Zn–C batteries.

Four formulations have been used to produce different poly(2-hydroxyethyl methacrylate) (PHEMA) thin films, containing singlet oxygen photosensitizer Rose Bengal (RB). The polymers have been characterized employing Thermogravimetric Analysis (TGA), Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) and UV-vis Absorption Spectroscopy. When irradiated with white light (400–700 nm) films generated singlet oxygen (1O2), as demonstrated by the reactivity with 1O2 trap 9,10-dimethylanthracene (DMA). Material with the highest RB loading (polymer A4, 835 nmol RB/g polymer) was able to perform up to ten cycles of DMA oxygenation reactions at high conversion rates (ca. 90%). Polymer A4 was also able to produce the complete eradication of a Pseudomonas aeruginosa planktonic suspension of 8 log10 CFU/mL, when irradiated with white light (total dose 72 J/cm2). The antimicrobial photodynamic effect was remarkably enhanced by adding potassium iodide (100 mM). In such conditions the complete bacterial reduction occurred with a total light dose of 24 J/cm2. Triiodide anion (I3−) generation was confirmed by UV-vis absorption spectroscopy. This species was detected inside the PHEMA films after irradiation and at concentrations ca. 1 M. The generation of this species and its retention in the matrix imparts long-lasting bactericidal effects to the RB@PHEMA polymeric hydrogels. The polymers here described could find potential applications in the medical context, when optimized for their use in everyday objects, helping to prevent bacterial contagion by contact with surfaces.

A series of poly(2-hydroxyethyl methacrylate) (PHEMA) thin films entrapping photosensitizer Rose Bengal (RB) and tetrabutylammonium iodide (TBAI) have been synthetized. The materials have been characterized by means of Thermogravimetric Analysis (TGA), Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR) and UV-vis Absorption spectroscopy. Irradiation of the materials with white light led to the generation of several bactericidal species, including singlet oxygen (1O2), triiodide anion (I3−) and hydrogen peroxide (H2O2). 1O2 production was demonstrated spectroscopically by reaction with the chemical trap 2,2′-(anthracene-9,10-diylbis(methylene))dimalonic acid (ABDA). In addition, the reaction of iodide anion with 1O2 yielded I3− inside the polymeric matrix. This reaction is accompanied by the formation of H2O2, which diffuses out the polymeric matrix. Generation of both I3− and H2O2 was demonstrated spectroscopically (directly in the case of triiodide by the absorption at 360 nm and indirectly for H2O2 using the xylenol orange test). A series of photodynamic inactivation assays were conducted with the synthesized polymers against Gram-negative bacteria Escherichia coli and Pseudomonas aeruginosa. Complete eradication (7 log10 CFU/mL) of both bacteria occurred after only 5 min of white light irradiation (400–700 nm; total energy dose 24 J/cm2) of the polymer containing both RB and TBAI. The control polymer without embedded iodide (only RB) showed only marginal reductions of ca. 0.5 log10 CFU/mL. The main novelty of the present investigation is the generation of three bactericidal species (1O2, I3− and H2O2) at the same time using a single polymeric material containing all the elements needed to produce such a bactericidal cocktail, although the most relevant antimicrobial activity is shown by H2O2. This experimental approach avoids multistep protocols involving a final step of addition of I−, as described previously for other assays in solution.