Linoleic Oxidation Research Articles

Anti-Alzheimer's Potency of Rich Phenylethanoid Glycosides Extract from Marrubium vulgare L.: In Vitro and In Silico Studies.

Marrubium vulgare L. (M. vulgare), the white horehound, is well known for treating inflammation-related diseases. In this context, we investigated the efficacy of M. vulgare ingredients in treating Alzheimer's disease using various in vitro and in silico antioxidant, anti-inflammatory, anti-cholinesterase, and anti-tyrosinase mechanisms. In our results, sixty-one components were tentatively identified using gas and liquid chromatography (GC-MS and LC-MSn) and categorized as hydrocarbons, fatty acids, and polyphenolics. The extract inhibited linoleic oxidation with an IC50 value of 114.72 µg/mL, captured iron (Fe2+) ions with an IC50 value of 164.19 µg/mL, and displayed reducing power. In addition, the extract showed radical-scavenging ability towards DPPH•, NO•, ABTS•+, and H2O2 assays compared to L-ascorbic acid and butylated hydroxytoluene. The DPPH• was scavenged by 77.62% at 100 µg/mL, and NO•, ABTS•+, and H2O2 were scavenged with IC50 values of 531.66, 117.51, and 143.10 µg/mL, respectively. M. vulgare also exhibited discriminating anti-inflammatory potency against cyclooxygenase (COX-2) with IC50 values of 619.15 µg/mL compared to celecoxib (p > 0.05). Notably, three Alzheimer's biomarkers, acetylcholinesterase (AChE), butyrylcholinesterase (BChE), and tyrosinase were significantly inhibited. The molecular docking study supposed that the phenylethanoid glycosides of samioside and forsythoside B inhibited AChE and tyrosinase enzymes with low binding affinities of -9.969 and -8.804 kcal/mol, respectively. Marruboside was a proper inhibitor of COX and BChE enzymes with a binding score of -10.218 and -10.306 kcal/mol, respectively. M. vulgare extract showed significant inhibitory actions, which suggest that it could have a promising potential as an anti-Alzheimer agent.

Lipid radicals and oxidized cholesteryl esters in low- and high-density lipoproteins in patients with β-thalassemia: Effects of iron overload and iron chelation therapy

Iron overload results in lipid peroxidation (LPO) and the oxidative modification of circulating lipoproteins, which contributes to cardiovascular complications in patients with β-thalassemia. Investigating LPO may provide opportunities for the development of novel therapeutic strategies; however, the chemical pathways underlying iron overload-induced LPO in β-thalassemia lipoproteins remain unclear. In this study, we identified various species of lipid radicals (L•), the key mediators of LPO, and oxidized cholesteryl esters (oxCE) derived from the in vitro oxidation of major core lipids, cholesteryl linoleate (CE18:2) and cholesteryl arachidonate (CE20:4); the levels of these radical products in low-density lipoproteins (LDL) and high-density lipoproteins (HDL) were measured and compared between β-thalassemia patients and healthy subjects by using a specific fluorescent probe for L• with a liquid chromatography-tandem mass spectrometric method. Our results demonstrated that iron overload substantially decreased the levels of CE18:2 and CE20:4 substrates and α-tocopherol, resulting in higher levels of full-length and short-chain truncated L• and oxCE products. In particular, CE epoxyallyl radicals (•CE-O) were observed in the lipoproteins of β-thalassemia, revealing the pathological roles of iron overload in the progression of LPO. In addition, we found that intermission for two weeks of iron chelators can increase the production of these oxidized products; therefore, suggesting the beneficial effects of iron chelators in preventing LPO progression. In conclusion, our findings partly revealed the primary chemical pathway by which the LPO of circulating lipoproteins is influenced by iron overload and affected by iron chelation therapy. Moreover, we found that •CE + O shows potential as a sensitive biomarker for monitoring LPO in individuals with β-thalassemia.

