Interaction of phosphatidylcholine and α-tocopherol on the oxidation of sunflower oil and content changes of phosphatidylcholine and tocopherol in the emulsion under singlet oxygen

Abstract: Interaction of phosphatidylcholine (PC) and α‐tocopherol (α‐Toc) on the oxidation of oil in the emulsion consisting of sunflower oil and water under singlet oxygen at 25 °C was studied by determining peroxide value (PV) and conjugated dienoic acid (CDA) contents. Singlet oxygen was produced by chlorophyll b under 1700 lux. Single addition of PC or α‐Toc decreased the values of peroxides and CDAs of oil in the emulsion via singlet oxygen quenching. PC and α‐Toc showed simply additive interaction in decreasing the singlet oxygen oxidation of oil in the emulsion. α‐Toc was a physical quencher of singlet oxygen in the emulsion, but PC involved chemical quenching in the antioxidant action. Chlorophyll and PC contents were decreased in the emulsion under singlet oxygen, while α‐Toc was not. α‐Toc protected chlorophyll and PC from degradation, and was a more important component than PC in the oil oxidation under singlet oxygen in the emulsion.     

Effects of Fatty Acid Composition and β‐Carotene on the Chlorophyll Photosensitized Oxidation of W/O Emulsion Affected by Phosphatidylcholine

Abstract: Chlorophyll photosensitized oxidation of W/O emulsion consisting of oils with different fatty acid composition was studied and β‐carotene effects on the singlet oxygen oxidation affected by phosphatidylcholine were evaluated by determining peroxide value (PV) and conjugated dienoic acid (CDA) contents. An emulsion was composed of purified oil (sunflower, soybean, canola, or olive oil), water, and xanthan gum (50:50:0.35, w/w/w) with addition of phosphatidylcholine (0 or 250 ppm) and β‐carotene (0, 1, 5, or 10 ppm). PV and CDA content of oil in the emulsion were increased with time under chlorophyll photosensitized oxidation, and the oxidation rate was higher in the emulsion consisting of sunflower or soybean oil whose polyunsaturated fatty acids content was high compared to canola or olive oil. Addition of β‐carotene to the emulsion significantly decreased the oil oxidation under chlorophyll photosensitization, however, co‐addition of phosphatidylcholine decreased the antioxidant activity of β‐carotene, suggesting an antagonistic antioxidation between them. Practical Application: The results of this study can be applied to the area of emulsion foods such as salad dressing to have improved texture and stability by decreasing the oil oxidation and providing desirable color by use of β‐carotene with phosphatidylcholine as emulsifier.     

Effects of solubility characteristics of sensitiser and pH on the photooxidation of oil in tuna oil-added acidic O/W emulsions

The effects of sensitisers and pH on the oil oxidation of acidic O/W emulsions were studied under light by measuring hydroperoxide content and headspace oxygen consumption in the emulsions. The emulsions consisted of canola and tuna oil (2:1 w/w, 32%), diluted acetic acid (64%), egg yolk powder (4%), chlorophyll b or erythrosine (5 μM), and/or diazabicyclooctane (DABCO) or sodium azide (0.5 M). The emulsion pH values were 2.67, 3.68, and 6.27. Chlorophyll increased oil oxidation in the emulsion under light via singlet oxygen production while erythrosine did not. DABCO significantly decreased photooxidation of the oil containing chlorophyll, suggesting singlet oxygen involvement. However, sodium azide increased photooxidation of the oil containing chlorophyll possibly via azide radical production under acidic conditions. The oil photooxidation was higher in the emulsion containing chlorophyll at pH 6.27 than at pH 2.67 or 3.68, primarily by singlet oxygen and secondarily by free radicals produced from hydroperoxide decomposition.     

