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<p>Iron-oxide magnetic nanoparticles (MNPs) have been extensively investigated as magnetically actuated nanocatalysts for diagnostic and therapeutic applications. However, because wüstite/magnetite/maghemite phases can interconvert, coexisting Fe<sup>2+</sup>/Fe<sup>3+</sup> species may redirect Fenton-like chemistry and generate reactive oxygen species (ROS) profiles that differ from the intended biocatalytic pathway. Here, we investigate monodisperse biphasic FeO@Fe<sub>3</sub>O<sub>4</sub> core-shell MNPs with an average particle size ⟨d⟩ = 9.6(5) nm, and their glucose-coated analogue, combining EPR radical analysis with toxicity testing in a 3D HepG2 hepatic spheroid model. Naked particles exhibited conventional Fenton-like behavior dominated by hydroxyl radicals (⋅OH), whereas glucose coating markedly suppressed ⋅OH while increasing hydroperoxyl radicals (⋅OOH; ≈55 pM at 60&#xa0;min), demonstrating ligand-controlled rerouting of the radical pathway. TEM mapping across spheroid cross-sections showed preferential MNP accumulation in the outer layer, with most observed events confined to the outer ≈10–15&#xa0;μm, corresponding to an approximately one-cell-thick rim; sparse deeper events were observed up to ≈30–35&#xa0;μm. MNPs produced dose- and time-dependent cytotoxicity in HepG2 spheroids, with IC<sub>50</sub> values of 29.3 (24&#xa0;h) and 10.8 (96&#xa0;h) µg·cm<sup>− 2</sup>, without evidence of lipid peroxidation or genotoxicity. MDA levels remained unchanged, the comet assay showed no increase in DNA damage, and γH2AX and phospho-H3 (p-H3) positive events were not detected. Our results show that glucose functionalization provides a simple route to modulate radical pathways and define operational windows for redox-active FeO@Fe<sub>3</sub>O<sub>4</sub> nano-reactors in oxidative nanomedicine.</p>

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Glucose coated FeO@Fe3O4 nanoparticles show tunable catalytic reactivity and safety in a 3D hepatic in vitro model

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年5月12日

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  • Marco A. Morales Ovalle,
  • Iza Rozman,
  • Elin L. Winkler,
  • Enio Lima Jr.,
  • Alja Štern,
  • Katja Kološa,
  • Bojana Žegura,
  • Gerardo F. Goya

摘要

Iron-oxide magnetic nanoparticles (MNPs) have been extensively investigated as magnetically actuated nanocatalysts for diagnostic and therapeutic applications. However, because wüstite/magnetite/maghemite phases can interconvert, coexisting Fe2+/Fe3+ species may redirect Fenton-like chemistry and generate reactive oxygen species (ROS) profiles that differ from the intended biocatalytic pathway. Here, we investigate monodisperse biphasic FeO@Fe3O4 core-shell MNPs with an average particle size ⟨d⟩ = 9.6(5) nm, and their glucose-coated analogue, combining EPR radical analysis with toxicity testing in a 3D HepG2 hepatic spheroid model. Naked particles exhibited conventional Fenton-like behavior dominated by hydroxyl radicals (⋅OH), whereas glucose coating markedly suppressed ⋅OH while increasing hydroperoxyl radicals (⋅OOH; ≈55 pM at 60 min), demonstrating ligand-controlled rerouting of the radical pathway. TEM mapping across spheroid cross-sections showed preferential MNP accumulation in the outer layer, with most observed events confined to the outer ≈10–15 μm, corresponding to an approximately one-cell-thick rim; sparse deeper events were observed up to ≈30–35 μm. MNPs produced dose- and time-dependent cytotoxicity in HepG2 spheroids, with IC50 values of 29.3 (24 h) and 10.8 (96 h) µg·cm− 2, without evidence of lipid peroxidation or genotoxicity. MDA levels remained unchanged, the comet assay showed no increase in DNA damage, and γH2AX and phospho-H3 (p-H3) positive events were not detected. Our results show that glucose functionalization provides a simple route to modulate radical pathways and define operational windows for redox-active FeO@Fe3O4 nano-reactors in oxidative nanomedicine.