Greater oxidation of dietary linoleate compared to palmitate in humans following an acute high-carbohydrate diet

We have previously demonstrated that dietary saturated fatty acids (SFA), when compared to polyunsaturated fatty acids (PUFA), are preferentially partitioned into oxidation pathways. However, it remains unclear if this preferential handling is maintained when hepatocellular metabolism is shifted toward fatty acid (FA) esterification and away from oxidation, such as when hepatic de novo lipogenesis (DNL) is upregulated. To investigate whether an acute upregulation of hepatic DNL influences dietary FA partitioning into oxidation pathways. 20 healthy volunteers (11 females) underwent a fasting baseline visit followed by two study days, 2-weeks apart. Prior to each study day, participants consumed an isocaloric high-carbohydrate diet (to upregulate hepatic DNL) for 3-days. On the two study days, participants consumed an identical standardised test meal that contained either [U13C]palmitate or [U13C]linoleate, in random order, to trace the fate of dietary FA. Blood and breath samples were collected over a 6h postprandial period and 13C enrichment in breath CO2 and plasma lipid fractions were measured using gas-chromatography-combustion-isotope ratio mass spectrometry. Compared to the baseline visit, fasting plasma triglyceride concentrations and markers of hepatic DNL, the lipogenic and stearyl-CoA desaturase indices, were significantly (p<0.05) increased after consumption of the high-carbohydrate diet. Appearance of 13C in expired CO2 and tracer recovery were significantly (p<0.05) higher after consumption of the meal containing [U13C]linoleate compared to [U13C]palmitate (5.1±0.5% vs. 3.7±0.4%), respectively. Incorporation of 13C into the plasma triglyceride and non-esterified fatty acid pool was significantly (p<0.001) greater for [U13C]palmitate compared to [U13C]linoleate. Dietary PUFA compared to SFA appear to be preferentially partitioned into oxidation pathways during an acute upregulation of hepatic DNL, thus consumption of a PUFA-enriched diet may help mitigate intrahepatic triglyceride accumulation in individuals at risk of cardiometabolic disease.

L-proline Interaction with Methyl Linoleate Oxidation Products Formation in Dry System and at Temperatures: For Understanding in Low-Moisture Foods

Dry and low-moisture foods could experience a significant loss in nutritional value due to the process of methyl linoleate oxidation. L-proline could interact with lipid oxidation products, potentially modifying their formation and reaction path. However, there was a lack of research on the interaction between L-proline and methyl linoleate oxidation products in dry and low-moisture food matrices, which was a concern given the potential impact on food safety and nutrition. To address this knowledge gap, a study investigated the interaction between L-proline and the oxidation products of methyl linoleate in a dry system. The study examined the formation of methyl linoleate oxidation products such as conjugated dienes, hydroperoxide, and hexanal in the absence and presence of varying moles of L-proline at different temperatures. The formation of conjugated diene, hydroperoxide, and hexanal was analyzed using UV spectrometer analysis, xylenol orange, and DNPH derivatization HPLC-UV analysis. The results showed that adding proline to methyl linoleate samples stabilized conjugated diene and decreased hydroperoxide and hexanal levels as temperature increased, compared to the control sample. This suggests that L-proline effectively interacted with methyl linoleate oxidation products and altered their formation and oxidation path in the dry system. Overall, this study provided a basis for significantly enhancing understanding of the reactions between L-proline and methyl linoleate oxidation products in dry and low-moisture foods, offered practical implications for the food industry, and paved the way for future research.

Kinetics and mechanism of methyl linoleate oxidation in cetyltrimethylammonium bromide micelles

Kinetics and mechanism of methyl linoleate oxidation in cetyltrimethylammonium bromide micelles

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

AbstractThis article discusses the oxidation of methyl linoleate in micelles, initiated by the lipid‐soluble initiator 2,2′‐azobis (2,4‐dimethylvaleronitrile) (AMVN). It was shown that the rate constant (ki) 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 (&gt;NO⋅), the ki depends on the concentration &gt;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.

Two C18 hydroxy-cyclohexenone fatty acids from mammalian epidermis: Potential relation to 12R-lipoxygenase and covalent binding of ceramides

