Formation Of Hydroperoxides Research Articles

The oxidative stress mechanism of Bacillus cereus spores induced by atmospheric pressure plasma jet

Emerging plasma technology has demonstrated its effectiveness in inactivating bacteria and spores, showing wide applicability in environment cleaning and in the food supply chain. Studies have revealed that the main reason of plasma-mediated bacterial inactivation were contributed to the oxidative damage on inner membranes (IMs) of cell, while few research paid attention to the oxidation stress process of lipid in spores’ IMs. This study investigated the impact of atmospheric pressure plasma jet (APPJ) treatment on spore inactivation, focusing on oxidative stress mechanisms and changes in membrane lipid composition. Results demonstrated that APPJ treatment induced significant oxidative stress within spores, characterized by elevated levels of reactive oxygen and nitrogen species (RONS). This oxidative stress led to the peroxidation of glycerophospholipids, particularly phosphatidylglycerol, phosphatidylcholine, and cardiolipin, major components of spore membranes. Subsequently, the rearrangement of membrane lipid and the formation of lipid hydroperoxide, caused by the released cations and RONS, accelerated membrane instability. These changes correlated with increased membrane permeability and structural damage observed via flow cytometry, indicating the critical role of membrane lipid peroxidation in spore inactivation. Furthermore, the study highlighted the potential of APPJ as a robust technology for enhancing food safety by targeting spore-forming pathogens throughout the food supply chain.

Evaluating the oxidative stability of triacylglycerols in rapeseed (Brassica napus) oleosomes

AbstractUnsaturated triacylglycerols (TAGs) are stored in natural droplets called oleosomes in seeds. The storage in oleosomes was suggested to increase TAGs' oxidative stability. In this study, we tested the oxidative stability of TAGs in rapeseed oleosomes and compared it with the one of TAGs stored as bulk oils or incorporated into oil‐in‐water emulsions stabilized by rapeseed lecithin. Oleosome oil‐in‐water emulsions (Фoil = 0.1) were created and stored along with the bulk oils and lecithin emulsions for 63 days at 40°C. The TAGs in oleosomes were more oxidatively stable than in the bulk oils and lecithin emulsions, as indicated by the 17‐day longer lag phase and a 1.6–1.8 times slower maximal hydroperoxide formation compared to the bulk oils and lecithin emulsions. Moreover, we made the first steps towards understanding the high stability of TAGs in oleosomes by monitoring the consumption of oleosome‐associated antioxidants (tocopherols and carotenoids). Using oleosome extracts could be a strategy to retard TAGs oxidation in oil‐in‐water emulsions.

Ni-based compounds in multiwalled graphitic shell for electrocatalytic oxygen evolution reactions

Here, we report a general strategy for designing a metal/carbon system, via a facile and environmentally friendly one-step approach, from metal acetate as an active electrocatalyst in oxygen evolution reaction (OER) during water decomposition. As a demonstration, a nanostructured Ni/C composite induced from nickel acetate is revealed in great detail. The resulting material is composed of: metallic nickel (Ni), nickel(II) oxide (NiO), and nickel carbide (Ni3C) coated with a graphitic shell and deposited on a carbon platform. Our findings underscore the prominent role of nickel species, including Ni0, Ni2+, and Ni3+, in driving the catalytic activity. Notably, the catalyst exhibits an overpotential of 170 mV, a Tafel slope of 49 mV·dec−1, an electrocatalytic surface area (ECSA) of 964.7 cm2, and a turnover frequency (TOF) value of 52.8 s−1, surpassing RuO2. The Raman spectra also suggest a graphitic "self-healing" phenomenon post-OER, attributed to the reduction of oxygen-containing groups. Carbon in the system (i) facilitates electron transfer, (ii) allows homogeneous distribution of Ni nanoparticles avoiding their agglomeration, and (iii) promotes durability of the electrocatalyst by serving as a protective barrier, shielding the core metal compounds. What is more, density functional theory (DFT) calculations allowed to optimized geometry of the model cluster Ni8O8(OH)8 describing two different sites on the β-NiOOH surface (001) and two different intermediates, (i)L-OOH and (ii)L-OOH. This facilitated to propose the reaction mechanisms involving both hydroxide ions and water molecules as reducers. Therefore, the chemisorption of OH− and H2O molecules at the NiOOH active center accompanied by bond breakage and the formation of a lattice hydroperoxide as an important intermediate is presumed. What is more, the proposed fabrication method for electroactive metal/carbon composites was validated with an iron and iron/nickel mixture.

