Quantum chemical evaluation of the role of $${{{\text{HO}}_{2}}^{ \cdot }}$$ radicals in the kinetics of the methyl linoleate oxidation in micelles

Soloviev, Mikhail; Moskalenko, I. V.; Плисс, Е. М.

doi:10.1007/s11144-019-01613-w

Cited by 11 publications

(14 citation statements)

References 39 publications

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“…Indeed, it has been shown that increased production of mitochondrial HO 2 • in cardiovascular conditions is associated with an increased cardiolipin oxidation, which represent a specific biomarker of mitochondrial oxidative stress [ 63 ]. The outcome of HO 2 • reaction with a different number of double bonds will be very distinct: IPLP, which requires PUFA with at least three double bonds present, produces racemic mixtures of hundreds of final products, whereas reaction with the most common fatty acid in CL, linoleic acids with two double bonds, yields “regular” lipid hydroperoxide [ 64 ].…”

Section: Properties Of the Perhydroxyl Radical (Ho 2 mentioning

confidence: 99%

“…In the hydrophobic milieu, H 2 O 2 undergoes homolytic splitting into two molecules of • OH, which instantly interact with another two H atoms of the same or adjacent linoleic acid followed by interaction of O 2 with formation of the stable linoleic hydroperoxide, which is still attached to CL. Molecular dynamic simulation studies have shown that upon oxidation, the molecule of linoleic acid changes its conformation ( Figure 4 ) [ 64 ], which may affect the ability of CL to maintain the superstructure of the mitochondrial enzyme complexes. Thus oxidatively damaged CL is a specific hallmark for the oxidative stress in mitochondria.…”

Section: The Isoprostane Pathway Of Lipid Peroxidationmentioning

confidence: 99%

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Cardiolipin, Perhydroxyl Radicals, and Lipid Peroxidation in Mitochondrial Dysfunctions and Aging

Panov

Dikalov

2020

Oxidative Medicine and Cellular Longevity

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Mitochondrial dysfunctions caused by oxidative stress are currently regarded as the main cause of aging. Accumulation of mutations and deletions of mtDNA is a hallmark of aging. So far, however, there is no evidence that most studied oxygen radicals are directly responsible for mutations of mtDNA. Oxidative damages to cardiolipin (CL) and phosphatidylethanolamine (PEA) are also hallmarks of oxidative stress, but the mechanisms of their damage remain obscure. CL is the only phospholipid present almost exclusively in the inner mitochondrial membrane (IMM) where it is responsible, together with PEA, for the maintenance of the superstructures of oxidative phosphorylation enzymes. CL has negative charges at the headgroups and due to specific localization at the negative curves of the IMM, it creates areas with the strong negative charge where local pH may be several units lower than in the surrounding bulk phases. At these sites with the higher acidity, the chance of protonation of the superoxide radical (O2•), generated by the respiratory chain, is much higher with the formation of the highly reactive hydrophobic perhydroxyl radical (HO2•). HO2• specifically reacts with the double bonds of polyunsaturated fatty acids (PUFA) initiating the isoprostane pathway of lipid peroxidation. Because HO2• is formed close to CL aggregates and PEA, it causes peroxidation of the linoleic acid in CL and also damages PEA. This causes disruption of the structural and functional integrity of the respirosomes and ATP synthase. We provide evidence that in elderly individuals with metabolic syndrome (MetS), fatty acids become the major substrates for production of ATP and this may increase several-fold generation of O2• and thus HO2•. We conclude that MetS accelerates aging and the mitochondrial dysfunctions are caused by the HO2•-induced direct oxidation of CL and the isoprostane pathway of lipid peroxidation (IPLP). The toxic products of IPLP damage not only PEA, but also mtDNA and OXPHOS proteins. This results in gradual disruption of the structural and functional integrity of mitochondria and cells.