A key requirement in forming the water permeability barrier in the mammalian epidermis is the oxidation of linoleate esterified in a skin-specific acylceramide by the sequential actions of 12R-lipoxygenase, epidermal lipoxygenase-3, andthe epoxyalcohol dehydrogenase SDR9C7 (short-chain dehydrogenase-reductase family 7 member 9). By mechanisms that remain unclear, this oxidation pathway promotes the covalent binding of ceramides to protein, forming a critical structure of the epidermal barrier, the corneocyte lipid envelope. Here, we detected, in porcine, mouse, and human epidermis, two novel fatty acid derivatives formed by KOH treatment from precursors covalently bound to protein: a "polar" lipid chromatographing on normal-phase HPLC just before omega-hydroxy ceramide and a "less polar" lipid nearer the solvent front. Approximately 100μg of the novel lipids were isolated from porcine epidermis, and the structures were established by UV-spectroscopy, LC-MS, GC-MS, and NMR. Each is a C18 fatty acid and hydroxy-cyclohexenone with the ring on carbons C9-C14 in the polar lipid and C8-C13 in the less polar lipid. Overnight culture of [14C]linoleic acid with whole mouse skin exvivo led to recovery of the 14C-labeled hydroxy-cyclohexenones. We deduce they are formed from covalently bound precursors during the KOH treatment used to release esterified lipids. KOH-induced intramolecular aldol reactions from a common precursor can account for their formation. Discovery of these hydroxy-cyclohexenones presents an opportunity for a reverse pathway analysis, namely to work back from these structures to identify their covalently bound precursors and relationship to the linoleate oxidation pathway.

Kinetic modeling of the reversal of antioxidant potency of α-, β-, γ- and δ-tocopherols in methyl linoleate peroxidation

Extended, chemically detailed kinetic models at the molecular basis are constructed to identify the reactions involved in the reversal of the antioxidant action of α-, β-, γ- and δ-tocopherols during methyl linoleate oxidation. The reaction mechanisms were numerically simulated and subjected to analysis to quantify the significance of individual chemical steps by the value-based method. Results of the obtained kinetic models agreed well with the experimental data. The significant individual reactions contributing to the observed antioxidant and pro-oxidant behavior of the different tocopherols were identified. It is revealed that the reverse order of antioxidant potency and a complex nonlinear dependency of the antioxidant potency of tocopherols with the increase in their concentration are due to the increasing contribution of pro-oxidant relative to the antioxidant reactions. Once the approach presented here can be applied to more complex systems, engineered optimization of antioxidant protection strategies may be reached.

Biochemical and Functional Characterization of Kidney Bean Protein Alcalase-Hydrolysates and Their Preservative Action on Stored Chicken Meat.

A new preservation approach is presented in this article to prolong the lifetime of raw chicken meat and enhance its quality at 4 °C via coating with highly soluble kidney bean protein hydrolysate. The hydrolysates of the black, red, and white kidney protein (BKH, RKH, and WKH) were obtained after 30 min enzymatic hydrolysis with Alcalase (E/S ratio of 1:100, hydrolysis degree 25–29%). The different phaseolin subunits (8S) appeared in SDS-PAGE in 35–45 kD molecular weight range while vicilin appeared in the molecular weight range of 55–75 kD. The kidney bean protein hydrolysates have considerable antioxidant activity as evidenced by the DPPH-scavenging activity and β-carotine-linolenic assay, as well as antimicrobial activity evaluated by disc diffusion assay. BKH followed by RKH (800 µg/mL) significantly (p ≤ 0.05) scavenged 95, 91% of DPPH and inhibited 82–88% of linoleic oxidation. The three studied hydrolysates significantly inhibited the growth of bacteria, yeast, and fungi, where BKH was the most performing. Kidney bean protein hydrolysates could shield the chicken meat because of their amphoteric nature and many functional properties (water and oil-absorbing capacity and foaming stability). The quality of chicken meat was assessed by tracing the fluctuations in the chemical parameters (pH, met-myoglobin, lipid oxidation, and TVBN), bacterial load (total bacterial count, and psychrophilic count), color parameters and sensorial traits during cold preservation (4 °C). The hydrolysates (800 µg/g) significantly p ≤ 0.05 reduced the increment in meat pH and TVBN values, inhibited 59–70% of lipid oxidation as compared to control during 30 days of cold storage via eliminating 50% of bacterial load and maintained secured storage for 30 days. RKH and WKH significantly (p ≤ 0.05) enhanced L*, a* values, thus augmented the meat whiteness and redness, while, BKH increased b* values, declining all color parameters during meat storage. RKH and WKH (800 µg/g) (p ≤ 0.05) maintained 50–71% and 69–75% of meat color and odor, respectively, increased the meat juiciness after 30 days of cold storage. BKH, RKH and WKH can be safely incorporated into novel foods.

