Major Oxidation Products Research Articles

Efficiency, products and mechanisms of ethyl acetate oxidative degradation in air non-thermal plasma

Ethyl acetate (EA) is a popular solvent and diluent in many products and one of the most ubiquitous organic pollutants of indoor air. Although EA’s ascertained toxicity is classified as low, exposure to its vapors at concentrations ⩾400 ppm causes serious problems in humans. EA is thus a frequent target in testing novel technologies for air purification. We report here an investigation of EA oxidative degradation in air at room temperature and atmospheric pressure induced by corona discharges. Three corona regimes, dc−, dc+ and pulsed +, were tested in the same reactor under various experimental conditions with regard to EA initial concentration (C0) and the presence of humidity in the system. The EA degradation process was monitored by gas chromatography (GC)–flame ionization detection, GC–mass spectrometry and Fourier transform infrared spectroscopy analysis of the treated gas. These analyses yielded the concentration of residual EA (C) and those of its major products of oxidation (CO2, CO) and revealed a few organic reaction intermediates formed along the oxidation chain. The process energy efficiency was determined as energy constant, kE (kJ−1 l) and as energy yield, EY (g kW−1 h−1). The efficiency depends on the type of corona (pulsed + >dc− >dc+), on the presence of humidity in the air (improvement in the case of dc−, little or no effect for dc+) and on C0 (kE increases linearly with 1/C0). CO2 and CO were the major carbon containing products, confirming the strong oxidizing power of air non-thermal plasma. Acetic acid and acetaldehyde were detected in very small amounts as reaction intermediates. The experimental results obtained in this work support the conclusion that different reactive species are involved in the initial step of EA oxidation in the case of dc− and dc+ corona air non-thermal plasma.

Mapping hydroxyl variability throughout the global remote troposphere via synthesis of airborne and satellite formaldehyde observations

The hydroxyl radical (OH) fuels tropospheric ozone production and governs the lifetime of methane and many other gases. Existing methods to quantify global OH are limited to annual and global-to-hemispheric averages. Finer resolution is essential for isolating model deficiencies and building process-level understanding. In situ observations from the Atmospheric Tomography (ATom) mission demonstrate that remote tropospheric OH is tightly coupled to the production and loss of formaldehyde (HCHO), a major hydrocarbon oxidation product. Synthesis of this relationship with satellite-based HCHO retrievals and model-derived HCHO loss frequencies yields a map of total-column OH abundance throughout the remote troposphere (up to 70% of tropospheric mass) over the first two ATom missions (August 2016 and February 2017). This dataset offers unique insights on near-global oxidizing capacity. OH exhibits significant seasonality within individual hemispheres, but the domain mean concentration is nearly identical for both seasons (1.03 ± 0.25 × 106 cm-3), and the biseasonal average North/South Hemisphere ratio is 0.89 ± 0.06, consistent with a balance of OH sources and sinks across the remote troposphere. Regional phenomena are also highlighted, such as a 10-fold OH depression in the Tropical West Pacific and enhancements in the East Pacific and South Atlantic. This method is complementary to budget-based global OH constraints and can help elucidate the spatial and temporal variability of OH production and methane loss.

Acetaldehyde reactions during wine bottle storage

Acetaldehyde is a major wine oxidation product. Here, three Cabernet Sauvignon wines, containing different levels of acetaldehyde from different micro-oxygenation (mOx) regimes, including yeast-mediated treatments, were aged under closures differing in oxygen ingress. Oxygen, phenolics, carbonyls and heterocyclic acetals were measured. Acetaldehyde levels at bottling was a significant factor in the phenolic compound profile after one year, with anthocyanins most affected, then flavonols, flavonoids and hydroxycinnamic acids, but there were negligible effects on benzoic acids. The effect of bottle closures with increased oxygen ingress had a similar trend. Increased acetaldehyde levels and oxygen ingress also yielded higher levels of the heterocyclic acetals from glycerol. These changes reflect aging, and suggest that managing mOx during production could be used to reduce the time needed to achieve some aged wine characteristics.

