We here present a new method for preparing ligand-free titania nanoparticles, which are easily amenable to surface functionalization in an aqueous environment. The specific advantage of this method is that it combines the advantages of nonaqueous synthetic processes (high crystallinity) to those of a surface functionalization in a water medium, which allows for a wider variety of biofunctional (and nonorganic-soluble) groups to be added on the nanoparticles. In particular, we report on the characterization of the three phases of synthesis, dispersion in water environment and surface functionalization of the nanoparticles, focusing on a qualitative evaluation of the surface adsorption mechanism.

Titania (anatase) nanoparticles were successfully PEGylated through the use of catechol (dopamine)-terminated PEG derivatives. The resulting materials were characterized by excellent stability at neutral pH and extremely low toxicity (phagocytic and nonphagocytic cell lines). In particular, we focused on the comparison between mono-and bis-catechol PEGs. Due to the double terminal anchorage on the titania surface, bis-catechol ligands can produce chains differing from classical monoanchored PEG in conformation (horseshoe-shaped vs brush) and thus the possibility of interactions with biomolecules. At the same time, less than quantitative catechol binding may lead to the presence of dangling chains with unbound catechols which can polymerize and eventually produce PEG/titania nanocomposite colloids. Our results on double-functional PEG2000 show the latter to be the case. Pluronic F127 was also used as a bifunctional ligand, leading to nanocomposite aggregates with an even larger organic content.

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