Synergistic effects of oxidative and acid stress on bacterial membranes of Escherichia coli and Staphylococcus simulans

Oxidative stress in combination with acid stress has been shown to inactivate a wide spectrum of microorganisms, including multi-resistant bacteria. This occurs e.g. in phagolysosomes or during treatment by cold atmospheric pressure plasmas (CAP) and possibly depends on the cell membrane. We therefore explored the effects of CAP-generated reactive oxygen and nitrogen species (RONS) on bacterial growth inhibition and membranes in neutral and acidic suspensions. We observed that growth inhibition was most efficient when bacteria were treated by a mix of short and long-lived RONS in an acidic environment. Membrane packing was affected mainly upon contact with short-lived RONS, while also acidity strongly modulated packing. Under these conditions, Gram-negative bacteria displayed large potassium release while SYTOX Green influx remained marginal. Growth inhibition of Gram-negative bacteria correlated well with outer membrane (OM) permeabilization that occurred upon contact with short and/or long-lived RONS in synergy with acidity. In Gram-positive bacteria, CAP impaired membrane potential possibly through pore formation upon contact with short-lived RONS while formation of membrane protein hydroperoxides was probably involved in these effects. In summary, our study provides a wide perspective on understanding inactivation mechanisms of bacteria by RONS in combination with acidity.

Interactions between lipid oxidation and anthocyanins from black carrots in ω-3 fatty acid-rich flaxseed oil-in-water emulsions

The application of anthocyanins as red colorants in lipid-containing foods such as oil-in-water emulsions is challenging due to their ability to act as antioxidants and their instability under various environmental conditions. In this study, we investigated the kinetics of black carrot anthocyanin degradation and the subsequent color loss influenced by lipid oxidation reactions in 1% (w/w) flaxseed oil-in-water emulsions stabilized by 0.1% (w/w) sodium dodecyl sulfate (SDS) at pH 2 upon storage at 35 °C for ten days under light and in the dark. Oxidatively stable Miglyol oil-in-water emulsions and SDS solutions were used as reference. The results showed simultaneous formation of lipid hydroperoxides and degradation of anthocyanins. The addition of anthocyanins decreased lipid hydroperoxide formation, confirming the antioxidant activity of anthocyanins through radical scavenging mechanism. The kinetic modelling of lipid oxidation and anthocyanin degradation are particularly important for estimating color stability in colored emulsion-based food systems such as dairy or non-dairy milk or yoghurt drinks.Graphical abstract

Insights into the catalytic effect of atmospheric organic trace species on the hydration of Criegee intermediates

The bimolecular reactions between Criegee intermediates (CIs) and atmospheric trace species have been extensively investigated, with a particular focus on the reaction with water, while the catalytic role of atmospheric organic compounds in hydration reactions was often neglected. In this study, we employed quantum chemical calculations and Born-Oppenheimer molecular dynamics (BOMD) simulations to investigate the catalytic effects of atmospheric organic amines, organic acids, and alcohols on the hydration reactions of CIs in the gas phase and at the gas-liquid interface. The catalytic reactions were found to follow a cyclic catalytic structure and a stepwise reaction mechanism. Gas-phase studies revealed that organic acids exhibited stronger catalytic effects compared to amines and alcohols, and the catalytic efficiency of amines and alcohols was similar to those of single water molecule. In addition, the catalytic reaction barriers of organic acids and alcohols were positively correlated with their gas-phase acidity (R2 = 0.94 to 0.97). A negative correlation was observed between the catalytic reaction barrier of amines and their gas-phase basicity (R2 = 0.84 to 0.90) and proton affinity (R2 = 0.84 to 0.92). At the gas-liquid interface, organic acids promoted the formation of hydroxyethyl hydroperoxide (HEHP, CH3CH(OH)(OOH)), organic acid ions, and H3O+, whereas the catalytic hydration of CIs by organic amines resulted in the formation of CH3CH(OH)OO and amine ions. Both HEHP and CH3CH(OH)OO can be further decomposed to form OH and HO2, or participate in new particles formation as precursors. This study complements the research gap on the reaction of CIs with water, providing valuable insights into the atmospheric sources of HEHP and HOx as well as the formation of secondary organic aerosols (SOAs).