Discrimination of chemical and biological sulfide oxidation in a hybrid two-phase process

Hydrogen sulfide having the detrimental effect on humans and ecosystems can be metabolized by sulfur-oxidizing bacteria (SOB) as an energy source, however, SOB cannot tolerate high sulfide levels. A hybrid two-phase process was therefore proposed in this work to enhance the high-level sulfide oxidation based on discrimination of abiotic versus biotic oxidation. Separate experiments were performed to investigate the chemical and biological oxidations of sulfide at 500–2000 mg l−1. Products distribution showed that thiosulfate and intermediate products were the major products (more than 88%) of chemical oxidation, while sulfate was the predominant product in the biological oxidation. Nonetheless, sulfate formation declined from 90.5 to 35.5% with increasing sulfide level due to sulfide toxicity. To enhance oxidation, the effect of pH and adaptation methods were investigated, where insignificant changes were observed. The hybrid process resulted in complete sulfide transformation in the abiotic phase into less toxic products, which were further oxidized in biotic phase. This enhanced sulfate formation by 41% (55) at 1000 mg l−1 (2000) sulfide compared to the conventional biological case. The superiority of this hybrid two-phase process especially at higher sulfide levels was shown to be mainly due to complete sulfide detoxification.

Oxidation of 2,6-di-tert-butylphenol with tert-butyl hydroperoxide catalyzed by iron porphyrin tetrasulfonate, iron porphyrin tetracarboxylate and their supported analogues in a water-methanol mixture.

In this study, two water-soluble iron porphyrins bearing sulfonate and carboxylate functionalities (FePTS and FePTC, respectively) and their supported analogues were used as catalysts for the oxidation of 2,6-di-tert-butylphenol (DTBP) in a water-methanol mixture. tert-Butyl hydroperoxide (TBHP) was the oxidant and the volume ratio of water to methanol in the mixture was 1-8. The major products of the DTBP oxidation were 3,3',5,5'-tetra-tert-butyl-4,4'-diphenoquinone (DPQ) and 4,4'-dihydroxy-3,3',5,5'-tetra-tert- butylbiphenyl (H2DPQ). Also 2,6-di-tert-butyl-1,4-benzoquinone (BQ) was the minor product of the oxidation. The results showed that FePTC was more catalytically active than FePTS in the oxidation and gave the highest TON and TOF values in comparison to those for metalloporphyrin and metallophthalocyanine based catalysts in the DTBP oxidation given in the literature. In addition, the ecotoxicity tests of the DTBP oxidation mixtures before and after oxidative catalytic treatment toward Artemia salina were performed. It was found that the toxicity of the catalytically treated DTBP mixture containing residual DTBP and products was lower than the catalytically untreated DTBP mixture.

Oxidation evaluation of free astaxanthin and astaxanthin esters in Pacific white shrimp during iced storage and frozen storage.

In this paper, the changes in free astaxanthin (F-AST) and astaxanthin esters (AST-Es) in Litopenaeus vannamei during iced storage and frozen storage were investigated. The liquid chromatography-atmospheric pressure chemical ionization tandem mass spectrometry method was used to quantify the molecular species of AST-Es in shrimp during storage. Based on the analysis of autoxidation products, apo-12-astaxanthinal and apo-13-astaxanthinone docosahexaenoic acid (DHA) ester were identified as the major oxidation products of F-AST and AST-Es in L. vannamei during storage. The total astaxanthin (T-AST) content decreased by 34.51% after 7 days in iced storage. In contrast, the content of T-AST decreased by 43.76% after 12 weeks in frozen storage. The content of F-AST decreased by 29.99% while 13-cis-astaxanthin increased after 3 days in iced storage, which indicated that degradation of AST was accompanied by isomerization. Total volatile basic nitrogen and T-AST content showed a significant negative correlation while in frozen storage, where the concentration of T-AST might be one indicator to evaluate shrimp freshness. The correlation coefficients between phenol oxidase, lipoxygenase, apo-12-astaxanthinal, and apo-13-astaxanthinone DHA ester were all greater than 0.97 (P < 0.01). This correlation indicates that phenol oxidase and lipoxygenase were the main internal factors to improve oxygenation of astaxanthin in L. vannamei. These results provide a theoretical basis for further study of oxidation and the degradation mechanism in astaxanthin, as well as a new idea for the development and utilization of astaxanthin compounds in Pacific white shrimp. © 2018 Society of Chemical Industry.