Effects of monoacylglycerols on the oil oxidation of acidic water/perilla oil emulsion under light in the presence of chlorophyll

Monoacylglycerol (MAG) effects on the oil photooxidation of an emulsion containing chlorophyll were studied. The emulsion consisted of equal weights of hexaneextracted perilla oil and 0.5% acetic acid, and 4 ppm chlorophyll b and MAG at 0, 1, or 1.5% were added. The oxidation was performed under 1,700 lx light at 25°C for 48 h. Singlet oxygen was involved in the oil oxidation of the emulsion containing chlorophyll under light. MAG protected chlorophyll and polyphenol compounds from degradation during the oxidation of the emulsion under light. MAG significantly decreased and decelerated headspace oxygen consumption and hydroperoxide production in the emulsion, and thus acted as antioxidant in photooxidation of the acidic water/perilla oil emulsion containing chlorophyll. Antioxidant activity of MAG in the photooxidation of the emulsion could be due to combined results of increased retention of polyphenols and decreased oxygen diffusion by forming a physical barrier.     

Effects of chlorophyll photosensitisation on the oxidative stability in oil-in-water emulsions

Effects of chlorophyll photosensitisation on the oxidative stability of oil-in-water (O/W) emulsions were determined by analysing headspace oxygen content, lipid hydroperoxides, and headspace volatiles. The roles of transition metals and singlet oxygen were tested by adding ethylenediaminetetraacetic acid (EDTA) and sodium azide, respectively. Emulsions with chlorophylls and visible light irradiation had significantly high lipid hydroperoxides and headspace volatiles and low headspace oxygen content (p < 0.05) after 32 h while samples without light irradiation did not show any significant changes (p > 0.05). Sodium azide did not show clear antioxidant capacities in O/W emulsion systems rather showed prooxidant properties at some concentration. Addition of EDTA, a metal chelator, accelerated the rates of lipid oxidation in a concentration dependent manner. EDTA may enhance the stability of chlorophylls in O/W emulsions and the resulting higher chlorophyll concentrations may generate more singlet oxygen thus accelerating the rates of lipid oxidation.     

Quenching Mechanism of β-Carotene on the Chlorophyll Sensitized Photooxidation of Soybean Oil

The effects of 0, 5, 10, and 20 ppm β-carotene on the oxidation of 0.033, 0.066, 0.165, 0.330, or 0.660M soybean oil in methylene chloride containing 4 ppm chlorophyll have been studied by measuring headspace oxygen depletion in gas-tight sample bottles during 24 hr of light storage. The oxygen depletion was measured by a thermal conductivity gas chromatograph. The rate of singlet oxygen formation in soybean oil by 4 ppm chlorophyll was 0.17 μmoles O₂/mL head-space during first 24 hr of storage. The quenching mechanism study of g-carotene on the chlorophyll sensitized photooxidation of soybean oil showed that g-carotene minimized the oxidation of soybean oil by quenching singlet oxygen. p-carotene did not quench chlorophy11.     

Evaluation of Antioxidant or Prooxidant Properties of Selected Amino Acids Using In Vitro Assays and in Oil‐in‐Water Emulsions Under Riboflavin Sensitization

The antioxidant properties of selected amino acids were tested using in vitro assays and oil‐in‐water (O/W) emulsions under riboflavin (RF) photosensitization. Headspace oxygen content, lipid hydroperoxides, and conjugated dienes were determined for the degree of oxidation. Riboflavin photosensitization was adapted as the oxidation driving force. In vitro assays showed that cysteine had the highest antioxidant properties followed by tryptophan and tyrosine. However, in O/W emulsions under RF photosensitization, tyrosine inhibited lipid oxidation whereas tryptophan acted as a prooxidant. Tryptophan accelerated the rates of oxidation in O/W emulsion without RF. The antioxidant properties of amino acids differed depending on the antioxidant determination methods, oxidation driving forces, and food matrices.     

