Pro-aromatic Natural Terpenes as Unusual "Slingshot" Antioxidants with Promising Ferroptosis Inhibition Activity

Chemistry. 2024 Dec 23;30(72):e202403320. doi: 10.1002/chem.202403320. Epub 2024 Nov 10.

Abstract

Ferroptosis is a cell death mechanism based on extensive cellular membrane peroxidation, implicated in neurodegenerative and other diseases. The essential oil component γ-terpinene, a natural monoterpene with a unique highly oxidizable pro-aromatic 1,4-cyclohexadiene skeleton, inhibits peroxidation of polyunsaturated lipid in model heterogeneous systems (micelles and liposomes). Upon H-atom abstraction, an unstable γ-terpinene-derived peroxyl radical is formed, that aromatizes to p-cymene generating HOO⋅ radicals. As HOO⋅ are small and hydrophilic radicals, they quickly diffuse outside the lipid core, blocking the radical chain propagation of polyunsaturated lipids. This unprecedented antioxidant "slingshot" mechanism explains why γ-terpinene shows a protective activity against ferroptosis, being effective at submicromolar concentrations in human neuroblastoma (SH-SY5Y) cells.

Keywords: Antioxidant; Essential oils; Ferroptosis; Lipid peroxidation; Superoxide.

MeSH terms

  • Antioxidants* / chemistry
  • Antioxidants* / pharmacology
  • Cell Line, Tumor
  • Cyclohexane Monoterpenes / chemistry
  • Cyclohexane Monoterpenes / pharmacology
  • Cymenes / chemistry
  • Cymenes / pharmacology
  • Ferroptosis* / drug effects
  • Humans
  • Lipid Peroxidation* / drug effects
  • Liposomes / chemistry
  • Monoterpenes / chemistry
  • Monoterpenes / pharmacology
  • Peroxides / chemistry
  • Peroxides / pharmacology
  • Terpenes / chemistry
  • Terpenes / pharmacology

Substances

  • Antioxidants
  • Cyclohexane Monoterpenes
  • gamma-terpinene
  • Cymenes
  • Terpenes
  • 4-cymene
  • perhydroxyl radical
  • Monoterpenes
  • Liposomes
  • Peroxides