Strong Antiproliferative Activity Observed in Hammett-Guided Electronic Modulation of GPx-Mimetic Pathways in Aryl Selenoureas

Organoselenium chemistry has undergone remarkable development over the past five decades, evolving from its initial association with high toxicity into a field with pivotal contributions to materials science, organic synthesis, catalysis, and Medicinal Chemistry. Among the diverse biological activit...

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Detalhes bibliográficos
Autores: Begines Aguilar, Paloma, Pérez-Lage, Clara I., Puerta, Adrián, Padrón, José M., López López, Óscar, Fernández-Bolaños Guzmán, José María
Formato: artículo
Estado:Versión publicada
Fecha de publicación:2026
País:España
Recursos:Universidad de Sevilla (US)
Repositorio:idUS. Depósito de Investigación de la Universidad de Sevilla
OAI Identifier:oai:dnet:idus________::ce2523f86f04ad4ffb02c06d6e53eee2
Acesso em linha:https://hdl.handle.net/11441/186294
https://doi.org/10.3390/ijms27083574
Access Level:acceso abierto
Palavra-chave:Selenoureas
Antioxidants
GPx-mimic
Hammett parameters
77Se-NMR
Antiproliferative properties
Descrição
Resumo:Organoselenium chemistry has undergone remarkable development over the past five decades, evolving from its initial association with high toxicity into a field with pivotal contributions to materials science, organic synthesis, catalysis, and Medicinal Chemistry. Among the diverse biological activities displayed by organoselenium compounds, their redox behaviour is particularly compelling, as many of these molecules act as efficient mimetics of the antioxidant enzyme glutathione peroxidase (GPx). In this work, we investigated the GPx-like activity of a series of N,N′-diaryl selenoureas toward the depletion of H2O2 and cumene hydroperoxide (CumOOH) as model ROS. Their reactivity was correlated with the electronic nature of the aryl substituents using a Hammett-type analysis, revealing a strong dependence of the reaction rate on remote electronic perturbations within the aromatic ring. Combined UV and NMR studies provided mechanistic evidence supporting a catalytic cycle in which selenoureas, operating at sub-stoichiometric loadings (1 mol%) and using a thiol as a cofactor-like molecule, can be used to efficiently scavenge ROS with half-lives of only a few minutes (~10–60 min). Furthermore, these selenoureas exhibited potent antiproliferative activity across several human solid tumour cell lines. Overall, these results offer mechanistic insight into the ROS-eliminating pathways of selenoureas and highlight their potential as chemopreventive or anticancer agents.