Effects of Phosphatidylcholine and Phosphatidylethanolamine on the Photooxidation of Canola Oil

ABSTRACT:  Effects of chlorophyll b, phosphatidylcholine (PC), and phosphatidylethanolamine (PE) on the oxidation of canola oil under 1700 lux light at 10 °C were studied by determining the headspace oxygen depletion and peroxide value. Chlorophyll b increased the oil oxidation under light via production of singlet oxygen. PC and PE did not affect the headspace oxygen depletion and peroxide formation in the oil in the absence of chlorophyll b at 10 °C; however, they increased in the presence of chlorophyll, with higher effect of PC than PE. Chlorophyll was degraded during the oil photooxidation and PC and PE decreased its photodecomposition with higher protection by PC than PE. There was no effect of light or singlet oxygen on PC and PE during the oil photooxidation. The results clearly showed that PC and PE were prooxidants in the photooxidation of canola oil containing chlorophyll b by protecting it from photodecomposition, and thus PC and PE should be removed from the oil containing chlorophyll to improve the photooxidative stability.     

Contribution of minor compounds to the singlet oxygen-related photooxidation of olive and perilla oil blend

This study evaluated contribution of natural minor compounds including carotenoids, tocopherols, polyphenols, and phosphatidylcholine (PC) to the stability of chlorophyll sensitized oxidation of olive and perilla oil blend under 2,500 lx light at 25°C for 48 h. The oxidation of the oil blend was evaluated by headspace oxygen consumption and peroxide values (POV). Minor compounds were also monitored. The headspace oxygen consumption and POV of the oil blend were increased with oxidation time; however, fatty acid composition was not significantly changed. Carotenoids, tocopherols, polyphenols, and PC were degraded during the oil oxidation, which was closely related with their singlet oxygen quenching. Correlations of the oil oxidation were higher with contents of carotenoids and PC (r ²>0.93) than with those of tocopherols or polyphenols, suggesting high contribution of carotenoids and PC to decreasing singlet oxygen-related photooxidation of olive and perilla oil blend.     

Effects of unrefined vegetable oil addition on the flavor acceptability and oil oxidation of tuna oil enriched emulsion under singlet oxygen

Food Science and Biotechnology - Addition effects of unrefined vegetable oil on the fishy flavor and singlet oxygen oxidation of tuna oil enriched O/W emulsion were studied by sensory evaluation...     

Singlet Oxygen Quenching Activities of Various Fruit and Vegetable Juices and Protective Effects of Apple and Pear Juices against Hematolysis and Protein Oxidation Induced by Methylene Blue Photosensitization

ABSTRACT:  Effects of various fruit and vegetable juices on rubrene oxidation induced by a chemical source of singlet oxygen in a microemulsion system have been studied. The singlet oxygen quenching activities of fruit and vegetable juices were greatly different with different juices. The apple and pear juices exhibited the highest antioxidative activity among the tested juices in singlet oxygen–induced rubrene oxidation, showing 56.69% and 59.34% inhibition, respectively. The grape, kumquat, red cabbage, and spinach juices also showed relatively strong antioxidative activity against singlet oxygen–induced rubrene oxidation. Lemon juice showed the least activity, resulting in 0.63% inhibition of rubrene oxidation. The singlet oxygen quenching activities of 1 mL of apple and pear juices were equivalent to 33.97 and 34.64 mg ascorbate, respectively. Singlet oxygen quenching activities of juices had very low correlation with both ABTS radical scavenging activity ( R ²= 0.11) and total phenolic contents ( R ² < 0.1). However, a high correlation ( R ²= 0.66) was found between the ABTS radical scavenging activities and total phenolic contents of juices. The apple and pear juices also significantly inhibited both erythrocyte lysis and protein oxidation induced by fluorescence light illumination in the presence of methylene blue. Electron spin resonance (ESR) spectroscopy data showed that the protective activities of these juices against biological damages induced by photodynamic ways were, to at least some extent, due to their singlet oxygen quenching abilities. This represents first report on the singlet oxygen quenching activities of the apple and pear juices, and their protective activities against photodynamically induced biological damages.     

