A bioinspired sulfur-Fe-heme nanozyme with selective peroxidase-like activity for enhanced tumor chemotherapy

Nat Commun. 2024 Dec 5;15(1):10605. doi: 10.1038/s41467-024-54868-w.

Abstract

Iron-based nanozymes, recognized for their biocompatibility and peroxidase-like activities, hold promise as catalysts in tumor therapy. However, their concurrent catalase-like activity undermines therapeutic efficacy by converting hydrogen peroxide in tumor tissues into oxygen, thus diminishing hydroxyl radical production. Addressing this challenge, this study introduces the hemin-cysteine-Fe (HCFe) nanozyme, which exhibits exclusive peroxidase-like activity. Constructed through a supramolecular assembly approach involving Fmoc-L-cysteine, heme, and Fe²⁺ coordination, HCFe distinctly incorporates heme and [Fe-S] within its active center. Sulfur coordination to the central Fe atom of Hemin is crucial in modulating the catalytic preference of the HCFe nanozyme towards peroxidase-like activity. This unique mechanism distinguishes HCFe from other bifunctional iron-based nanozymes, enhancing its catalytic selectivity even beyond that of natural peroxidases. This selective activity allows HCFe to significantly elevate ROS production and exert cytotoxic effects, especially against cisplatin-resistant esophageal squamous cell carcinoma (ESCC) cells and their xenografts in female mice when combined with cisplatin. These findings underscore HCFe's potential as a crucial component in multimodal cancer therapy, notably in augmenting chemotherapy efficacy.

MeSH terms

  • Animals
  • Antineoplastic Agents / chemistry
  • Antineoplastic Agents / pharmacology
  • Catalysis
  • Cell Line, Tumor
  • Cisplatin / pharmacology
  • Cysteine* / chemistry
  • Cysteine* / metabolism
  • Female
  • Heme* / chemistry
  • Heme* / metabolism
  • Hemin / chemistry
  • Hemin / metabolism
  • Humans
  • Hydrogen Peroxide / chemistry
  • Hydrogen Peroxide / metabolism
  • Iron* / chemistry
  • Iron* / metabolism
  • Mice
  • Mice, Inbred BALB C
  • Mice, Nude
  • Peroxidase / metabolism
  • Reactive Oxygen Species / metabolism
  • Sulfur* / chemistry
  • Sulfur* / metabolism
  • Xenograft Model Antitumor Assays

Substances

  • Sulfur
  • Iron
  • Cysteine
  • Heme
  • Peroxidase
  • Reactive Oxygen Species
  • Antineoplastic Agents
  • Cisplatin
  • Hemin
  • Hydrogen Peroxide