Transformations of the Bis(thiourea)gold(I) Complex in Alkaline Medium and Interaction of Thiourea with HAuCl4

The interaction of AuCl 4 - with thiourea (tu) at various Сtu/СAu ratios and transformations of the bis(thiourea)gold(I) complex in an alkaline aqueous solution have been studied. Both processes lead to a set of products. It has been demonstrated that formamidine disulfide is not the major product of thiourea oxidation. The precipitate forming upon the treatment of AuCl 4 - with an alkali contains Au2S and an organic part, which is likely a polymeric compound [Au(tu-H)]n.

Zwitterionic, cationic, and anionic perfluoroalkyl and polyfluoroalkyl substances integrated into total oxidizable precursor assay of contaminated groundwater

The total oxidizable precursor (TOP) assay can be useful for integrating precursors to perfluoroalkyl acids (pre-PFAAs) into the assessment of sites contaminated by per- and polyfluoroalkyl substances (PFAS). Current research gaps include risks of instrumental matrix effects due to the complexity of post-oxidation extracts, potential reproducibility issues during TOP itself, and limited information for zwitterionic and cationic pre-PFAAs. We first investigated a suitable method for the analysis of groundwater samples, using liquid chromatography high-resolution mass spectrometry (UHPLC-HRMS). Initial sample pre-treatment through filtration could affect the dissolved PFAS concentrations and was therefore avoided. Amending the postoxidation samples with methanol allowed for improved precision and low instrumental matrix effects. We also documented the oxidation yields of 23 anionic, neutral, zwitterionic, and cationic precursor compounds of PFAAs. These precursor compounds were amenable to TOP conversion. The total oxidative yield of 6:2 fluorotelomer sulfonamidoalkyl betaine (6:2 FTAB), for instance, was 80 mol%, with C3-C5 PFCAs as major oxidation products (minor: C6-C7 PFCAs). The method was applied to determine a wide range of PFAS (n = 41) without oxidation as well as ΔPFCA via persulfate oxidation in AFFF-impacted groundwater samples from fire-equipment testing sites in Ontario and Newfoundland, Canada. Summed PFAS concentrations as high as 5 mg L−1 were reported before oxidation, and post-oxidation increases of PFCAs up to + 2300% were observed. A significant contribution of increases in individual PFCAs was attributed to precursors such as 6:2 FTAB, fluorotelomer sulfonates (6:2 FtS, 8:2 FtS), perfluorooctane sulfonamidoalkyl amine (PFOSAm), and perfluorohexane sulfonamide (FHxSA) at the active firefighting training site.

Oxidation of ethanol and hydrocarbon mixtures in a pressurised flow reactor

This paper presents a study of the oxidation of iso-octane, ethanol, toluene and their mixtures in a pressurised turbulent flow reactor operating at 900–930 K, 10 bar, and an equivalence ratio of 0.058. A large set of fuels is investigated, including neat iso-octane, ethanol, toluene, their binary mixtures, gasoline reference fuels (PRF91 and TRF91), and their mixtures with ethanol. The resulting species are measured along the length of the reactor and simulated using existing kinetic models from the literature.The existing models are found to reproduce measurements of the major oxidation products of iso-octane, ethanol, their binary mixtures, as well as that of PRF91 and PRF91/ethanol mixtures. However, significant differences are observed between the measurement and simulation of neat toluene. Adjustment is then made to the rate constants of key reactions in the toluene model. The adjusted model, whilst more accurately reproducing neat toluene oxidation, does not significantly improve the modelling of toluene containing mixtures. This suggests that further investigations should focus on the oxidation of neat toluene, as well as the chemical interactions of toluene containing mixtures.