Molecular dynamics simulation and experimental research on the oxidation reaction of methyl linoleate at low oxygen and high temperature

The pyrolysis and low-oxygen high-temperature oxidation process of methyl linoleate containing two unsaturated double bonds were analyzed by kinetic analysis, density functional theory calculation and ReaxFF-MD considering it as a substitute for biodiesel. The combined system of TG-FTIR-MS was used to analyze the escape characteristics of multi-component gas product during the pyrolysis as well as high-temperature oxidation of methyl linoleate under low-oxygen. The ReaxFF-MD molecular dynamics method was used to analyze the effect of initial reaction path of the thermal decomposition of methyl linoleate and the oxygen content on the oxidation reaction products. The results show that the pyrolysis of methyl linoleate has reaction activation energy of 58.2 kJ/mol, while, for the high-temperature oxidation process under low oxygen, it is 58.79 kJ/mol. The main gaseous products are CO2, CH4, CO/C2H4, H2O and products containing C–H, C–O, CO and other functional groups. Through DFT calculations and ReaxFF-MD, we found that breaking of C–O bond leading to the formation of smaller CH3 radical and decarboxylation to form CO2 constitute the initiation mechanism for the pyrolysis of methyl linoleate pyrolysis and high-temperature oxidation in presence of low oxygen. The double bond of methyl linoleate is prone to generate C7H10 intermediates with higher carbon content during the pyrolysis process. At the same time, through simulation, we found that oxygen and fuel are mixed as soon as possible at the beginning of the combustion of methyl linoleate which helps to reduce the production of C2 products from the pyrolysis of methyl linoleate.

Study on transition metal ion Fe3+ catalyzed biodiesel oxidation and inhibition mechanism

Methyl linoleate is used as an alternative component of biodiesel. The catalytic oxidation of biodiesel is studied in the presence of iron acetate using methyl linoleate as the alternative component. The composition of the products obtained from the oxidation process of methyl linoleate is analyzed by GC–MS and liquid phase microextraction. Density functional theory is used to calculate the electronic effects of the related reactants and products and the related catalytic oxidation reaction paths are derived. The results show that during the process of catalytic oxidation of methyl linoleate in biodiesel, mainly the catalytic cracking reaction of C–H and C–C bonds and Fenton-like reaction occur. The combination of two antioxidants, TEPA and [MI][C6H2(OH)3COO], can effectively inhibit the catalytic oxidation of Cu2+ and Fe3+ and interrupt the chain reaction of the oxidation process. The negative value of the electrostatic potential of ferric acetate is relatively large, it is obviously alkaline, and has a certain ability to bind with H. The irregular structure of the iron acetate unit cell makes the O–Fe bond in the molecule easy to break, which is beneficial for the catalytic oxidation process.

Kinetic model of polyunsaturated fatty acids oxidation in micelles

A kinetic model of polyunsaturated fatty acids (PUFAs) radical chain oxidation in micelles is presented, taking into account the diffusion of active intermediates between aqueous and organic phases, and its effect on the detailed mechanism of the process. The model made it possible to indirectly involve the structural changes of micelles and their kinetic characteristics by varying the actual values of the reactions rate constants. The modeling results are in good agreement with experimental data for the oxidation of methyl linoleate and linoleic acid.

Study on the mechanism of auto-oxidation of Jatropha biodiesel and the oxidative cleavage of C[sbnd]C bond

Jatropha biodiesel was obtained according to the continuous preparation process which included vapor esterification - transesterification - methanol steam distillation. Accelerated oxidation of small Jatropha biodiesel was obtained by the Rancimat method. GC–MS and liquid phase micro-extraction were used to study and analyze the components in the oxidation process of Jatropha curcas biodiesel. The electronic effects of the related reactants and products were calculated by density functional theory, followed by the deduction of the related chemical reaction paths. Experimental investigation shows that methyl linoleate is the main factor affecting the oxidation stability of the Jatropha biodiesel. The main volatile products at the initial stages of the oxidation of methyl linoleate are hexanal, methyl octanoate, styrene, and 2-heptenal. The cis/trans-3-octyl-oxiranyl octanoic acid methyl ester (18.03% yield) is produced by the reaction of peroxy acid and methyl oleate during the oxidation of methyl oleate. The hydrogen extraction reaction is difficult to occur, and the oxidation reaction energy barrier is relatively high due to the relatively large bond energy of the CH bond in the methyl stearate molecule. In this manuscript, the auto-oxidation mechanism of the biodiesel fatty acid methyl esters at the initial stage of oxidation, the path of oxidative cleavage of the CC bond of Jatropha biodiesel and the formation process of ethylene oxide structure are obtained through DFT calculation and analysis of the oxidation products.

