Cleavage of a Peroxide Bond via a Dual Attack by Functional Mimics of Glutathione Peroxidase DOI
Rakesh Kumar, Amirul Islam, Rudra Shankar Pati

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 17, 2024

Abstract Nonmetal‐containing peroxidase enzymes, including glutathione (GPx), and peroxiredoxins, control cellular redox levels by catalyzing the reduction of H 2 O . The remarkably higher reactivity GPx enzyme as compared to fully dissociated synthetic selenolate/thiolate molecule is probably due dual‐attack on peroxide bond (HO 1 −O H) enzyme; first one a nucleophilic attack moiety atom second at acidic “parked proton” from Trp or His residue present enzyme's active site, leading facile cleavage O−O bond. Herein, we report two compounds ( ), having selenolate (Se − ) proton donor (imidazolium −COOH group) moieties, which showed excellent GPx‐like activity via combined effect that donates electrons antibonding (σ*) orbital imidazolium carboxylic acid side chain forms strong H‐bonding with facilitates more efficiently. exhibit remarkable ability in protecting Cu(I)‐complex [TpmCu(CH 3 CN)] + 9 against acting sacrificial antioxidant, thereby preventing metal‐mediated ROS production.

Language: Английский

Cleavage of a Peroxide Bond via a Dual Attack by Functional Mimics of Glutathione Peroxidase DOI
Rakesh Kumar, Amirul Islam, Rudra Shankar Pati

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 17, 2024

Abstract Nonmetal‐containing peroxidase enzymes, including glutathione (GPx), and peroxiredoxins, control cellular redox levels by catalyzing the reduction of H 2 O . The remarkably higher reactivity GPx enzyme as compared to fully dissociated synthetic selenolate/thiolate molecule is probably due dual‐attack on peroxide bond (HO 1 −O H) enzyme; first one a nucleophilic attack moiety atom second at acidic “parked proton” from Trp or His residue present enzyme's active site, leading facile cleavage O−O bond. Herein, we report two compounds ( ), having selenolate (Se − ) proton donor (imidazolium −COOH group) moieties, which showed excellent GPx‐like activity via combined effect that donates electrons antibonding (σ*) orbital imidazolium carboxylic acid side chain forms strong H‐bonding with facilitates more efficiently. exhibit remarkable ability in protecting Cu(I)‐complex [TpmCu(CH 3 CN)] + 9 against acting sacrificial antioxidant, thereby preventing metal‐mediated ROS production.

Language: Английский

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