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Inhibition of hydrocarbon autoxidation by nitroxide-catalyzed cross-dismutation of hydroperoxyl and alkylperoxyl radicals.

ABSTRACT: Nitroxides are putative intermediates in the accepted reaction mechanisms of the diarylamine and hindered amine antioxidants that are universally added to preserve synthetic and natural hydrocarbon-based materials. New methodology which enables monitoring of hydrocarbon autoxidations at low rates of radical generation has revealed that diarylnitroxides and hindered nitroxides are far better inhibitors of unsaturated hydrocarbon autoxidation than their precursor amines, implying intervention of a different mechanism. Experimental and computational investigations suggest that the nitroxides catalyze the cross-dismutation of hydroperoxyl and alkylperoxyl radicals to yield O₂ and a hydroperoxide, thereby halting the autoxidation chain reaction. The hydroperoxyl radicals - key players in hydrocarbon combustion, but essentially unknown in autoxidation - are proposed to derive from a tunneling-enhanced intramolecular (1,4-) hydrogen-atom transfer/elimination sequence from oxygenated radical addition intermediates. These insights suggest that nitroxides are preferred additives for the protection of hydrocarbon-based materials from autoxidation since they exhibit catalytic activity under conditions where their precursor amines are less effective and/or inefficiently converted to nitroxides in situ.

SUBMITTER: Harrison KA

PROVIDER: S-EPMC6053651 | biostudies-literature | 2018 Jul

REPOSITORIES: biostudies-literature

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Inhibition of hydrocarbon autoxidation by nitroxide-catalyzed cross-dismutation of hydroperoxyl and alkylperoxyl radicals.

Harrison Kareem A KA Haidasz Evan A EA Griesser Markus M Pratt Derek A DA

Chemical science 20180611 28

Nitroxides are putative intermediates in the accepted reaction mechanisms of the diarylamine and hindered amine antioxidants that are universally added to preserve synthetic and natural hydrocarbon-based materials. New methodology which enables monitoring of hydrocarbon autoxidations at low rates of radical generation has revealed that diarylnitroxides and hindered nitroxides are far better inhibitors of unsaturated hydrocarbon autoxidation than their precursor amines, implying intervention of a ...[more]

PMID: 30079220

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Project description:The unique ability of nitrone spin traps to detect and characterize transient free radicals by electron paramagnetic resonance (EPR) spectroscopy has fueled the development of new spin traps with improved properties. Among a variety of free radicals in chemical and biological systems, superoxide radical anion (O(2)(•-)) plays a critical role as a precursor to other more oxidizing species such as hydroxyl radical (HO(•)), peroxynitrite (ONOO(-)), and hypochlorous acid (HOCl), and therefore the direct detection of O(2)(•-) is important. To overcome the limitations of conventional cyclic nitrones, that is, poor reactivity with O(2)(•-), instability of the O(2)(•-) adduct, and poor cellular target specificity, synthesis of disubstituted nitrones has become attractive. Disubstituted nitrones offer advantages over the monosubstituted ones because they allow bifunctionalization of spin traps, therefore accommodating all the desired spin trap properties in one molecular design. However, because of the high number of possible disubstituted analogues as candidate, a systematic computational study is needed to find leads for the optimal spin trap design for biconjugation. In this paper, calculation of the energetics of O(2)(•-) and HO(2)(•) adduct formation from various disubstituted nitrones at PCM/B3LYP/6-31+G(d,p)//B3LYP/6-31G(d) level of theory was performed to determine the most favorable disubstituted nitrones for this reaction. In addition, our results provided general trends of radical reactivity that is dependent upon but not exclusive to the charge densities of nitronyl-C, the position of substituents including stereoselectivities, and the presence of intramolecular H-bonding interaction. Unusually high exoergic ΔG(298K,aq)'s for O(2)(•-) and HO(2)(•) adduct formation were predicted for (3S,5S)-5-methyl-3,5-bis(methylcarbamoyl)-1-pyrroline N-oxide (11-cis) and (4S,5S)-5-dimethoxyphosphoryl-5-methyl-4-ethoxycarbonyl-1-pyrroline N-oxide (29-trans) with ΔG(298K,aq) = -3.3 and -9.4 kcal/mol, respectively, which are the most exoergic ΔG(298K,aq) observed thus far for any nitrone at the level of theory employed in this study.

Dataset Information

Inhibition of hydrocarbon autoxidation by nitroxide-catalyzed cross-dismutation of hydroperoxyl and alkylperoxyl radicals.

Publications

Inhibition of hydrocarbon autoxidation by nitroxide-catalyzed cross-dismutation of hydroperoxyl and alkylperoxyl radicals.

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