Development and Application of a Peroxyl Radical Clock Approach for Measuring Both Hydrogen-Atom Transfer and Peroxyl Radical Addition Rate Constants.

The rate-determining step in free radical lipid peroxidation is the propagation of the peroxyl radical, where generally two types of reactions occur: (a) hydrogen-atom transfer (HAT) from a donor to the peroxyl radical; (b) peroxyl radical addition (PRA) to a "C═C" double bond. Peroxyl radical clocks have been used to determine the rate constants of HAT reactions (kH), but no radical clock is available to measure the rate constants of PRA reactions (kadd). In this work, we modified the analytical approach on the linoleate-based peroxyl radical clock to enable the simultaneous measurement of both kH and kadd. Compared to the original approach, this new approach involves the use of a strong reducing agent, LiAlH4, to completely reduce both HAT and PRA-derived products and the relative quantitation of total linoleate oxidation products with or without reduction. The new approach was then applied to measuring the kH and kadd values for several series of organic substrates, including para- and meta-substituted styrenes, substituted conjugated dienes, and cyclic alkenes. Furthermore, the kH and kadd values for a variety of biologically important lipids were determined for the first time, including conjugated fatty acids, sterols, coenzyme Q10, and lipophilic vitamins, such as vitamins D3 and A.

Effect of Cysteine on the Antioxidant Activity of Nitroxyl Radicals during the Oxidation of Methyl Linoleate in Micelles

Using the model of methyl linoleate (LH) oxidation in micelles, the effect of cysteine on the antioxidant activity of nitroxyl radicals (NR) in micelles is studied. It is found that cysteine enhances the antioxidant effect of NR with a low reduction potential of the oxoammonium cation + nitroxyl radical pair, which is due to the formation of the corresponding hydroxylamines (HA).

Phenolics Contents, Xanthine Oxidoreductase Inhibitory Potential, Antibacterial and Antioxidant Activities of Cachrys libanotis L. Root Extracts

To date, no studies have investigated the phytochemical screening and biological activities of Cachrys libanotis L. traditionally used for the treatment of gout and rheumatism. Therefore, we aimed to investigate, for the first time, the phytochemical contents, the xanthine oxidoreductase inhibition, antibacterial, and antioxidant activities of extracts derived from the roots of C. libanotis L. Roots were submitted to extraction and fractionation using three different solvents sequentially, in the ascending order of polarity. Subsequently, XOR was purified from bovine milk and its inhibition was evaluated using xanthine/XOR system. The antioxidant activities were assessed employed superoxide scavenging, β- carotene bleaching, DPPH scavenging, ferrous iron chelation and FRAP assays). The antibacterial activity was tested by disc diffusion assay against 11 ATCC strains. Extraction and fractionation gave crude extract (CrE), hexane extract (HxE), chloroform extract (ChE), ethyle acetate extract (EAE) and aqueous extract (AqE). EAE exhibited the highest XOR inhibitory effect. CrE exhibited the highest effect as DPPH scavenger. All fractions exhibited a good activity against linoleate oxidation. Both CrE and AqE had an excellent chelating activity. Extracts showed a medium reducing power with greatest value exhibited by EAE. The plant extracts exhibited moderate to good antibacterial activity where the HxE extract had the strongest antimicrobial activity. From the obtained results, C. libanotis roots might be helpful in preventing or slowing the progress of gout, and it could be used as an additive in the food industry providing good protection against oxidative damage.&#x0D; Keywords: Cachrys libanotis, polyphenols, oxidative stress, xanthine-oxidoreductase (XOR), antimicrobial.