Oxidation Stability of O/W Emulsion Prepared with Linolenic Acid Enriched Diacylglycerol

The sn‐1,3‐regiospecific Rhizomucor miehei lipase (Lipozyme RM IM) was employed to produce structured diacylglycerol (SL‐DAG), which contained 67.3 mol% DAG with 27.2 area% of C18:3. To investigate the oxidative stability of the SL‐DAG in emulsion form, 5% oil‐in‐water (O/W) emulsions were prepared with 200 and 400 ppm sinapic acid. It was shown that the hydroperoxide values of the control (without any antioxidant) was the highest (117.7 meq/L) on day 43 of storage and thereafter the value decreased. However, the emulsions with 200 and 400 ppm sinapic acid resulted in slow oxidation degree until day 64 of storage (30.3 and 7.3 meq/L, respectively). Aldehyde measurements for the 200 ppm sinapic acid emulsion (12.8 mmol/mol) and the 400 ppm sinapic acid emulsion (7.5 mmol/mol) also showed better oxidative stability than that for the 200 ppm catechin emulsion (27.4 mmol/mol) and the control (52.7 mmol/mol). Although the SL‐DAG in the emulsions contains high levels of polyunsaturated fatty acids, the degree of oxidation in the emulsions can be reduced when sinapic acid is used as an antioxidant.     

QUENCHING MECHANISMS AND KINETICS OF CAROTENOIDS IN RIBOFLAVIN PHOTOSENSITIZED SINGLET OXYGEN OXIDATION OF VITAMIN D2

The oxidation of vitamin D₂ in a solution of 12% water, 88% acetone and 15 ppm ribqflavin under light or dark was studied by measuring the headspace oxygen. Ribofiavin accelerated the oxidation of vitamin D₂ by singlet oxygen under light, but did not affect vitamin D₂ oxidation under dark. Quenching mechanisms and kinetics within the range of 0–20 ppm β‐cawtene or fucoxanthin and with 0–80 ppm retinyl acetate or retinol on 15 ppm riboflavin photosensitized singlet oxygen oxidation of vitamin D₂ were also studied. The rate of singlet oxygen formation by 15 ppm riboflavin was 1.78 umole oxygen/mL headspace‐hour. The reaction rate constant of vitamin D₂ with singlet oxygen was 2.2 times 10⁷ M^?1A s^?1. The carotenoids minimized the oxidation of vitamin D₂ by quenching singlet oxygen. The total quenching rate constants of retinol, retinyl acetate, jucoxanthin and ft‐carotene were in the order of 1.22 times 10⁸, 5.98 times 10⁸, 1.78 times 10⁹ and 5.00 times 10⁹M^?1. s^?1 respectively, which suggests that as the number of double bonds of carotenoids increases, the quenching rate constant ofcarotenoid increases.     

Effects of catechins and green tea extract on the photosensitized singlet oxygen oxidation of linoleic acid in a model system as compared with α-tocopherol

Effects of catechins and green tea extract (GTE) on the photosensitized singlet oxygen oxidation of linoleic acid were studied. Epigallocatechin gallate (EGCG) showed the highest antioxidant activity, followed by gallocatechin gallate, epigallocatechin, and epicatechin in a decreasing order. α-Tocopherol showed strong antioxidative activity at the initial oxidation stage, but its antioxidative property rapidly decreased with illumination time. EGCG showed significantly stronger antioxidative activity than α-tocopherol at the later oxidation stage (p<0.05) due to the higher stability of EGCG. Unlike α-tocopherol, GTE possessed strong antioxidative activity even at the later oxidation stage. Overall, GTE was a better antioxidant than α-tocopherol for the protection of linoleic acid from singlet oxygen oxidation. Electron spin resonance (ESR) spectroscopy and visible-spectroscopic data showed unambiguous evidences that the protective activity of GTE against the photosensitized oxidation of linoleic acid was due to the singlet oxygen quenching mechanism.     

Oxidative stability of oil-in-water emulsions with α-tocopherol,charged emulsifier,and different oxidative stress

α-Tocopherol is known to show different activity depending on the concentration and food matrix. Effects of α-tocopherol at the concentrations of 0, 0.1, 0.5, and 1.0 mM were determined in oil-in-water (O/W) emulsions containing anionic, neutral, and cationic emulsifiers under different types of oxidative stress including riboflavin photosensitization, photooxidation, and autoxidation. Headspace oxygen depletion, lipid hydroperoxides, and conjugated dienes were analyzed to determine the oxidative stability of O/W emulsions. α-Tocopherol served as an antioxidant in O/W emulsion with a cationic emulsifier irrespective of oxidative stress. α-Tocopherol acted as an antioxidant in O/W emulsion with a neutral emulsifier at riboflavin photosensitization while a prooxidant at photooxidation. However, in samples with an anionic emulsifier, α-tocopherol activity differed from the concentration and types of oxidative stress. Therefore, cationic transition metals or reactive oxygen species generated from RF photosensitization could play key roles of α-tocopherol in O/W emulsion.     

