SharathBabu Bidare N, Shivangi Shivangi, Valiyaveettil Aswathi, Annaraj Balakumaran, Mugesh Govindasamy
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, 560012, India.
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore, 560012, India.
Free Radic Biol Med. 2025 Jun 24;238:275-292. doi: 10.1016/j.freeradbiomed.2025.06.047.
Glutathione peroxidases (GPXs) are a family of selenoenzymes that protect mammalian cells from oxidative damage by catalyzing the glutathione (GSH)-dependent reduction of peroxides. Among the eight human GPX isoforms (GPX1-8), GPX4 plays a critical role in suppressing ferroptosis, an iron-dependent, non-apoptotic form of cell death driven by the accumulation of lipid hydroperoxides. Ferroptosis has been implicated in the pathogenesis of various degenerative disorders, including neurodegenerative diseases. The development of GPX4 functional mimetics represents a promising strategy to prevent ferroptosis and its associated pathologies. Here, we report the design and synthesis of Compd. 5, a selenium-based small molecule that functionally mimics GPX4 activity. Compd. 5 robustly protects neurons from ferroptosis induced by diverse metabolic stressors, including GPX4 knockdown. Notably, Compd. 5 retains its anti-ferroptotic efficacy even under GSH-deficient conditions, highlighting its potential utility in contexts of impaired cellular GSH availability. Mechanistic studies demonstrate that Compd. 5 directly reduces HpETE-PE (hydroperoxy-eicosatetraenoyl-phosphatidylethanolamine), a key phospholipid hydroperoxide that drives ferroptosis, thereby closely recapitulating the ferroptosis-suppressive function of GPX4. This study provides compelling evidence that rationally designed GPX4 functional mimetics robustly suppress ferroptosis across diverse cell types under a broad spectrum of ferroptosis-inducing conditions. Thus, Compd. 5, a synthetic selenium-based small molecule with specific GPX4-like activity, represents a new class of anti-ferroptotic agents with significant translational potential for the treatment of neurodegenerative and other ferroptosis-driven diseases.
谷胱甘肽过氧化物酶(GPXs)是一类硒酶,通过催化依赖谷胱甘肽(GSH)的过氧化物还原反应,保护哺乳动物细胞免受氧化损伤。在人类的八种GPX同工型(GPX1 - 8)中,GPX4在抑制铁死亡中起关键作用,铁死亡是一种由脂质氢过氧化物积累驱动的铁依赖性、非凋亡性细胞死亡形式。铁死亡与包括神经退行性疾病在内的各种退行性疾病的发病机制有关。开发GPX4功能模拟物是预防铁死亡及其相关病理的一种有前景的策略。在此,我们报告了化合物5的设计与合成,这是一种基于硒的小分子,其功能模拟GPX4活性。化合物5能强有力地保护神经元免受多种代谢应激源诱导的铁死亡,包括GPX4基因敲低。值得注意的是,即使在GSH缺乏的条件下,化合物5仍保留其抗铁死亡功效,突出了其在细胞内GSH可用性受损情况下的潜在应用价值。机制研究表明,化合物5直接还原HpETE - PE(氢过氧化二十碳四烯酰磷脂酰乙醇胺),这是一种驱动铁死亡的关键磷脂氢过氧化物,从而紧密模拟了GPX4的铁死亡抑制功能。这项研究提供了令人信服的证据,即合理设计的GPX4功能模拟物在广泛的铁死亡诱导条件下能强有力地抑制多种细胞类型中的铁死亡。因此,化合物5作为一种具有特定GPX4样活性的合成硒基小分子,代表了一类新型抗铁死亡药物,在治疗神经退行性疾病和其他铁死亡驱动的疾病方面具有显著的转化潜力。