Titanium based complexes with melanin precursors as a tool for directing melanogenic pathways

Bioinspired melanin based hybrid materials hold huge promise for developing multifunctional systems for a considerable set of applications. Yet, control of melanogenic pathway is a big challenge to allow rational design of nanostructured systems with tuned structures and improved properties. This study proves the ability of titanium ions interactions with melanin precursors in directing melanogenic pathway. To this purpose complementary spectroscopic evidences were collected to reveal that in the presence of a TiO2-sol, amino-acid complex of Ti(IV) ions and DOPA actually inhibits its cyclization, during oxidative process, thus leading to DOPA-based polyphenols, stable even in oxidative environment, rather than eumelanin. This hugely impacts on the biological properties of the final hybrid systems which, discloses relevant and durable antioxidant behavior but poor antimicrobial activity differently from DHICA-based hybrid nanostructures. Overall this study, discloses the high potential of ceramic templated approach in combination with the selection of melanin precursor in achieving a fine tuning of physico-chemical as well as bioactivity of melanin-TiO2 nanostructures, opening new scenarios towards the design of cutting-edge biomaterials with tailored biological properties.