抗氧化剂茶多酚反相微乳液的制备

制备茶多酚在亚油酸-水-乙醇体系的反相微乳液,使其成功地添加到亚油酸中,并研究该微乳液体系的相形为、电导率、粒径分布、流变及抗氧化能力等特性。结果表明：当油相亚油酸质量分数大于24% 时,可形成油包水型微乳液。该微乳液体系粒径均一,表现为剪切变稀的流变特征,且具有温度触变性。过氧化值测试结果表明：相比空白微乳液,水相添加0.01 g/mL茶多酚对亚油酸氧化的抑制率为68.32%,添加0.1 g/mL茶多酚对亚油酸氧化的抑制率为92.42%。     

Effects of lipophilic and hydrophilic antioxidants in oil-in-water emulsions under chlorophyll photosensitization

Antioxidative or prooxidative properties of α-tocopherol, Trolox, ascorbic acid, and ascorbyl-palmitate at the concentration of 0.1 and 1.0 mM were determined in oil-in-water (O/W) emulsions under chlorophyll photosensitization. Headspace oxygen depletion, lipid hydroperoxides, and headspace volatile analyses were conducted to determine the oxidative stability of O/W emulsions. For 32 h visible light irradiation, depleted headspace oxygen content in O/W emulsions were in the order of samples containing Trolox, ascorbic acid, ascorbyl palmitate, α-tocopherol, without antioxidants under light, and samples in the dark, which implies that all the added compounds acted prooxidant. These prooxidative properties of added compounds can be observed in the results of lipid hydroperoxides and headspace volatiles. Samples containing ascorbic acid and ascorbyl palmitate retained higher chlorophyll content than those containing Trolox up to 16 h. Increases of concentration of Trolox, ascorbic acid, and ascorbyl palmitate from 0.1 to 1.0 mM increased the lipid oxidation products whereas α-tocopherol decreased the degree of lipid oxidation implying α-tocopherol may not share the same prooxidant mechanisms compared to other compounds in chlorophyll sensitized O/W emulsions.     

Direct Spectroscopic Observation of Singlet Oxygen Quenching and Kinetic Studies of Physical and Chemical Singlet Oxygen Quenching Rate Constants of Synthetic Antioxidants (BHA,BHT, and TBHQ) in Methanol

Abstract: Singlet oxygen quenching by synthetic antioxidants (BHA, BHT, and TBHQ) was directly observed by spectroscopic monitoring of luminescence at 1268 nm. The luminescence data showed unambiguous evidence of singlet oxygen quenching by synthetic phenolic antioxidants with the highest activity for TBHQ, followed by BHA and BHT. The protective activities of these synthetic antioxidants on α-terpinene oxidation with chemically-induced singlet oxygen under dark further confirmed their singlet oxygen quenching abilities. Total singlet oxygen quenching rate constants (k_r + k_q) of BHA, BHT, and TBHQ were determined in a system containing α-terpinene (as a singlet oxygen trap) and methylene blue (as a sensitizer) during light irradiation, and the values were 5.14 × 10⁷, 3.41 × 10⁶, and 1.99 × 10⁸ M⁻¹s⁻¹, respectively. After the k_r value of α-terpinene was first determined, the k_r values of the synthetic antioxidants were calculated by measuring their relative reaction rates with singlet oxygen to that of α-terpinene under the identical conditions. The k_r values of the BHA, BHT, and TBHQ were 3.90 × 10⁵, 1.23 × 10⁵, and 2.93 × 10⁶, M⁻¹s⁻¹. The percent partition of chemical quenching over total singlet oxygen quenching (k_r × 100)/(k_r + k_q) for BHA, BHT, and TBHQ were 0.76%, 3.61%, and 1.47%, respectively. The results showed that the synthetic antioxidants quench singlet oxygen almost exclusively through the mechanism of physical quenching. This represents the first report on the singlet oxygen quenching mechanism of these synthetic antioxidants. Practical Application: The synthetic antioxidants, especially TBHQ, have been found to have a strong singlet oxygen quenching ability. This article also clearly showed that singlet oxygen quenching by synthetic antioxidants was mainly by the physical quenching mechanism. The results suggested that these synthetic antioxidants, especially TBHQ, could be used practically for the protection of the food components such as edible oils and vitamins against singlet oxygen induced oxidations without significant losses of antioxidant activity during storage under light.     

