Non-volatile Oxidation Products Research Articles

Mechanisms of the Formation of Nonvolatile and Volatile Oxidation Products from Methyl Linoleic Acid at High Temperatures.

The impact of the oxidation of linoleic acid cannot be overlooked in daily food consumption. This study used gas chromatography-mass spectrometry (GC-MS) to identify both nonvolatile oxidation products and volatile oxidation products of methyl linoleic acid at 180 °C and density function theory to investigate oxidation mechanisms. An analysis of nonvolatile oxidation products revealed the presence of three primary oxidation products. The three primary oxidation products were identified as hydroperoxides, peroxide-linked dimers, and heterocyclic compounds in a ratio of 2.70:1:3.69 (mmol/mmol/mmol). The volatile components of secondary oxidation products were found including aldehydes (40.77%), alkanes (19.89%), alcohols (9.02%), furans (6.11%), epoxides (0.46%), and acids (2.50%). DFT calculation proved that the secondary oxidation products mainly came from peroxides (77%). Finally, we look forward to our research contributing positively to lipid autoxidation and human health.

Study of the Antioxidant Capacity and Oxidation Products of Resveratrol in Soybean Oil.

Resveratrol (3,5,4'-trihydroxystilbene), a naturally occurring polyphenol that is widely utilized in functional food due to its antioxidant, anti-inflammatory, anti-cancer and anti-aging properties. In the present study, the antioxidant capacity and oxidation products of resveratrol in soybean oil were investigated. The antioxidant activity of resveratrol was evaluated by employing various in vitro antioxidant assays such as DPPH scavenging activities, ferric reducing abilities (FRAP) and oxygen radical absorbance capacity (ORAC). Furthermore, monitoring the peroxide value and the acid value of soybean oil with the addition of 200-1000 μg/g of resveratrol at 60 and 180 °C. It was found that when the concentration of resveratrol in soybean oil was 600 µg/g, the antioxidant capacity was most effective. Resveratrol and its thermal degradation products were identified using liquid chromatography-mass spectrometry (LC-MS) and gas chromatography-mass spectrometry (GC-MS). There were seven nonvolatile oxidation products with mass-to-charge ratios of 138.03, 171.04, 185.10, 157.03, 436.13, 244.07 and 306.09 kg/C and two volatile oxidation products with mass-to-charge ratios of 100.05 and 158.13 kg/C were identified. The research findings may provide essential information for the development of resveratrol as functional oils in future.

Effect of plasma-activated water (PAW) soaking on the lipid oxidation of sardine (Sardina pilchardus) fillets

The efficacy of plasma-activated water (PAW) as a chemical-free and environmentally friendly preservative has been documented for a variety of foods, but the onset of lipid oxidation induced by plasma-reactive species has been less extensively studied. In this work, global indices (peroxide value, UV specific absorbance) and direct analytical determinations of volatile and non-volatile oxidation products were performed on sardine lipids extracted from fish fillets immersed in PAW (treatments) and distilled water (controls) for 10–30 min. Evidence of PAW-induced lipid oxidation was provided by higher UV specific absorbances and higher levels of C5-C9 secondary volatile oxidation products in the treated samples. However, the degree of fatty acid oxidation was not sufficient to cause a significant reduction in nutritionally valuable eicosapentaenoic acid and docosahexaenoic acid. Twelve cholesterol oxidation products (COPs) were identified in the sardine lipids, but no significant differences in total COPs content were found between PAW processed and control samples.

Oxidative stability, oxidation pattern and α-tocopherol response of docosahexaenoic acid (DHA, 22:6n–3)-containing triacylglycerols and ethyl esters

DHA is most often used in supplements either in its triacylglycerol or ethyl ester form. Currently, there is only little published data on the differences in the oxidative stability and α-tocopherol response between the two lipid structures, as well as on the oxidation patterns of pure DHA. This study investigated the oxidative stability, α-tocopherol response and oxidation pattern of DHA incorporated in triacylglycerols and as ethyl esters with an untargeted approach after oxidation at 50 °C in the dark. Liquid and gas chromatographic methods with mass spectrometric detection and nuclear magnetic resonance spectroscopy were applied. DHA was more stable in triacylglycerols than as ethyl esters without α-tocopherol addition. With α-tocopherol added the opposite was observed. The oxidation products formed during triacylglycerol and ethyl ester oil oxidation were mostly similar, but also some structure-related differences were detected in both volatile and non-volatile oxidation products.

