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Reaction between Peroxy and Alkoxy Radicals Can Form Stable Adducts.

ABSTRACT: Peroxy (RO₂) and alkoxy (RO) radicals are prototypical intermediates in any hydrocarbon oxidation. In this work, we use computational methods to (1) study the mechanism and kinetics of the RO₂ + OH reaction for previously unexplored "R" structures (R = CH(O)CH₂ and R = CH₃C(O)) and (2) investigate a hitherto unaccounted channel of molecular growth, R'O₂ + RO. On the singlet surface, these reactions rapidly form ROOOH and R'OOOR adducts, respectively. The former decomposes to RO + HO₂ and R(O)OH + O₂ products, while the main decomposition channel for the latter is back to the reactant radicals. Decomposition rates of R'OOOR adducts varied between 103 and 0.015 s^-1 at 298 K and 1 atm. The most long-lived R'OOOR adducts likely account for some fraction of the elemental compositions detected in the atmosphere that are commonly assigned to stable covalently bound dimers.

SUBMITTER: Iyer S

PROVIDER: S-EPMC6727596 | biostudies-literature | 2019 May

REPOSITORIES: biostudies-literature

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Reaction between Peroxy and Alkoxy Radicals Can Form Stable Adducts.

Iyer Siddharth S Rissanen Matti P MP Kurtén Theo T

The journal of physical chemistry letters 20190412 9

Peroxy (RO2) and alkoxy (RO) radicals are prototypical intermediates in any hydrocarbon oxidation. In this work, we use computational methods to (1) study the mechanism and kinetics of the RO2 + OH reaction for previously unexplored "R" structures (R = CH(O)CH2 and R = CH3C(O)) and (2) investigate a hitherto unaccounted channel of molecular growth, R'O2 + RO. On the singlet surface, these reactions rapidly form ROOOH and R'OOOR adducts, resp ...[more]

PMID: 30958011

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Project description:Covalent bond formations of free radical metabolites with biomolecules like DNA and proteins are thought to constitute a major mechanism of toxicity and carcinogenesis. Glutathione (GSH) is generally accepted as a radical scavenger protecting the cell. In the present study, we investigated a semiquinone radical (SQ(?-)) metabolite of the semivolatile 4-chlorobiphenyl, using electron paramagnetic resonance spectroscopy, and oxygen consumption. Proton nuclear magnetic resonance ((1)H NMR) and liquid chromatography-mass spectrometry (LC-MS) were also employed to elucidate the radical interaction with DNA, amino acids, and GSH. We found that DNA and oligonucleotides stabilized SQ(?-) by electron delocalization in the ?-stacking system, resulting in persistent radical intercalated, rather than forming a covalent bond with SQ(?-). This finding was strongly supported by the semiempirical calculation of the semioccupied molecular orbital and the linear combination of the atomic orbitals, indicating 9.8 kcal mol(-1) energy gain. The insertion of SQ(?-) into the DNA strand may result in DNA strand breaks and interruption of DNA replication process or even activate radical mediated secondary reactions. The presence of amino acids resulted in a decrease of the electron paramagnetic resonance (EPR) signal of SQ(?-) and correlated with their isoelectric points. The pH shifts the equilibrium of the dianions of hydroquinone and influenced indirectly the formation of SQ(?-). Similar findings were observed with GSH and Cys. GSH and Cys functioned as indirect radical scavengers; their activities depend on their chemical equilibria with the corresponding quinones, and their further reaction via Michael addition. The generally accepted role of GSH as radical scavenger in biological systems should be reconsidered based upon these findings, questioning the generally accepted view of radical interaction of semiquinones with biologically active compounds, like DNA, amino acids, proteins, and radical scavengers like GSH.

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Reaction between Peroxy and Alkoxy Radicals Can Form Stable Adducts.

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Reaction between Peroxy and Alkoxy Radicals Can Form Stable Adducts.

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