Gas-to-particle partitioning of major biogenic oxidation products: a study on freshly formed and aged biogenic SOA

Abstract. Secondary organic aerosols (SOAs) play a key role in climate change and air quality. Determining the fundamental parameters that distribute organic compounds between the phases is essential, as atmospheric lifetime and impacts change drastically between the gas and particle phase. In this work, gas-to-particle partitioning of major biogenic oxidation products was investigated using three different aerosol chemical characterization techniques. The aerosol collection module, the collection thermal desorption unit, and the chemical analysis of aerosols online are different aerosol sampling inlets connected to a proton-transfer reaction time-of-flight mass spectrometer (ACM-PTR-ToF-MS, TD-PTR-ToF-MS, and CHARON-PTR-ToF-MS, respectively, referred to hereafter as ACM, TD, and CHARON). These techniques were deployed at the atmosphere simulation chamber SAPHIR to perform experiments on the SOA formation and aging from different monoterpenes (β-pinene, limonene) and real plant emissions (Pinus sylvestris L.). The saturation mass concentration C* and thus the volatility of the individual ions was determined based on the simultaneous measurement of their signal in the gas and particle phase. A method to identify and exclude ions affected by thermal dissociation during desorption and ionic dissociation in the ionization chamber of the proton-transfer reaction mass spectrometer (PTR-MS) was developed and tested for each technique. Narrow volatility distributions with organic compounds in the semi-volatile (SVOCs – semi-volatile organic compounds) to intermediate-volatility (IVOCs – intermediate-volatility organic compounds) regime were found for all systems studied. Despite significant differences in the aerosol collection and desorption methods of the proton-transfer-reaction (PTR)-based techniques, a comparison of the C* values obtained with different techniques was found to be in good agreement (within 1 order of magnitude) with deviations explained by the different operating conditions of the PTR-MS. The C* of the identified organic compounds were mapped onto the two-dimensional volatility basis set (2D-VBS), and results showed a decrease in C* with increasing oxidation state. For all experiments conducted in this study, identified partitioning organic compounds accounted for 20–30 % of the total organic mass measured from an aerosol mass spectrometer (AMS). Further comparison between observations and theoretical calculations was performed for species found in our experiments that were also identified in previous publications. Theoretical calculations based on the molecular structure of the compounds showed, within the uncertainties ranges, good agreement with the experimental C* for most SVOCs, while IVOCs deviated by up to a factor of 300. These latter differences are discussed in relation to two main processes affecting these systems: (i) possible interferences by thermal and ionic fragmentation of higher molecular-weight compounds, produced by accretion and oligomerization reactions, that fragment in the m∕z range detected by the PTR-MS and (ii) kinetic influences in the distribution between the gas and particle phase with gas-phase condensation, diffusion in the particle phase, and irreversible uptake.

7-Ketocholesterol enhances leukocyte adhesion to endothelial cells via p38MAPK pathway.

7-Ketocholesterol is a major dietary cholesterol oxidation product found in high concentrations in atherosclerotic plaques, which contribute to the development of atherosclerosis. This study aimed to investigate the effects of 7-ketocholesterol on endothelial inflammation, as well as the underlying mechanisms. Pretreatment of human umbilical vein endothelial cells (HUVEC) with 7-ketocholesterol significantly enhanced the total interactions between human monocytic cells (THP-1 cell line) and TNFα-activated HUVECs under physiological flow conditions, compared to pretreatment with cholesterol (TNFα+50 μM cholesterol: 13.1 ± 0.54 cells/CPF, TNFα+50 μM 7-ketocholesterol: 18.9 ± 0.35 cells/CPF, p < 0.01). 7-Ketocholesterol enhanced the expression of E-selectin, ICAM-1, and VCAM-1 proteins. It also activated p38 mitogen-activated protein kinase (MAPK), and treatment with a p38 MAPK inhibitor inhibited both E-selectin expression via ATF-2 activation and 7-ketocholesterol-induced THP-1 adhesion to HUVECs. These findings suggest that 7-ketocholesterol enhances leukocyte–endothelial interactions by upregulating the expression of adhesion molecules, presumably via the p38 MAPK-dependent pathway.