Forecasting of catalytic activity of phthalimide compounds in the process of liquid-phase aerobic oxidation of alkylaromatic hydrocarbons

The authors calculated the single occupied molecular orbital energies of the substrate radical and the phthalimide catalyst radical by the Hartree-Fock quantum chemical method (PM7). According to the research, low numerical values of ∆Esomo characterise N-hydroxyphthalimide derivatives containing electron-donating substituents in their structure and possess high catalytic activity. Application of such compounds allows ones to intensify essentially the process of alkylaromatic hydrocarbons aerobic liquid-phase oxidation with preservation of feedstock conversion high parameters and selectivity of its hydroperoxide formation. The calculated data are in good agreement with the experimentally obtained data. Hence, the proposed method can be used to evaluate the catalytic activity of phthalimide compounds with respect to a wide range of aromatic hydrocarbons.

The effects of ecdysterone and enalapril on nitric oxide synthesis and the markers of oxidative stress in streptozotocin-induced diabetes in rats: a comparative study.

Cardiovascular functions in diabetes greatly depend on constitutive NOS (cNOS) activity. A comparative study of the effects of a steroid hormone ecdysterone and enalapril, an ACE inhibitor widely used to treat cardiac disorders on cNOS, inducible NOS (iNOS), xanthine oxidoreductase (XOR) activity, RNS, ROS, and lipid peroxidation in heart tissue in experimental diabetes was conducted. The rat model of diabetes was established by streptozotocin injection. NOS activity, NO2-, NO3-, uric acid, nitrosothiols, hydroperoxide, superoxide, and diene conjugate formation were studied spectrophotomerically. In diabetes, cNOS downregulation correlated with a dramatic fall of NO2- production and ~4.5-fold elevation of nitrosothiols, which agreed with a steep rise of iNOS activity, while NO3- remained close to control. Dramatic activation of XOR was observed, which correlated with the elevation of both superoxide production and nitrate reductase activity and resulted in strong lipid peroxidation. Ecdysterone and enalapril differently affected RNS metabolism. Ecdysterone moderately restored cNOS but strongly suppressed iNOS, which resulted in the reduction of NO3-, but full restoration of NO2- production. Enalapril better restored cNOS but less effectively suppressed iNOS, which promoted NO3- formation. Both drugs similarly inhibited XOR, which equally alleviated oxidative stress and lipid peroxidation. The synergistic action of iNOS and XOR was a plausible explanation for strong lipid peroxidation, abolished by the inhibition of iNOS and XOR by ecdysterone or enalapril. Complementary effects of ecdysterone and enalapril on cNOS, iNOS, and RNS are a promising basis for their combined use in the treatment of cardiovascular disorders caused by cNOS dysfunction in diabetes.

Ozonolysis of Terpene Flavor Additives in Vaping Emissions: Elevated Production of Reactive Oxygen Species and Oxidative Stress.

The production of e-cigarette aerosols through vaping processes is known to cause the formation of various free radicals and reactive oxygen species (ROS). Despite the well-known oxidative potential and cytotoxicity of fresh vaping emissions, the effects of chemical aging on exhaled vaping aerosols by indoor atmospheric oxidants are yet to be elucidated. Terpenes are commonly found in e-liquids as flavor additives. In the presence of indoor ozone (O3), e-cigarette aerosols that contain terpene flavorings can undergo chemical transformations, further producing ROS and reactive carbonyl species. Here, we simulated the aging process of the e-cigarette emissions in a 2 m3 FEP film chamber with 100 ppbv of O3 exposure for an hour. The aged vaping aerosols, along with fresh aerosols, were collected to detect the presence of ROS. The aged particles exhibited 2- to 11-fold greater oxidative potential, and further analysis showed that these particles formed a greater number of radicals in aqueous conditions. The aging process induced the formation of various alkyl hydroperoxides (ROOH), and through iodometric quantification, we saw that our aged vaping particles contained significantly greater amounts of these hydroperoxides than their fresh counterparts. Bronchial epithelial cells exposed to aged vaping aerosols exhibited an upregulation of the oxidative stress genes, HMOX-1 and GSTP1, indicating the potential for inhalation toxicity. This work highlights the indirect danger of vaping in environments with high ground-level O3, which can chemically transform e-cigarette aerosols into new particles that can induce greater oxidative damage than fresh e-cigarette aerosols. Given that the toxicological characteristics of e-cigarettes are mainly associated with the inhalation of fresh aerosols in current studies, our work may provide a perspective that characterizes vaping exposure under secondhand or thirdhand conditions as a significant health risk.

