PBA-Derived Heteroatom-Doped Mesoporous Graphitic Spheroids as Peroxidase Nanozyme for In Vitro Tumor Cells Detection

Inspired by the two kinds of naturally occurring peroxidases (POD) with vanadium or heme (iron)-based active catalytic centers, we have developed a dual metal-based nanozyme with dual V and Fe-based active catalytic centers. Co-doping of graphene with heteroatoms has a synergistic effect on the catalytic properties of the nanomaterial as the distances of migration of the substrates drastically reduce. However, a few studies have reported the codoping of heterometallic elements in the graphene structure due to the complexity of the synthesis procedures. Herein, we report the synthesis of in situ doped bimetallic VNFe@C mesoporous graphitic spheroids nanozyme via pyrolysis without the assistance of any template assisted method. The Prussian-blue analog-based precursor material was synthesized by a facile one-step low-temperature synthesis procedure. The bimetallic spheroids showed an excellent affinity toward H₂O₂, with a K_m value of 0.26 mM when compared to 0.436 for the natural POD, which is much better than the natural POD, which was utilized to detect tumor cells in vitro through the intracellular H₂O₂ produced by these cells under high oxidative stress. The VNFe@C mesoporous spheroids generate dual reactive oxygen species, including the ^•OH and ^•O₂H^- radicals, in the presence of H₂O₂, which are responsible for the POD-like activity of these nanozymes, while the bimetallic V/Fe doping plays a synergistic role in the enhancement of the activity of codoped graphitic spheroids.