An In Silico study of TiO₂ nanoparticles interaction with twenty standard amino acids in aqueous solution

Titanium dioxide (TiO₂) is probably one of the most widely used nanomaterials, and its extensive exposure may result in potentially adverse biological effects. Yet, the underlying mechanisms of interaction involving TiO₂ NPs and macromolecules, e.g., proteins, are still not well understood. Here, we perform all-atom molecular dynamics simulations to investigate the interactions between TiO₂ NPs and the twenty standard amino acids in aqueous solution exploiting a newly developed TiO₂ force field. We found that charged amino acids play a dominant role during the process of binding to the TiO₂ surface, with both basic and acidic residues overwhelmingly preferred over the non-charged counterparts. By calculating the Potential Mean Force, we showed that Arg is prone to direct binding onto the NP surface, while Lys needs to overcome a ~2 kT free energy barrier. On the other hand, acidic residues tend to form "water bridges" between their sidechains and TiO₂ surface, thus displaying an indirect binding. Moreover, the overall preferred positions and configurations of different residues are highly dependent on properties of the first and second solvation water. These molecular insights learned from this work might help with a better understanding of the interactions between biomolecules and nanomaterials.