Molecular mechanisms and atmospheric implications of the simplest criegee intermediate and hydrochloric acid chemistry in the gas phase and at the aqueous interfaces

The atmospheric chemistry of Criegee Intermediates has become a frontier research point in environmental pollution in recent years. In this work, quantum chemical calculations and Born-Oppenheimer Molecular Dynamics (BOMD) simulations were employed to explore the gas phase and aqueous interface behavior of the simplest Criegee Intermediate (sCI, CH2OO) and hydrochloric acid (HCl) reaction. Quantum chemical calculations have revealed that the product of ClCH2OOH (CMHP) formation from the CH2OO + HCl reaction without and with water molecule undergoes a barrierless or near barrierless process in the gas phase. The results of the rate coefficients calculated by the master equation indicate that the gas-phase CMHP formation from the reaction of CH2OO + HCl could compete with the hydrolysis of CH2OO with (H2O)2 at the altitude of 15 km. BOMD simulations at the aqueous interfaces show that the CH2OO + HCl reaction occurs through stepwise mechanisms that are distinct from those in the gas phase. Three different interfacial reaction channels were identified: i) CMHP direct formation, ii) water-mediated CMHP formation, and iii) HCl-mediated hydroxymethyl hydroperoxide (HMHP) formation, and completed in picosecond time scales. Considering the harsh reaction conditions between CH2OO and HCl at the interface (i.e., the two molecules must be sufficiently close to form the CH2OO-HCl complex), the route of HMHP formation via the hydrolysis of CH2OO remains the main atmospheric loss pathway of CH2OO at the aqueous interfaces. Interestingly, molecular dynamic simulations in nanosecond time scales reveal that the formed CMHP in the gas phase has a tendency to aggregate with sulfuric acids, ammonia, and water molecules to form stable clusters within 213–278 K. The present results for the CMHP and HMHP formations from the sCI-HCl chemistry in the atmosphere will enhance our comprehension of the atmospheric behavior of Criegee intermediates in urban and marine pollution areas.

Enhancing Phototoxicity in Human Colorectal Tumor Cells Through Nanoarchitectonics for Synergistic Photothermal and Photodynamic Therapies.

Phototherapies are promising for noninvasive treatment of aggressive tumors, especially when combining heat induction and oxidative processes. Herein, we show enhanced phototoxicity of gold shell-isolated nanorods conjugated with toluidine blue-O (AuSHINRs@TBO) against human colorectal tumor cells (Caco-2) with synergic effects of photothermal (PTT) and photodynamic therapies (PDT). Mitochondrial metabolic activity tests (MTT) performed on Caco-2 cell cultures indicated a photothermal effect from AuSHINRs owing to enhanced light absorption from the localized surface plasmon resonance (LSPR). The phototoxicity against Caco-2 cells was further increased with AuSHINRs@TBO where oxidative processes, such as hydroperoxidation, were also present, leading to a cell viability reduction from 85.5 to 39.0%. The molecular-level mechanisms responsible for these effects were investigated on bioinspired tumor membranes using Langmuir monolayers of Caco-2 lipid extract. Polarization-modulation infrared reflection-absorption spectroscopy (PM-IRRAS) revealed that the AuSHINRs@TBO incorporation is due to attractive electrostatic interactions with negatively charged groups of the Caco-2 lipid extract, resulting in the expansion of surface pressure isotherms. Upon irradiation, Caco-2 lipid extract monolayers containing AuSHINRs@TBO (1:1 v/v) exhibited ca. 1.0% increase in surface area. This is attributed to the generation of reactive oxygen species (ROS) and their interaction with Caco-2 lipid extract monolayers, leading to hydroperoxide formation. The oxidative effects are facilitated by AuSHINRs@TBO penetration into the polar groups of the extract, allowing oxidative reactions with carbon chain unsaturations. These mechanisms are consistent with findings from confocal fluorescence microscopy, where the Caco-2 plasma membrane was the primary site of the cell death induction process.

