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Nanometric TiO₂ is largely employed in cosmetics, but in vitro toxic effects have been reported when nano-TiO₂ is exposed to UV light. The photoreactivity of TiO₂ largely depends on its crystal phase, namely, anatase and rutile. Surface acidity, which is also dependent on crystal structure, may impart a positive or negative charge to the nanomaterial surface and ultimately modulate particle adhesion to tissues. Three nanometric TiO₂ powders with a different crystal lattice and surface charge (anatase, rutile, and anatase/rutile) have been employed here to investigate their interaction with the skin and to examine the molecular mechanisms of the TiO₂-induced oxidative damage. The strength of the interaction of nano-TiO₂ with skin has been revealed by chemiometric mapping (μ-XRF and SEM-EDS) after tissue washing. Positively charged anatase and anatase/rutile, but not negatively charged rutile, were strongly held on the skin surface and were able to promote a structural rearrangement of the lipid bilayer in the stratum corneum (DSC and Raman) under controlled indoor illumination (UVA &lt; 1 mW/m²). Under the same conditions, cell-free reactivity tests (ROS-mediated free-radical release and lipoperoxidation) indicated that anatase and anatase/rutile are more reactive than rutile, suggesting a ROS-mediated oxidative mechanism that may alter the structure of the stratum corneum. Both the higher oxidative potential and the stronger adhesion to skin of anatase and anatase/rutile TiO₂ may explain the stronger disorganization induced by these two samples and suggests the use of rutile to produce safer TiO₂-based cosmetic and pharmaceutical products.

Crystalline Phase Modulates the Potency of Nanometric TiO2 to Adhere to and Perturb the Stratum Corneum of Porcine Skin under Indoor Light

Crystalline Phase Modulates the Potency of Nanometric TiO₂ to Adhere to and Perturb the Stratum Corneum of Porcine Skin under Indoor Light