Having thus described the origin and uses of the pigment, we now come to the question, what is lithopone? It is, in short, a chemical compound usually consisting of 30.5 per cent zinc sulphide, 1.5 per cent zinc oxide and 68 per cent barium sulphate, but these proportions vary slightly in the different makes. Lithopone of this composition is sold as the highest grade, either as red seal or green seal, as it best suits the idea of the manufacturer. Many manufacturers, especially in Europe, sell and also export other brands under other seals, containing 24, 20, 18 and as little as 12 per cent of zinc sulphide with very small percentages of zinc oxide, the balance being usually barium sulphate, but sometimes certain portions of China clay or gypsum (calcium sulphate) or whiting (calcium carbonate). Such brands are not a chemical compound, but mechanical mixtures of the chemically compounded lithopone and the admixtures referred to.

As mentioned above, these oxide NPs are harmful in part because both anatase and rutile forms are semiconductors and produce ROS. Particularly, P25 kind has band-gap energies estimated of 3.2 and 3.0 eV, equivalent to radiation wavelengths of approximately 388 and 414 nm, respectively. Irradiation at these wavelengths or below produces a separation of charge, resulting in a hole in the valence band and a free electron in the conduction band, due to the electron movement from the valence to conduction bands. These hole–electron pairs generate ROS when they interact with H₂O or O₂ [43,44]. It was described that they can cause an increase in ROS levels after exposure to UV-visible light [45]. The NBT assay in the studied samples showed that bare P25TiO₂NPs produce a large amount of ROS, which is drastically reduced by functionalization with vitamin B2 (Fig. 5). This vitamin, also known as riboflavin, was discovered in 1872 as a yellow fluorescent pigment, [46] but its function as an essential vitamin for humans was established more than sixty years later, and its antioxidant capacity was not studied until the end of the XX century [47,48]. This antioxidant role in cells is partially explained because the glutathione reductase enzyme (GR) requires it for good functionality. This enzyme is the one in charge of the conversion of oxidized glutathione to its reduced form which acts as a powerful inner antioxidant and can quench the ROS [49,50]. The cost of this action is that the glutathione is converted to the oxidized form and needs to be recovered by the GR. Consequently, the cells need more vitamin B2. Another glutathione action is the protection against hydroperoxide. This activity is also mediated by riboflavin. Therefore, local delivery of this vitamin seems to significantly help the cells in their fight to keep the oxidative balance, once they are exposed to high levels of ROS.

Total zinc and barium sulphate

Total Zinc (as ZnS)