Structure–reactivity relationships in the ionic-liquid-catalyzed oxidation of cumene: Cation effects

Cumene oxidation is a key step in the industrial synthesis of phenol via cumyl hydroperoxide (CHP) formation. Ionic liquids (ILs) are attractive as green, metal-free alternatives catalysts for this reaction, but few studies have explored their potential. The study of the relationship between the structure and catalytic performance of ILs is crucial for the development of ionic liquids with excellent performance. In this study, we aimed to establish a theoretical protocol to evaluate the catalytic activity of ILs for cumene oxidation, as well as the structure–activity relationship, using density functional theory calculations. The calculations showed that the catalytic activity of the studied ILs decreased as follows: 1-n-butyl-3-methylimidazolium bromide > 1-butyl-1-methylpyrrolidinium bromide > N-n-butylpyridinium bromide > triethylammonium bromide > 1-n-butyl-2-methylpyrrolinium bromide. Moreover, the polarity, solubility, and maximum electrostatic potential of the ILs were linearly correlated with their catalytic activity. The theoretical predictions were verified by experiment. Additionally, DFT calculation and EPR analysis demonstrated that the catalytic activity of ionic liquids originates from the formation of hydrogen-abstracting radicals. Furthermore, using 1-butyl-1-methylpyrrolidinium bromide as a representative catalyst, we optimized the reaction conditions, a cumene conversion of 24.2 % and a CHP selectivity of > 90 % were obtained. Compared with the aqueous NaOH as a stabilizing agent, the reaction time is reduced by 8 h. This study provides new insights for designing efficient, low-cost, and environmentally friendly catalysts for cumene oxidation.

Formation of alkoxymethyl hydroperoxides and alkyl formates from simplest Criegee intermediate (CH2OO) + ROH (R=CH3, CH3CH2, and (CH3)2CH) reaction systems

Formation of alkoxymethyl hydroperoxides and alkyl formates from simplest Criegee intermediate (CH2OO) + ROH (R=CH3, CH3CH2, and (CH3)2CH) reaction systems

Role of Hydroperoxyl Radicals in Heterogeneous Oxidation of Oxygenated Organic Aerosols.

Heterogeneous oxidative aging of organic aerosols (OA) occurs ubiquitously in the atmosphere, initiated by oxidants, such as the hydroxyl radicals (•OH). Hydroperoxyl radicals (HO2•) are also an important oxidant in the troposphere, and its gas-phase chemistry has been well studied. However, the role of HO2• in heterogeneous OA oxidation remains elusive. Here, we carry out •OH-initiated heterogeneous oxidation of several OA model systems under different HO2• conditions in a flow tube reactor and characterize the molecular oxidation products using a suite of mass spectrometry instrumentation. By using hydrogen-deuterium exchange (HDX) with thermal desorption iodide-adduct chemical ionization mass spectrometry, we provide direct observation of organic hydroperoxide (ROOH) formation from heterogeneous HO2• and peroxy radicals (RO2•) reactions for the first time. The ROOH may contribute substantially to the oxidation products, varied with the parent OA chemical structure. Furthermore, by regulating RO2• reaction pathways, HO2• also greatly influence the overall composition of the oxidized OA. Last, we suggest that the RO2• + HO2• reactions readily occur at the OA particle interface rather than in the particle bulk. These findings provide new mechanistic insights into the heterogeneous OA oxidation chemistry and help fill the critical knowledge gap in understanding atmospheric OA oxidative aging.

Carotenoid-dependent singlet oxygen photogeneration in light-harvesting complex 2 of Ectothiorhodospira haloalkaliphila leads to the formation of organic hydroperoxides and damage to both pigments and protein matrix.

