Towards the development of a novel bioinspired functional material: Synthesis and characterization of hybrid TiO₂/DHICA-melanin nanoparticles

Abstract

A large number of recent literature data focus on modification/modulation of surface chemistry of inorganic materials in order to improve their functional properties. Melanins, a wide class of natural pigments, are recently emerging as a powerful organic component for developing bioinspired active material for a large number of applications from organoelectronics to bioactive compounds.

Here we report the use of the approach referred as “chimie douce”, involving in situ formation of the hybrids through reactions of precursors under mild conditions, to prepare novel hybrid functional architectures based on eumelanin like 5,6 dihydroxyindole-2-carboxylic acid (DHICA) polymer and TiO₂. Two synthesis procedures were carried out to get DHICA-melanin coated TiO₂ nanoparticles as well as mixed DHICA/TiO₂ hybrid nanostructures. Such systems were characterized through EPR, FT-IR and fluorescence spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and TEM microscopy in order to assess the effect of synthesis path as well as of DHICA content on structural, morphological and optical properties of TiO₂ nanostructures. In particular, EPR, FT-IR spectra and TGA analysis confirmed the presence of DHICA-melanin in these samples. TEM measurements indicated the formation of the nanoparticles having relatively narrow size distribution with average particle size of about 10 nm. DHICA-melanin does act as a morphological agent affecting morphology of hybrid nanostructures. XRD analysis proved that TiO₂ hybrid nanoparticles kept anatase structures for DHICA-melanin contents within the range of investigated compositions, i.e. up to 50% wt/wt.