PM2.5-bound silicon-containing secondary organic aerosols (Si-SOA) in Beijing ambient air

Volatile methyl siloxanes (VMS) have been widely used in personal care products and industrial applications, and are an important component of VOCs (volatile organic compounds) indoors. They have sufficiently long lifetimes to undergo long-range transport and to form secondary aerosols through atmospheric oxidation. To investigate these silicon-containing secondary organic aerosols (Si-SOA), we collected PM2.5 samples during 8th-21st August 2018 (summer) and 3rd-23rd January 2019 (winter) at an urban site of Beijing. As the oxidation of VMS mainly results in hydrophilic polar semi-volatile and non-volatile oxidation products, the differences between total water-soluble Si and total water-soluble inorganic Si were used to estimate water-soluble organic Si, considered to be secondary organic Si (SO–Si). The average concentrations of SO–Si during the summer and winter campaigns were 4.6 ± 3.7 and 13.2 ± 8.6 ng m−3, accounting for approximately 80.1 ± 10.1% and 80.2 ± 8.7% of the total water-soluble Si, and 1.2 ± 1.2% and 5.0 ± 6.9% of total Si in PM2.5, respectively. The estimated Si-SOA concentrations were 12.7 ± 10.2 ng m−3 and 36.6 ± 23.9 ng m−3 on average in summer and winter, which accounted for 0.06 ± 0.07% and 0.16 ± 0.22% of PM2.5 mass, but increased to 0.26% and 0.92% on certain days. We found that net solar radiation is positively correlated with SO–Si levels in the summer but not in winter, suggesting seasonally different formation mechanisms.

Characterization of Non-volatile Oxidation Products Formed from Triolein in a Model Study at Frying Temperature.

Frying allows cooking food while promoting their organoleptic properties, imparting crunchiness and flavor. The drawback is the oxidation of triacylglycerides (TAGs), leading to the formation of primary oxidized TAGs. Although they have been associated with chronic and degenerative diseases, they are precursors of pleasant flavors in fried foods. Nevertheless, there is a lack of knowledge about the oxidation species present in foods and their involvement in positive/negative health effects. In this work, high-resolution (HR) C30 reversed-phase (RP)-liquid chromatography (LC)-tandem HR mass spectrometry (MS/MS) was used to identify primary oxidation TAGs resulting from heating triolein (160 °C, 5 min). This allows simulating the initial heating process of frying oils usually used to prepare fried foods, such as chips, crisps, and snacks. Beyond hydroxy, dihydroxy, hydroperoxy, and hydroxy-hydroperoxy derivatives, already reported in phospholipids oxidized by Fenton reaction, new compounds were identified, such as dihydroxy-hydroperoxy-triolein derivatives and positional isomers (9/10- and 9/12-dihydroxy-triolein derivatives). These compounds should be considered when proposing flavor formation pathways and/or mitigating lipid-derived reactive oxygen species occurring during food frying.

Influence of relative humidity on oxidation of the free and encapsulated oil fractions in freeze-dried microencapsulated oils

The objective of this work was to evaluate the effect of relative humidity (RH) on oxidation of the free and encapsulated oil fractions of dried microencapsulated oils (DMOs) during long-term storage at 30 °C. Sunflower and fish oils with different tocopherol content were encapsulated in a milk-based encapsulation matrix. The total non-volatile oxidation products and tocopherol were quantitated. Results showed that 0% and 32% RH were, respectively, the most unfavourable and favourable conditions against lipid oxidation. The 32% RH atmosphere exerted a great protective effect on the free oil as compared to 0% RH, while no or a negligible effect was found in the encapsulated oil. Except for the samples most susceptible to oxidation, the free oil remarkably oxidized more slowly than the encapsulated oil regardless of RH. Therefore, there were factors other than moisture that determined the oxidation rate in the free and encapsulated fractions of the DMOs.

A follow-up oxidation study in dried microencapsulated oils under the accelerated conditions of the Rancimat test

Abstract The aim of this research was to study lipid oxidation in dried microencapsulated oils (DMOs) under Rancimat test conditions (100 °C, 20 L air/h). Samples were prepared by freeze-drying of sunflower-oil-in-water emulsions containing sodium caseinate and lactose. Lipid oxidation was evaluated in the free and encapsulated oil fractions of DMOs by quantitation of total non-volatile lipid oxidation products and their distribution in oxidized triacylglycerol monomers, dimers and oligomers. Peroxide value (PV), polymers and tocopherol levels, when indicated, were also determined. Results showed that oxidation in the free oil fraction of DMOs was responsible for the Rancimat response. Oxidation of the free oil fractions exhibited well-defined induction periods (IPs) as detected by either PV determination, direct analysis of polymers or analysis of total non-volatile oxidation products. During the IP, oxidized triacylglycerol monomers were the only oxidation products formed in the free oil fractions, and the end of the IP was marked by the start of significant polymerization. Contrasting results were obtained in the encapsulated oil fractions, wherein oxidation increased gradually from the start of the test but no IP was detected.