Earlier, it was suggested that carotenoids in light-harvesting complexes 2 (LH2) can generate singlet oxygen, further oxidizing bacteriochlorophyll to 3-acetyl-chlorophyll. In the present work, it was found that illumination of isolated LH2 preparations of purple sulfur bacterium Ectothiorhodospira haloalkaliphila with light in the carotenoid absorption region leads to the photoconsumption of molecular oxygen, which is accompanied by the formation of hydroperoxides of organic molecules in the complexes. Photoformation of two types of organic hydroperoxides were revealed: highly lipophilic (12 molecules per one LH2) and relatively hydrophobic (68 per one LH2). It has been shown that illumination leads to damage to light-harvesting complexes. On the one hand, photobleaching of bacteriochlorophyll and a decrease in its fluorescence intensity are observed. On the other hand, the photoinduced increase in the hydrodynamic radius of the complexes, the reduction in their thermal stability, and the change in fluorescence intensity indicate conformational changes occurring in the protein molecules of the LH2 preparations. Inhibition of the processes described above upon the addition of singlet oxygen quenchers (L-histidine, Trolox, sodium L-ascorbate) may support the hypothesis that carotenoids in LH2 preparations are capable of generating singlet oxygen, which, in turn, damage to protein molecules.

OxyR-regulated T6SS functions in coordination with siderophore to resist oxidative stress.

The formation of reactive oxygen species is harmful and can destroy intracellular macromolecules such as lipids, proteins, and DNA, even leading to bacterial death. To cope with this situation, microbes have evolved a variety of sophisticated mechanisms, including antioxidant enzymes, siderophores, and the type VI secretion system (T6SS). However, the mechanism of oxidative stress resistance in Cupriavidus pinatubonensis is unclear. In this study, we identified Reut_A2805 as an OxyR ortholog in C. pinatubonensis, which positively regulated the expression of T6SS1 by directly binding to its operon promoter region. The study revealed that OxyR-regulated T6SS1 combats oxidative stress by importing iron into bacterial cells. Moreover, the T6SS1-mediated outer membrane vesicles-dependent iron acquisition pathway played a crucial role in the oxidative stress resistance process. Finally, our study demonstrated that the T6SS1 and siderophore systems in C. pinatubonensis exhibit different responses in combating oxidative stress under low-iron conditions, providing a comprehensive understanding of how bacterial iron acquisition systems function in diverse conditions.IMPORTANCEThe ability to eliminate reactive oxygen species is crucial for bacterial survival. Continuous formation of hydroperoxides can damage metalloenzymes, disrupt DNA integrity, and even result in cell death. While various mechanisms have been identified in other bacterial species to combat oxidative stress, the specific mechanism of oxidative stress resistance in C. pinatubonensis remains unclear. The importance of this study is that we elucidate the mechanism that OxyR-regulated T6SS1 combats oxidative stress by importing iron with the help of bacterial outer membrane vesicle. Moreover, the study highlights the contrasting responses of T6SS1- and siderophore-mediated iron acquisition systems to oxidative stress. This study provides a comprehensive understanding of bacterial iron acquisition and its role in oxidative stress resistance in C. pinatubonensis under low-iron conditions.

Photoinduced Removal of Molecular Oxygen from Solutions

We propose a new, simple and general procedure of light-driven deoxygenation of solutions based on hydroperoxides formation upon irradiation. Efficient and fast removal of molecular oxygen is caused by photosensitized...

The role of lipid oxidation pathway in reactive oxygen species-mediated cargo release from liposomes.

Reactive oxygen species (ROS)-mediated photooxidation is an efficient method for triggering a drug release from liposomes. In addition to the release of small molecules, it also allows the release of large macromolecules, making it a versatile tool for controlled drug delivery. However, the exact release mechanism of large macromolecules from ROS-sensitive liposomes is still unclear. There are no studies on the effect of lipid oxidation on the release of cargo molecules of different sizes. By using HPLC-HRMS method we analyzed the oxidation products of ROS-sensitive DOTAP lipid in phthalocyanine-loaded DOTAP:Cholesterol:DSPE-PEG liposomes after 630 nm light irradiation of different durations. Shorter illumination time (1-2 minutes) led to the formation of hydroperoxides and vic-alcohols predominantly. Longer 9-minute irradiation resulted already in aldehydes generation. Interestingly, the presence of epoxides/mono-hydroperoxides and vic-alcohols in a lipid bilayer ensured a high 90% release of small hydrophilic cargo molecules i.e. calcein, but not large (≥10 KDa) macromolecules. Oxidation till aldehydes was mandatory to deliver e.g. dextrans of 10-70 kDa with ca. 30% efficiency. Molecular dynamics simulations revealed that the formation of aldehydes is required to form pores or even fully disrupt the lipid membrane, while e.g. presence of hydroperoxides is enough to make the bilayer more permeable just for water and small molecules. This is an important finding that shed a light on the release mechanism of different cargo molecules from ROS-sensitive drug delivery systems.

