Journal ArticleDOI
The Catalytic Mechanism of Diarylamine Radical-Trapping Antioxidants
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TLDR
The results presented here have significant implications in the future design of antioxidant additives: diarylamines designed to yield intermediate alkoxyamines that undergo the retro-carbonyl-ene reaction are likely to be much more effective than existing compounds and will display catalytic radical-trapping activities at lower temperatures due to lower barriers to regeneration.Abstract:
Diarylamine radical-trapping antioxidants are important industrial additives, finding widespread use in petroleum-derived products. They are uniquely effective at elevated temperatures due to their ability to trap multiple radicals per molecule of diarylamine. Herein we report the results of computational and experimental studies designed to elucidate the mechanism of this remarkable activity. We find that the key step in the proposed catalytic cycle–decomposition of the alkoxyamine derived from capture of a substrate-derived alkyl radical with a diarylamine-derived nitroxide–proceeds by different mechanisms depending on the structure of both the substrate and the diarylamine. N,N-Diarylalkoxyamines derived from saturated substrates and diphenylamines decompose by N–O homolysis followed by disproportionation. Alternatively, those derived from unsaturated substrates and diphenylamines, or saturated substrates and N-phenyl-β-naphthylamine, decompose by an unprecedented concerted retro-carbonyl-ene reaction....read more
Citations
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Journal ArticleDOI
Insight into the mechanism of ferroptosis inhibition by ferrostatin-1.
Giovanni Miotto,Monica Rossetto,Maria Luisa Di Paolo,Laura Orian,Rina Venerando,Antonella Roveri,Ana-Marija Vučković,Valentina Bosello Travain,Mattia Zaccarin,Lucio Zennaro,Matilde Maiorino,Stefano Toppo,Fulvio Ursini,Giorgio Cozza +13 more
TL;DR: GPx4 and fer-1 in the presence of ferrous iron produces, by distinct mechanism, the most relevant anti-ferroptotic effect, i.e the disappearance of initiating lipid hydroperoxides.
Journal ArticleDOI
Factors That Control C-C Cleavage versus C-H Bond Hydroxylation in Copper-Catalyzed Oxidations of Ketones with O2.
TL;DR: The role of hppH is uncovered to act not only as a base in the transformation but also as a reductant of the peroxide to the corresponding α-hydroxy ketone, allowing the tuning of reduction efficiency toward higher driving forces, if required.
Journal ArticleDOI
The Potency of Diarylamine Radical-Trapping Antioxidants as Inhibitors of Ferroptosis Underscores the Role of Autoxidation in the Mechanism of Cell Death.
TL;DR: It is shown that diarylamine RTAs used to protect petroleum-derived products from autoxidation can be potent inhibitors of ferroptosis, and further support the argument that lipid peroxidation (autoxidation) plays a major role in the mechanism of cell death induced by either GPX4 inhibition, gpx4 deletion, or GSH depletion.
Journal ArticleDOI
Methods for determining the efficacy of radical-trapping antioxidants.
Bo Li,Derek A. Pratt +1 more
TL;DR: The purpose of this review is to provide a comprehensive overview of different approaches to measure the kinetics of the reactions of radical-trapping antioxidants with peroxyl radicals, and their use to study the inhibition of hydrocarbon (lipid) autoxidation in homogeneous solution, as well as biphasic media and cell culture.
Journal ArticleDOI
Maximizing the reactivity of phenolic and aminic radical-trapping antioxidants: just add nitrogen!
TL;DR: Heterocyclic diarylamines have real potential to increase the longevity of petroleum-derived products in a variety of applications where diphenylamines are currently used, and it is demonstrated that they could be used synergistically with less reactive, less expensive, phenolic RTAs.
References
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Journal ArticleDOI
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Journal ArticleDOI
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Journal ArticleDOI
Advances in Radical-Trapping Antioxidant Chemistry in the 21st Century: A Kinetics and Mechanisms Perspective
Keith U. Ingold,Derek A. Pratt +1 more
TL;DR: The radicals produced by H-atom abstraction from the enol (or keto) form of HP-136 and related compounds (see Scheme 6) may not react with O2, but they do trap peroxyland carboncentered radicals.
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