Nonvolatile Oxidation Products of Glucose in Maillard Model Systems: Formation of Saccharinic and Aldonic Acids and Their Corresponding Lactones

By using pyrolysis-gas chromatography-mass spectrometry-based methodologies, nonvolatile oxidation products of isotopically labeled glucose/glycine model systems were studied through a postpyrolytic in situ derivatization technique by using trimethylsilyldiethylamine. Analysis of the data indicated that the known reactive sugar intermediates such as glucosone and its deoxy derivatives can undergo in Maillard model systems three types of transformations: oxidation of the aldehydic groups into carboxylic acids, oxidative cleavage of alpha-dicarbonyl moieties into aldonic acids, and benzylic acid rearrangement of 1-deoxy-glucosone into saccharinic acids. The aldonic and saccharinic acids were identified through silylation of their lactone derivatives, and their origin was verified through (13)C-labeling studies. The following lactones were identified in glucose and glucose/glycine model systems: trans-dihydro-3,4-bis[(trimethylsilyl)oxy]-2(3 H)-furanone, cis-dihydro-3,4-bis[(trimethylsilyl)oxy]-2(3H)-furanone, 2-C-methyl-2,3,5-tris-O-(trimethylsilyl)-D-ribonic acid gamma-lactone, 3-deoxy-2,5,6-tris-O-(trimethylsilyl)-D-ribo-hexonic acid gamma-lactone, 2-deoxy-3,5-bis-O-(trimethylsilyl)-pentonic acid gamma-lactone, and 2,3,5-tris-O-(trimethylsilyl)-D-arabinonic acid gamma-lactone. The observed reduction in color and aroma in Maillard reactions performed under oxidative conditions may be attributed to the oxidation of reactive dicarbonyls into the corresponding carboxylic acids or their corresponding lactones.

Simulating the detailed chemical composition of secondary organic aerosol formed on a regional scale during the TORCH 2003 campaign in the southern UK

Abstract. Following on from the companion study (Johnson et al., 2006), a photochemical trajectory model (PTM) has been used to simulate the chemical composition of organic aerosol for selected events during the 2003 TORCH (Tropospheric Organic Chemistry Experiment) field campaign. The PTM incorporates the speciated emissions of 124 non-methane anthropogenic volatile organic compounds (VOC) and three representative biogenic VOC, a highly-detailed representation of the atmospheric degradation of these VOC, the emission of primary organic aerosol (POA) material and the formation of secondary organic aerosol (SOA) material. SOA formation was represented by the transfer of semi- and non-volatile oxidation products from the gas-phase to a condensed organic aerosol-phase, according to estimated thermodynamic equilibrium phase-partitioning characteristics for around 2000 reaction products. After significantly scaling all phase-partitioning coefficients, and assuming a persistent background organic aerosol (both required in order to match the observed organic aerosol loadings), the detailed chemical composition of the simulated SOA has been investigated in terms of intermediate oxygenated species in the Master Chemical Mechanism, version 3.1 (MCM v3.1). For the various case studies considered, 90% of the simulated SOA mass comprises between ca. 70 and 100 multifunctional oxygenated species derived, in varying amounts, from the photooxidation of VOC of anthropogenic and biogenic origin. The anthropogenic contribution is dominated by aromatic hydrocarbons and the biogenic contribution by α- and β-pinene (which also constitute surrogates for other emitted monoterpene species). Sensitivity in the simulated mass of SOA to changes in the emission rates of anthropogenic and biogenic VOC has also been investigated for 11 case study events, and the results have been compared to the detailed chemical composition data. The role of accretion chemistry in SOA formation, and its implications for the results of the present investigation, is discussed.

