Tannic Acid-Induced Interfacial Ligand-to-metal Charge Transfer and the Phase Transformation of Fe3O4 Nanoparticles for the Photothermal Bacteria Destruction

An iron oxide (Fe3O4)-mediated photothermal treatment has been revealed as the next generation of noninvasive and nontoxic theranostic nanoagents compared with other inorganic nanoparticles. Nevertheless, iron oxide with NIR-mediated activity is limited by its inability to be mass produced and its long-lasting photon-to-thermal conversion. Herein, we develop using a green reagent, tannic acid (TNA), which assisted hydrothermal reaction to generate black Fe3O4 nanoparticles by using commercially available nanoptical gamma-Fe2O3 NPs as a starting material. The phase transformation from gamma-Fe2O3 to the reduced form of Fe3O4 is assisted by TNA in the solution phase. Based on the formation of the interfacial TNA-Fe chelation and the delicate phase transformation from gamma-Fe2O3 to Fe3O4 structures, the colloidal black Fe3O4 nanoparticles exhibit broad absorption that covers the visible and NIR wavelengths. Specific interfacial ligand-to-metal charge transfers between the TNA and iron ions at the surface of iron oxide nanoparticles, improves the absorbance and leads to the highest photon-to-thermal conversion (eta = 35.7%) at 808 nm compared with other iron oxide nanomaterials. After modifying d-mannose (MA) onto the surface of the Fe3O4@TNA nanoparticles, the local heat can efficiently transfer from the Fe3O4@TNA nanoparticles to the vicinity of the bacterial FimH adhesion molecule, causing extensive photothermal injury to O157:H7 and ESBL strain bacteria with over 99% cell death at 200 ppm[Fe] with 808 nm light at 2.25 mW/cm2. Based on its robust photostability, Fe3O4@TNA@MA shows photothermal bactericidal recyclability through magnetic collection, adhesion, and photothermal processes.