A PVA film for detecting lipid oxidation intended for food application

Lipid oxidation is a big contributor to food deterioration. The objective of this study was to develop an intelligent film for visually detecting lipid oxidation, based on the colorimetric reaction of Schiff’s reagent and aldehydes—the major volatile lipid oxidation products. A polyvinyl alcohol (PVA) film containing Schiff’s reagent was formed, with the elasticity modulus of 0.27 MPa and the tensile strength of 19.17 MPa. The PVA film was exposed to various concentration (0–7.02 mg/L) of gaseous hexanal—the major aldehyde formed during lipid oxidation, the color change of the PVA film was measured by CIELab scale. The color of PVA film changed from colorless to purple after exposure to hexanal. As the hexanal concentration increased, the color change of the PVA film was more obvious. A linear relationship was found between the hexanal concentration and the color change. The developed PVA film could be an indicator for lipid oxidation of food when incorporated as a minor component of food packaging.

Multienzyme Cascade Bioreactor for a 10 min Digestion of Genomic DNA into Single Nucleosides and Quantitative Detection of Structural DNA Modifications in Cellular Genomic DNA.

Identification and quantification of chemical DNA modifications provide essential information on genomic DNA changes, for example, epigenetic modifications and abnormal DNA lesions. In this vein, it requires to digest genomic DNA strands into single nucleosides, facilitating the mass spectrometry analysis. However, rapid digestion of such supramacromolecule DNA of several millions Daltons (molecular weight) into single nucleosides remains very challenging. Here, we constructed an immobilized benzonase capillary bioreactor and further tandemly coupled with immobilized snake venom phosphodiesterase and alkaline phosphatase capillary bioreactor to form a novel three-enzyme cascade bioreactor (BenzoSAC bioreactor). In these constructions, the chosen enzymes were immobilized onto synthetic porous capillary silica monoliths. With the tailor-made porous structure and high immobilized capacity and high digestion rate of benzonase, genomic DNA of >99.5% can be digested into single nucleosides within only 10 min when passing through the BenzoSAC bioreactor by microinjection pump. In contrast, traditional digestion requires 8-24 h. By offline coupling this benzoSAC bioreactor with liquid chromatography-tandem mass spectrometry, we detected 5-hydroxymethylcytosine, a major oxidation product of the epigenetically crucial 5-methylcytosine, in genomic DNA isolated from ladder cancer (T24) cells. The newly synthesized BenzoSAC bioreactor and the proposed mass spectrometry detection are promising for fast identification and analysis of structural modifications in DNA.

Investigation of the oxidation of methyl vinyl ketone (MVK) by OH radicals in the atmospheric simulation chamber SAPHIR

Abstract. The photooxidation of methyl vinyl ketone (MVK) was investigated in the atmospheric simulation chamber SAPHIR for conditions at which organic peroxy radicals (RO2) mainly reacted with NO (“high NO” case) and for conditions at which other reaction channels could compete (“low NO” case). Measurements of trace gas concentrations were compared to calculated concentration time series applying the Master Chemical Mechanism (MCM version 3.3.1). Product yields of methylglyoxal and glycolaldehyde were determined from measurements. For the high NO case, the methylglyoxal yield was (19 ± 3) % and the glycolaldehyde yield was (65 ± 14) %, consistent with recent literature studies. For the low NO case, the methylglyoxal yield reduced to (5 ± 2) % because other RO2 reaction channels that do not form methylglyoxal became important. Consistent with literature data, the glycolaldehyde yield of (37 ± 9) % determined in the experiment was not reduced as much as implemented in the MCM, suggesting additional reaction channels producing glycolaldehyde. At the same time, direct quantification of OH radicals in the experiments shows the need for an enhanced OH radical production at low NO conditions similar to previous studies investigating the oxidation of the parent VOC isoprene and methacrolein, the second major oxidation product of isoprene. For MVK the model–measurement discrepancy was up to a factor of 2. Product yields and OH observations were consistent with assumptions of additional RO2 plus HO2 reaction channels as proposed in literature for the major RO2 species formed from the reaction of MVK with OH. However, this study shows that also HO2 radical concentrations are underestimated by the model, suggesting that additional OH is not directly produced from RO2 radical reactions, but indirectly via increased HO2. Quantum chemical calculations show that HO2 could be produced from a fast 1,4-H shift of the second most important MVK derived RO2 species (reaction rate constant 0.003 s−1). However, additional HO2 from this reaction was not sufficiently large to bring modelled HO2 radical concentrations into agreement with measurements due to the small yield of this RO2 species. An additional reaction channel of the major RO2 species with a reaction rate constant of (0.006 ± 0.004) s−1 would be required that produces concurrently HO2 radicals and glycolaldehyde to achieve model–measurement agreement. A unimolecular reaction similar to the 1,5-H shift reaction that was proposed in literature for RO2 radicals from MVK would not explain product yields for conditions of experiments in this study. A set of H-migration reactions for the main RO2 radicals were investigated by quantum chemical and theoretical kinetic methodologies, but did not reveal a contributing route to HO2 radicals or glycolaldehyde.