Mechanisms of lipid oxidation in water-in-oil emulsions and oxidomics-guided discovery of targeted protective approaches

Lipid oxidation is an inevitable event during the processing, storage, and even consumption of lipid-containing food, which may cause adverse effects on both food quality and human health. Water-in-oil (W/O) food emulsions contain a high content of lipids and small water droplets, which renders them vulnerable to lipid oxidation. The present review provides comprehensive insights into the lipid oxidation of W/O food emulsions. The key influential factors of lipid oxidation in W/O food emulsions are presented systematically. To better interpret the specific mechanisms of lipid oxidation in W/O food emulsions, a comprehensive detection method, oxidative lipidomics (oxidomics), is proposed to identify novel markers, which not only tracks the chemical molecules but also considers the changes in supramolecular properties, sensory properties, and nutritional value. The microstructure of emulsions, components from both phases, emulsifiers, pH, temperature, and light should be taken into account to identify specific oxidation markers. A correlation of these novel oxidation markers with the shelf life, the organoleptic properties, and the nutritional value of W/O food emulsions should be applied to develop targeted protective approaches for limiting lipid oxidation. Accordingly, the processing parameters, the application of antioxidants and emulsifiers, as well as packing and storage conditions can be optimized to develop W/O emulsions with improved oxidative stability. This review may help in emphasizing the future research priorities of investigating the mechanisms of lipid oxidation in W/O emulsion by oxidomics, leading to practical solutions for the food industry to prevent oxidative rancidity in W/O food emulsions.     

Effects of Green Tea Extract and α‐Tocopherol on the Lipid Oxidation Rate of Omega‐3 Oils,Incorporated into Table Spreads,Prepared using Multiple Emulsion Technology

Abstract: This study examined the effectiveness of fat and water soluble antioxidants on the oxidative stability of omega (ω)‐3 rich table spreads, produced using novel multiple emulsion technology. Table spreads were produced by dispersing an oil‐in‐water (O/W) emulsion (500 g/kg 85 camelina/15 fish oil blend) in a hardstock/rapeseed oil blend, using sodium caseinate and polyglycerol polyricinoleate as emulsifiers. The O/W and oil‐in‐water‐in‐oil (O/W/O) emulsions contained either a water soluble antioxidant (green tea extract [GTE]), an oil soluble antioxidant (α‐Tocopherol), or both. Spreads containing α‐Tocopherol had the highest lipid hydroperoxide values, whereas spreads containing GTE had the lowest (P < 0.05), during storage at 5 °C, while p‐Anisidine values did not differ significantly. Particle size was generally unaffected by antioxidant type (P < 0.05). Double emulsion (O/W/O) structures were clearly seen in confocal images of the spreads. By the end of storage, none of the spreads had significantly different G′ values. Firmness (Newtons) of all spreads generally increased during storage (P < 0.05). Practical Application: Lipid oxidation is a major problem in omega‐3 rich oils, and can cause off‐odors and off‐flavors. Double emulsion technology was used to produce omega‐3 enriched spreads (O/W/O emulsions), wherein the omega‐3 oil was incorporated into the inner oil phase, to protect it from lipid oxidation. Antioxidants were added to further protect the spreads by reducing lipid oxidation. Spreads produced had good oxidative stability and possessed functional (omega‐3 addition) properties.