5,6-Dihydroxyindole-2-carboxylic Acid-TiO2 Charge Transfer Complexes in the Radical Polymerization of Melanogenic Precursor(s)

A combination of biomedical and technological applications is generating, over the past decades, the wellestablished interest toward melanins and melanogenesis. Several compounds have been explored to promote/catalyze oxidative polymerization of melanogenic precursors, such as 5,6-dihydroxyindole-2-carboxylic acid (DHICA), to melanin-like biopolymers in vitro. TiO2 has shown a photocatalytic activity driving DHICA polymerization and leading to the formation of melanin−TiO2 hybrid nanostructures with unique biocide behavior even under visible light. However, the mechanism of melanin formation in those hybrids is not yet well understood although a ligand to metal charge transfer (LMCT) process involving DHICA and Ti4+ ions was hypothesized. Here, we focus on melanin formation and apply a complementary analysis, by using photoluminescence (PL), UV−vis, electron paramagnetic resonance (EPR), and nuclear magnetic resonance (NMR) spectroscopy to reveal the mechanism of DHICA polymerization in the presence of a TiO2-sol. This study discloses TiO2 potentialities to drive and template DHICA polymerization to melanin via LMCT-based photo-oxidative process.