Modeling secondary organic aerosol formation from oxidation of α-pinene, β-pinene, and d-limonene

The biogenic species α-pinene, β-pinene, and d-limonene are among the most abundant monoterpenes emitted globally. They are also important precursors to secondary organic aerosol (SOA) formation in the atmosphere. This study involves the development of proposed oxidation mechanisms for these three species. Semi- and non-volatile oxidation products with the potential to lead to SOA formation are predicted explicitly. Simulation code that describes the gas-phase oxidation mechanisms including reactions that lead to ozone (O 3) formation is coupled to an equilibrium absorptive partitioning code. The coupled model is used to simulate both gas-phase chemistry and SOA formation associated with oxidation of these three species in chamber experiments involving single as well as multiple oxidants. For the partitioning model, required molecular properties of the oxidation products are taken from the literature or estimated based on structural characteristics. The predicted O 3 and SOA concentrations are typically within ±50% of measured values for most of the experiments except for the experiments with low initial hydrocarbon concentrations and the nitrate radical experiments with α-pinene. The developed model will be used to update a gas-phase chemical mechanism and a SOA formation module used in a three-dimensional air quality model.

Nanoparticle formation by ozonolysis of inducible plant volatiles

Abstract. We present the first laboratory experiments of aerosol formation from oxidation of volatile organic species emitted by living plants, a process which for half a century has been known to take place in the atmosphere. We have treated white cabbage plants with methyl jasmonate in order to induce the production of monoterpenes and certain less-volatile sesqui- and homoterpenes. Ozone was introduced into the growth chamber in which the plants were placed, and the subsequent aerosol formation and growth of aerosols were monitored by measuring the particle size distributions continuously during the experiments. Our observations show similar particle formation rates as in the atmosphere but much higher growth rates. The results indicate that the concentrations of nonvolatile oxidation products of plant released precursors needed to induce the nucleation are roughly an order-of-magnitude higher than their concentrations during atmospheric nucleation events. Our results therefore suggest that if oxidized organics are involved in atmospheric nucleation events, their role is to participate in the growth of pre-existing molecular clusters rather than to form such clusters through homogeneous or ion-induced nucleation.

Bioconversion of (+)-valencene in submerged cultures of the ascomycete Chaetomium globosum

Submerged cultures of the ascomycete Chaetomium globosum oxidised the exogenous sesquiterpene (+)-valencene to nootkatone via the stereoselective generation of alpha-nootkatol. Inhibition experiments suggested that the first introduction of oxygen, the rate-limiting step of the bioconversion, may have been catalysed by a cytochrome-P450-monooxygenase. However, nootkatone was not the final metabolite: further flavour-active and inactive, non-volatile oxidation products were identified. (+)-Valencene and the flavour-active mono-oxyfunctionalised transformation products, alpha-nootkatol, nootkatone, and valencene-11,12-epoxide accumulated preferably inside the fungal cells. Di- and poly-oxygenated products, such as nootkatone-11,12-epoxide, were found solely in the culture medium, indicating an active transport of these metabolites into the extracellular compartment during (+)-valencene detoxification. These metabolic properties may have contributed to the high tolerance of the fungus towards the exogenous hydrocarbon.

Adsorption and desorption reactions of bicyclic aromatic compounds at polycrystalline and Pt(111) studied by DEMS

The adsorption of naphthalene, tetraline and biphenyl at Pt(111), roughened Pt(111) and polycrystalline Pt electrodes was studied using differential electrochemical mass spectrometry (DEMS). From the amount of CO 2 evolved during oxidation of the adsorbate layers, coverages were estimated to be around 0.2 nmol cm −2 for all three molecules. However, in the case of naphthalene and tetraline, oxidation charges per CO 2 molecule are somewhat (20–30%) larger than expected theoretically, indicating that oxidation does not lead only to CO 2, but also to other, nonvolatile oxidation products. Adsorbed biphenyl can be largely desorbed at potentials in the hydrogen region and below as biphenyl itself from Pt(111) and as the completely hydrogenated product bicyclohexyl from a roughened Pt(111). Interestingly a usual polycrystalline electrode is much less active towards hydrogenation, leading to cyclohexylbenzene as the main desorption product. Less than half of the adsorbate formed from naphthalene or tetraline can be desorbed under the same conditions, again the Pt(111) surface being the least, and the roughened Pt(111) being the most active surface for complete hydrogenation.