Catalytic oxidative desulfurization of dibenzothiophene utilizing molybdenum and vanadium oxides supported on MCM-41

As a series of bimetallic nanocatalysts, molybdenum/vanadium oxides supported on the silica (MoO3/V2O5/MCM-41) were prepared by the impregnation. Their catalytic activity in the oxidation of dibenzothiophene was investigated using H2O2 as an oxidant. Textures and surface properties of the prepared catalysts were characterized using FT-IR, XRD, FESEM-EDX and N2 adsorption/desorption techniques. The effects of main process variables including H2O2/DBT molar ratio, catalyst dosage, reaction temperature and reaction time were analyzed by employing the response surface methodology (RSM). The effect of the MoO3/V2O5 loading on the catalytic performance of the catalysts was also investigated. The results indicated that the catalytic activity of the catalyst was increased by enhancing the MoO3/V2O5 content. Thus, the catalyst with high MoO3/V2O5 loading (20%MoO3/20%V2O5/60%MCM-41) indicated the highest catalytic activity and could convert 99.06% of dibenzothiophene under the optimum conditions. Mass and FT-IR analysis demonstrated that the major product of dibenzothiophene oxidation was its corresponding sulfone. The catalyst could be recycled five times without any considerable reduction in its catalytic activity. The kinetics of the reaction fitted the pseudo-first-order equation pretty well. Eventually, a reaction mechanism for the catalytic oxidation of DBT in the presence of MoO3/V2O5/MCM-41 was proposed.

Electrochemical Abatement of Atrazine Solutions Using an Undivided Stirred Tank Cell with Pt or BDD Anode

&lt;p&gt;Nowadays, the increasing pollution of natural water effluents with herbicides, such as atrazine (ATZ, 2-chloro-4-ethylamino-6-isopropylamino-s-triazine), is an emerging problem that has not received the sufficient attention. This work presents a study on ATZ degradation under an electrochemical advanced oxidation process (EAOP), such as anodic oxidation (AO). The degradation of 175 mL of 10 and 40 mg L&lt;sup&gt;-1&lt;/sup&gt; ATZ solutions was studied using Pt or BDD as anode. The assays were made with a stirred tank cell, using a supporting electrolyte of 0.050 mM of Na&lt;sub&gt;2&lt;/sub&gt;SO&lt;sub&gt;4&lt;/sub&gt; at pH 3.0 by applying 0.18, 0.27 and 0.37 A cm&lt;sup&gt;-2&lt;/sup&gt;. The degradation rate increased by increasing current density, regardless of the anode employed. Greater amounts of ATZ were removed at higher organic load. The pesticide decay always obeyed a pseudo-first-order kinetics. A high degradation efficiency of 97%-99% was obtained by the more powerful AO-BDD process at 0.37 A cm&lt;sup&gt;-2&lt;/sup&gt;. High performance liquid chromatography (HPLC) was used to follow the evolution of major oxidation products by AO-BDD, such as desethyl atrazine, desethyl desisopropyl atrazine and cyanuric acid.&lt;/p&gt;

P-132 - Identification of risk factors and biomarkers of diagnostic and prognostic value associated with clinical progression and severity of cerebral cavernous malformations

