Assessing Mn as an antioxidant agent in bioactive glasses by quantification of catalase and superoxide dismutase enzymatic mimetic activities

The antioxidant activity of Mn as additive in a 45S5 type glass system with and without P2O5 was studied by mimicking the activity of catalase (CMA) and superoxide dismutase (SOD) enzymes. Glasses were melted either under oxidizing or reducing atmosphere (N2/H2) to compare the processing influence on the Mn oxidation state. Thermal (DTA) and optical (UV-Vis) characterizations of the glass powders were carried out to obtain further insight into the structural role of Mn. A correlation of in vitro apatite formation between Tris buffer solution and Simulated Body Fluid (SBF) was performed to optimise Mn substitution, where a decrease in apatite formation was observed by increasing Mn content. Despite this, glasses with up to 1.0 mol% MnO did not show any delay in apatite formation and maintained their CMA and SOD activity. The antioxidant effect of Mn can be attributed to the interconversion Mn2+ <-> Mn3+ occurring on the glass surface through a heterogeneous catalysis. P2O5 plays an important role in the antioxidant effect of the glass, possibly by charge balancing Mn ions and forming more stable units compared to those formed with Ca and Na. The amount of Mn2+ is predominant in the glass network with respect to Mn3+ in all synthetized glasses. Moreover, glass melting in a reducing atmosphere further avoided Mn oxidation.