ВЫДЕЛЕНИЕ ГИДРОПЕРОКСИДА ВТОР-БУТИЛБЕНЗОЛА ИЗ ПРОДУКТОВ ЖИДКОФАЗНОГО ОКИСЛЕНИЯ ВТОР-БУТИЛБЕНЗОЛА МЕТОДОМ ЭКСТРАКЦИИ

Hydroperoxides of alkylaromatic hydrocarbons are valuable products of organic synthesis, which are widely used as initiators of polymerization and liquid-phase oxidation of hydrocarbons, as well as an epoxidizing agent. In addition, hydroperoxides are intermediates in the production of phenol and its alkyl derivatives. In this paper, a method is proposed for the isolation of tertiary hydroperoxide of sec-butylbenzene from the products of its liquid-phase aerobic oxidation by extraction with aqueous solutions of various solvents (methanol, ethanol, isopropanol, dimethylformamide, acetone and acetonitrile). The influence of the nature of the solvent, its concentration and the initial concentration of hydroperoxide on this process has been studied. Based on the experimental data obtained, it was found that 75-80% solutions of methanol and ethanol were the most effective in the extraction process. A high distribution coefficient is observed for a 75% methanol solution and is 1.24. It has been shown that up to 60% of the hydroperoxide can be extracted by single extraction. Carrying out a five-stage extraction of products of liquid-phase oxidation of second-butylbenzene with a 75% ethanol solution makes it possible to obtain concentrated up to 95% sec-butylbenzene hydroperoxide. Its structure was confirmed by IR spectroscopy. In this case, the isolated unreacted hydrocarbon can be directed to re-oxidation while maintaining a high rate, conversion and selectivity of hydroperoxide formation. The resulting concentrated tertiary hydroperoxide of sec-butylbenzene was subjected to sulfuric acid decomposition in a methyl ethyl ketone medium. It has been established that the products of this reaction are phenol and methyl ethyl ketone. At room temperature and a catalyst content of 0.8% by weight phenol and methyl ethyl ketone with yields of 88 and 71%, respectively, were obtained from hydroperoxide loading.

Revealing the low to moderate temperature oxidation kinetics of 1,2,4-trimethylbenzene sensitized by dimethyl ether

Low to moderate temperature oxidation has been a vital topic in the combustion chemistry due to its critical role in controlling the combustion characteristics such as autoignition and pollutant emissions. Low temperature oxidation kinetics of alkanes and oxygenated biofuels have been widely explored, while that of branched aromatics is poorly understood. This work aims to investigate the low to moderate temperature oxidation kinetics of 1,2,4-trimethylbenzene (TMB, C9H12), which is a multi-branched alkylbenzene with weak low temperature oxidation reactivity. To enhance the low temperature oxidation reactivity of TMB, dimethyl ether (DME) was added to efficiently provide chain initiators. The oxidation experiment of TMB/DME mixture was performed with an atmospheric jet stirred reactor coupled with synchrotron vacuum ultraviolet radiation photoionization mass spectrometry. The negative temperature coefficient (NTC) behavior, as well as featured aromatic intermediates, especially phenyl hydroperoxides and unexpected highly oxygenated molecules (HOMs), were observed in the experiment. The detection of these fingerprint aromatic intermediates provide crucial evidence for revealing the low to moderate oxidation kinetics of TMB. In addition, a kinetic model was developed to provide in-depth kinetic analysis. The results demonstrate that the active chain initiators produced from DME oxidation trigger the low temperature chain-branching reactions of TMB. The chain recycling process is further sustained due to the regeneration of active intermediates such as phenyl hydroperoxides and •OH radicals. Aromatic intermediates with chemical compositions of C9H12Ox and C9H10Ox were measured and identified to be key indicators for the low temperature chemistry of TMB. In particular, the aromatic HOMs (C9H12O6 and C9H10O5) are fingerprint intermediates produced from the third O2 addition and subsequent reactions of TMB. Besides, the sensitivity analysis indicates that the interaction kinetics between TMB and DME by sharing the highly sensitive reactions of hydroperoxides and •OH radicals. The present work extends the conceptual reaction schemes proposed in alkanes towards branched aromatics, especially sequential O2 addition reactions that contributing to the formation of phenyl hydroperoxides and HOMs.