Cerebral Cavernous Malformation (CCM) is a major cerebrovascular disease with a prevalence of 0.3–0.5% in the general population and highly variable clinical expressivity. It may cause various symptoms at any age, including recurrent headaches, neurological deficits, seizures, and intracerebral hemorrhage, and has been associated with loss-of-function mutations in three CCM genes, CCM1 (KRIT1), CCM2 and CCM3. However, growing evidence in animal models demonstrates that loss of CCM genes is not sufficient to cause CCM disease, suggesting the contribution of additional triggers occurring locally in the neurovascular microenvironment, including stress factors. Indeed, we found that both cellular and animal models of CCM disease show an enhanced sensitivity to oxidative stress and inflammatory insults due to defects in mechanisms involved in cellular defense against these stressful conditions, including antioxidant responses and autophagy. Furthermore, we provide novel insights into the identification of risk factors and biomarkers associated with CCM disease progression and severity, including the accumulation of major glycation and oxidation products, which may serve as early objective predictors of disease outcome and provide better options for disease prevention and treatment.

Quantitative determination of major oxidation products in edible oils by direct NP-HPLC-DAD analysis

The objective of the present study was to explore the possibilities of the direct analysis of vegetable oils by normal-phase HPLC-DAD to evaluate the amounts of the main oxidation products of triacylglycerols containing linoleate, i.e. hydroperoxy-, keto- and hydroxy-dienes. A follow-up of oxidation at 40 °C of trilinolein, used as a simplified model lipid system, high-linoleic sunflower oil and high-oleic sunflower oil was performed to evaluate samples with different fatty acid compositions and different oxidation levels. The results showed that the HPLC-DAD method proposed allows for determining the concentrations of mono-hydroperoxydienes in edible oils without applying any isolation or derivatization step. The method was found to be direct, sensitive (LOQ 0.06 mmol/kg oil), precise (CV ≤ 5%) and also accurate, with 99% of analyte recovery. It also enabled the estimation of the minor amounts of ketodienes, but not those of hydroxydienes, which presented wide chromatographic bands and coeluted with a number of different minor oxidation compounds.

Gas-Phase Reactions of Isoprene and Its Major Oxidation Products.

Isoprene carries approximately half of the flux of non-methane volatile organic carbon emitted to the atmosphere by the biosphere. Accurate representation of its oxidation rate and products is essential for quantifying its influence on the abundance of the hydroxyl radical (OH), nitrogen oxide free radicals (NO x), ozone (O3), and, via the formation of highly oxygenated compounds, aerosol. We present a review of recent laboratory and theoretical studies of the oxidation pathways of isoprene initiated by addition of OH, O3, the nitrate radical (NO3), and the chlorine atom. From this review, a recommendation for a nearly complete gas-phase oxidation mechanism of isoprene and its major products is developed. The mechanism is compiled with the aims of providing an accurate representation of the flow of carbon while allowing quantification of the impact of isoprene emissions on HO x and NO x free radical concentrations and of the yields of products known to be involved in condensed-phase processes. Finally, a simplified (reduced) mechanism is developed for use in chemical transport models that retains the essential chemistry required to accurately simulate isoprene oxidation under conditions where it occurs in the atmosphere-above forested regions remote from large NO x emissions.

Time-resolved method to distinguish protein/peptide oxidation during electrospray ionization mass spectrometry

Electrospray ionization mass spectrometry (ESI-MS) is one of the most prevalent techniques used to monitor protein/peptide oxidation induced by reactive oxygen species (ROSs). However, both corona discharge (CD) and electrochemistry (EC) can also lead to protein/peptide oxidation during ESI. Because the two types of oxidation occur almost simultaneously, determining the extent to which the two pathways contribute to protein/peptide oxidation is difficult. Herein, a time-resolved method was introduced to identify and differentiate CD- and EC-induced oxidation. Using this approach, we separated the instantaneous CD-induced oxidation from the hysteretic EC-induced oxidation, and the effects of the spray voltage and flow rate of the ESI source on both oxidation types were investigated with a homemade ESI source. For angiotensin II analogue (b-DRVYVHPF-y), the dehydrogenation and oxygenation species were the detected EC-induced oxidation products, while the oxygenation species were the major CD-induced oxidation products. This time-resolved approach was also applicable to a commercial HESI source, in which both CD and EC were responsible for hemoglobin and cytochrome c oxidation with upstream grounding while CD dominated the oxidation without upstream grounding.