Oxidation of dietary linoleate occurs to a greater extent than dietary palmitate in vivo in humans

It has been suggested that dietary polyunsaturated fatty acids (PUFA) are partitioned into oxidation pathways to a greater extent than dietary saturated fatty acids (SFA). Whilst this has been demonstrated in animal models, evidence in humans is lacking. The potential divergence in the metabolic fate of these dietary fatty acids (FA) may explain some of the reported differences in ectopic fat deposition with SFA and PUFA enriched diets. To compare whole-body oxidation of dietary palmitate and linoleate after consumption of a single test meal. In a randomized, crossover design 24 healthy volunteers (12 males and 12 females, matched for age and BMI) underwent two study days separated by 2-week washout period. During each study day participants consumed a standardized test meal which contained [U13C]palmitate or [U13C]linoleate. Blood and breath samples were collected over the 6h postprandial period and the 13C enrichment in breath CO2 samples and plasma lipid fractions was determined. Appearance of 13C in expired CO2 was significantly (p<0.05) increased after consumption of the meal containing [U13C]linoleate compared to the meal containing [U13C]palmitate. The recovery of tracer was 8.9±1.2% [U13C]linoleate vs. 5.6±0.4% [U13C]palmitate (p<0.05). The incorporation of 13C from [U13C]palmitate was greater in plasma triacylglycerol and non-esterified fatty acids than [U13C]linoleate, whereas the incorporation of 13C from [U13C]linoleate was greater than [U13C]palmitate in plasma phospholipids. Although 13CO2 was significantly (p<0.05) higher in females compared to males after consumption of [U13C]palmitate, there was no difference in 13CO2 between sexes after consumption of [U13C]linoleate. We demonstrate that whole-body oxidation of dietary linoleate is comparatively higher than that of dietary palmitate in humans following consumption of a single mixed-test meal. We found indications of sexual dimorphism for dietary palmitate but not dietary linoleate. http://www.clinicaltrials.org/ ID number NCT03587753.

Features of Methyl Linoleate Oxidation in Triton X-100 Micellar Buffer Solutions

Features of Methyl Linoleate Oxidation in Triton X-100 Micellar Buffer Solutions

Influence of β-Carotene and Lycopene on Oxidation of Ethyl Linoleate in One- and Disperse-Phased Model Systems.

The induction period (IP) of ethyl linoleate stressed at 60 °C was monitored via the formation of hydroperoxides. The addition of lycopene (1% w/w) increased the IP from 7.0 to 10.0 h to prove the strong antioxidative potential in contrast to β-carotene with pro-oxidative effects (IP: 6.0 h), both showing strong scavenging activity under fast degradation. When peroxidation was induced by singlet oxygen, both carotenoids effectively inhibited the formation of hydroperoxides, with quenching activity only observed at low singlet oxygen concentrations, while scavenging still dominated. Thus, carotenoids did not interact with the introduced singlet oxygen but rather with the radical intermediates of fat oxidation. These experiments were then transferred to lecithin-based micelles more related to biological systems, where singlet oxygen was generated in the outer aqueous phase. Lycopene and β-carotene delayed or inhibited lipid peroxidation depending on concentration. In this setup, β-carotene showed exclusively quenching activity, while lycopene was additionally degraded to about 70%.

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

The process of lipid peroxidation (LPO) plays an extremely important role in the human body due to the fact that its uncontrolled development can lead to oxidative stress and a number of serious diseases. The traditional approach to the analysis of the mechanism and kinetics of LPO is based on the well-known ideas that emerged from the study of radical-chain oxidation of hydrocarbons in a homogeneous medium. However, the distinctive feature of LPO is that this process is heterogeneous and the processes of diffusion of active intermediates between the aqueous and hydrocarbon phases should play a significant role in it. In the present work, an attempt has been made to theoretically estimate the contribution of these processes to the oxidation kinetics of model substances used in practice in the study of LPO. In the course of the calculations, a quantum chemical and kinetic analysis of the role of hydroperoxyl radical in the radical-chain mechanism of oxidation of methyl linoleate in micelles was carried out. The molecular dynamics method shows the important role of changing the dynamic rigidity of a hydrocarbon fragment of a chain during the formation of a peroxyl radical and hydroperoxyl group during the oxidation of a substrate in a heterogeneous medium. Quantum chemical calculations of the thermodynamics of reactions involving $${{{\text{HO}}_{2}}^{ \cdot }}$$ radicals and the effects of their solvation made it possible to estimate the kinetic constants of the reaction rates. Using kinetic modeling, their relative contribution to the oxidation kinetics was revealed. In this case, it is possible to explain a number of anomalies associated with the oxidation of polyunsaturated fatty acids and their esters in micelles compared with their oxidation in a homogeneous hydrocarbon medium.