Ultraviolet-induced degradation of Ziegler-Natta and metallocene catalyzed polyethylenes

The metallocene revolution has aroused a storm of interest and associated questions regarding the performance and durability of polyolefins. This new technology has impacted the additives used to stabilize and process polymers. In this work, Ziegler-Natta and metallocene polyethylene (PE) samples were exposed to natural weather conditions under high doses of ultraviolet radiation, high temperature, and increased humidity. Weather-induced degradation of the two sets of PEs was studied using gel permeation chromatography, mechanical properties testing, differential scanning calorimetry, and Fourier transform infrared spectroscopy. The gel permeation chromatography analysis indicated the change in molecular weight distribution and molecular weights of metallocene PE to be more stable than conventional Ziegler-Natta PE. The tensile properties of metallocene PE are known to have higher values than Ziegler-Natta PE. The former exhibited a lower drop rate in mechanical properties when exposed to natural weather. Formations of nonvolatile carbonyl oxidation products, which absorb in the infrared region with a maximum absorbance level at 1742 cm−1 were determined. This indicated a higher rate of photo-oxidative and thermal degradation of Ziegler-Natta PE as compared with metallocene PE. The ultraviolet stabilization of metallocene PE may require different doses and a new kind of stabilizer system that can impart a longer useful lifetime and are cost effective for PE used for outdoor purposes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1591–1596, 2000

Postcolumn chemiluminescence, ultraviolet and evaporative light-scattering detectors in high-performance liquid chromatographic determination of triacylglycerol oxidation products

Postcolumn chemiluminescence (CL), ultraviolet (UV) and evaporative light-scattering (ELS) detectors were compared in the HPLC of triacylglycerol (TAG) oxidation products. Polar lipid fractions from autoxidized TAG samples were first separated from non-polar material by solid-phase extraction and then analysed by RP-HPLC in combination with UV-CL and UV-ELS detectors. TAG hydroperoxides were detected with a CL detector, oxidation products containing conjugated diene structures with a UV detector and all non-volatile oxidation products with an ELS detector. More accurate characterization of the oxidation products was possible by combining the information from different detectors. For samples at early stages of oxidation, the CL and UV detectors were more suitable because of their better sensitivity and selectivity compared with the ELS detector.

Effect of nonvolatile oxidation products on sensory characteristics of frying oils

Effect of nonvolatile oxidation products on sensory characteristics of frying oils

Thermooxidative degradation of nitrile-butadiene rubber

Results are presented on: (a) the nonisothermal degradation of nitrile-butadiene rubber (NBR) from TG, DTG and DTA data; (b) the accelerated isothermal thermal degradation of NBR at 80°, 90° and 105° from the change in weight versus time data; (c) the accelerated isothermal thermal degradation of NBR at 80°, 90° and 105° from the change in relative elongation at break with time. The thermal analysis data showed that the following processes occur successively during the nonisothermal heating of NBR in air: (1) the volatilization of the plasticizer and other ingredients; (2) the exothermic absorption of oxygen to yield nonvolatile oxidation products; (3) the decomposition of these products or their further interaction with oxygen to form volatile products. The results obtained from the three kinds of measurements were correlated to give a realistic picture of the processes responsible for the changes in the mechanical properties of the material as a consequence of its heating.

Lymphatic absorption of nonvolatile oxidation products of heated oils in the rat.

The lymphatic absorption of nonvolatile oxidation products (NVOP) formed during heating of fats was studied. Heated colza or soybean oils or synthetic triglycerides containing a definite aromatic or alicyclic fatty acid were fed to thoracic duct-cannulated rats. Tritium-labeled triolein was added to each dietary fat, as an internal standard, in order to calculate the percentage of lymphatic absorption of the ingested NVOP. Results show that 4% of the total polymeric acids, 53% of the total oxidized monomeric acids and 96% of the total cyclic monomeric acids were recovered in the lymphatic lipids. Gas liquid and quantitative thin layer chromatography of these 3 classes indicated that, within a NVOP class, the various constituents did not present the same absorption rate. The lymphatic absorptions of individual oxidized monomers were between 25 and 93%. Concerning the polymer fraction, the lymphatic recoveries were 1% (nonpolar dimers), 6.8% (polar dimers) and 12% (polar oligomers). Aromatic acids were absorbed to a lesser degree (50-60%) than cyclohexenic acids (91-98%).

Low‐temperature dielectric spectrum of thermally oxidized polyethylene

AbstractThree loss peaks in the dielectric spectra of thermally oxidized polyethylene at temperatures below 50°K are each apparently associated with specific species of nonvolatile oxidation products involving hydrogen atoms. We report how each is influenced by room‐temperature rolling, heat treatment, isotopic substitution, and chemical attack. One, the Vincett‐Phillips peak, is susceptible to attack by Cu2+, Fe3+, and HI, and is attributed to a hydroperoxide species. Its rapid and easy determination has promise in the study of polyethylene oxidation. Carson's (higher‐frequency) peak is tentatively attributed to an alcohol species and a new (lower‐frequency higher‐temperature) peak is described but not yet attributed. A few additional observations are made on the loss peaks associated with antioxidants of the substituted phenol type, as reported by Thomas and King.