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Section: Properties Of the Perhydroxyl Radical (Ho 2 mentioning

confidence: 99%

Section: The Isoprostane Pathway Of Lipid Peroxidationmentioning

confidence: 99%

Cardiolipin, Perhydroxyl Radicals, and Lipid Peroxidation in Mitochondrial Dysfunctions and Aging

Panov

Dikalov

2020

Oxidative Medicine and Cellular Longevity

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“…In addition, in the case of the oxidation of methyl linoleate in micelles initiated by AMVN, in contrast to AAPH, [34] HO 2 * is not formed, which is confirmed by the absence of oxidation inhibition in the presence of SOD (concentration in solution 100 U/mL). Presumably, the source of hydroperoxyl radicals are non-recombined peroxyl radicals of methyl linoleate.…”

Section: Chemistryselectmentioning

confidence: 65%

Oxidation of Methyl Linoleate in Triton X‐100 Micelles Initiated by Lipid‐soluble Initiator 2,2′‐Azobis (2,4‐dimethylvaleronitrile)

2023

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This article discusses the oxidation of methyl linoleate in micelles, initiated by the lipid-soluble initiator 2,2'-azobis (2,4dimethylvaleronitrile) (AMVN). It was shown that the rate constant (k i ) is initiated in micelles for AMVN significantly lower than the known rate constant of initiation in true solutions. This can be explained by the reduced probability of AMVN radicals leaving the cage and an increase in the rate of chain termination between initiator radicals under conditions of low oxygen content. This conclusion was confirmed by quantum chemical calculations. Surprisingly, when determining the AMVN initiation rate constant for the consumption of nitroxyl radicals (> NO * ), the k i depends on the concentration > NO * , this is due to the dependence of the probability of the nitroxyl radical and initiator radicals in micelles meeting on their concentration. Upon initiation of AMVN, no hydroperoxyl radical is expelled.

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“…• contribution increases the rate constant of polyunsaturated fatty acid oxidation. 20 However, HO 2…”

Section: Homentioning

confidence: 99%

“…HO 2 • initiates the lipid peroxidation of polyunsaturated fatty acids with the formation of unstable and reactive fatty acid molecules, which contribute to membrane and tissue damage . HO 2 • contribution increases the rate constant of polyunsaturated fatty acid oxidation …”

Section: Introductionmentioning

confidence: 99%

Melamine Barbiturate as a Light-Induced Nanostructured Supramolecular Material for a Bioinspired Oxygen and Organic Radical Trap and Stabilization

et al. 2023

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Use of coantioxidant systems is a prospective way to increase the effectiveness of antioxidant species in tissue repair and regeneration. In this paper, we introduce a novel scheme of a reactive oxygen species (ROS) trap and neutralization during self-assembly of supramolecular melamine barbiturate material. The performed reaction chain mimics the biological process of ROS generation in key stages and enables one to obtain stable hydroperoxyl and organic radicals in a melamine barbiturate structure. Melamine barbiturate also neutralizes hydroxyl radicals, and the effectiveness of the radical trap is controlled with ROS scavenger incorporation. The number of radicals dramatically increases during light-inducing and depends on pH. The proposed scheme of the ROS trap and neutralization opens a way to the use of supramolecular assemblies as a component of coantioxidant systems and a source of organic radicals.

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Quantum chemical evaluation of the role of $${{{\text{HO}}_{2}}^{ \cdot }}$$ radicals in the kinetics of the methyl linoleate oxidation in micelles

Cited by 11 publications

References 39 publications

Cardiolipin, Perhydroxyl Radicals, and Lipid Peroxidation in Mitochondrial Dysfunctions and Aging

Cardiolipin, Perhydroxyl Radicals, and Lipid Peroxidation in Mitochondrial Dysfunctions and Aging

Oxidation of Methyl Linoleate in Triton X‐100 Micelles Initiated by Lipid‐soluble Initiator 2,2′‐Azobis (2,4‐dimethylvaleronitrile)

Melamine Barbiturate as a Light-Induced Nanostructured Supramolecular Material for a Bioinspired Oxygen and Organic Radical Trap and Stabilization

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