Chemistry and Reactions of Reactive Oxygen Species in Foods

ABSTRACT: Reactive oxygen species (ROS) is formed enzymatically, chemically, photochemically, and by irradiation of food. It is also formed by the decomposition and the inter-reactions of ROS. The hydroxy radical is the most reactive ROS and then followed by singlet oxygen. Reactions of ROS with food components produce undesirable volatile compounds and carcinogens, destroy essential nutrients, and change the functionalities of proteins, lipids, and carbohydrates. Lipid oxidation by ROS produces low-molecular-weight volatile aldehydes, alcohols, and hydrocarbons. ROS causes crosslink or cleavage of proteins. ROS produces low-molecular-weight carbonyl compounds from carbohydrates. Vitamins are easily oxidized by ROS, especially singlet oxygen. The singlet oxygen reaction rate was the highest in β-carotene followed by tocopherol, riboflavin, vitamin D, and ascorbic acid.     

Chemistry and reactions of reactive oxygen species in foods

Reactive oxygen species (ROS) are formed enzymatically, chemically, photochemically, and by irradiation of food. They are also formed by the decomposition and the inter-reactions of ROS. Hydroxy radical is the most reactive ROS, followed by singlet oxygen. Reactions of ROS with food components produce undesirable volatile compounds and carcinogens, destroy essential nutrients, and change the functionalities of proteins, lipids, and carbohydrates. Lipid oxidation by ROS produces low molecular volatile aldehydes, alcohols, and hydrocarbons. ROS causes crosslink or cleavage of proteins and produces low molecular carbonyls from carbohydrates. Vitamins are easily oxidized by ROS, especially singlet oxygen. The singlet oxygen reaction rate was the highest in ss-carotene, followed by tocopherol, riboflavin, vitamin D, and ascorbic acid.     

Activated oxygen species and oxidation of food constituents.

Activated oxygen species which may be important in initiating oxidative changes in foods include singlet oxygen, hydroxyl radical, ozone, superoxide anion (perhydroxyl radical at low pH), and hydrogen peroxide. Chemical and enzymic reactions known to occur in biological materials can generate singlet oxygen, hydroxyl radical, superoxide anion, and hydrogen peroxide. Ozone is primarily a product of photoreactions in polluted air. Reactions involving singlet oxygen, hydroxyl radical, and ozone with food constituents can ultimately yield peroxides which decompose to initiate oxidative chain reactions. Superoxide anion and hydrogen peroxide are relatively inert toward organic molecules but can decompose to produce the more reactive singlet oxygen and hydroxyl radical. Inhibition of reactions initiated by reactive oxygen species in foods should be very important in preserving the oxidative stability of foods. The generation, detection, measurement, reaction, and inhibition of reactions of active oxygen species are surveyed in this review.     

Activated oxygen species and oxidation of food constituents

Activated oxygen species which may be important in initiating oxidative changes in foods include singlet oxygen, hydroxyl radical, ozone, superoxide anion (perhydroxyl radical at low pH), and hydrogen peroxide. Chemical and enzymic reactions known to occur in biological materials can generate singlet oxygen, hydroxyl radical, superoxide anion, and hydrogen peroxide. Ozone is primarily a product of photoreactions in polluted air. Reactions involving singlet oxygen, hydroxyl radical, and ozone with food constituents can ultimately yield peroxides which decompose to initiate oxidative chain reactions. Superoxide anion and hydrogen peroxide are relatively inert toward organic molecules but can decompose to produce the more reactive singlet oxygen and hydroxyl radical. Inhibition of reactions initiated by reactive oxygen species in foods should be very important in preserving the oxidative stability of foods. The generation, detection, measurement, reaction, and inhibition of reactions of active oxygen species are surveyed in this review.     

Mechanisms of photochemistry and reactive oxygen production by fullerene suspensions in water

Buckminsterfullerene (C60) is a known photosensitizer that produces reactive oxygen species (ROS) in the presence of light; however, its properties in aqueous environments are still not well understood or modeled. In this study, production of both singlet oxygen and superoxide by UV photosensitization of colloidal aggregates of C60 in water was measured by two distinct methods: electron paramagnetic resonance (EPR) with a spin trapping compound, and spectrophotometric detection of the reduced form of the tetrazolium compound XTT. Both singlet oxygen and superoxide were generated by fullerol suspensions while neither was detected in the aqu/nC60 suspensions. A mechanistic framework for photosensitization that takes into account differences in C60 aggregate structure in water is proposed to explain these results. While theory developed for single molecules suggests that alterations to the C60 cage should reduce the quantum yield for the triplet state and associated ROS production, the failure to detect ROS production by aqu/nC60 is explained in part by a more dense aggregate structure compared with the hydroxylated C60.     

Effects of Riboflavin Photosensitized Oxidation on the Volatile Compounds of Soymilk

ABSTRACT: Soymilks with or without added riboflavin in serum bottles were stored under light or in dark at 20 °C. The headspace oxygen and volatile compounds were determined by gas chromatography. Riboflavin had significant effects on the headspace oxygen depletion and volatile compounds formation in soymilk under light ( P < 0.05). Riboflavin did not have significant effects on the formation of volatile compounds and the depletion of headspace oxygen in dark ( P > 0.05). The volatile compounds increased under light, but not in dark as the added riboflavin increased. Storage temperature at 4 °C or 20 °C did not have significant difference in the effect of riboflavin on the headspace oxygen depletion in soymilk under light. Hexanal, an important beany flavor compound, was identified as the major volatile compound in the riboflavin photosensitized soymilk. Singlet oxygen oxidation was involved in the formation of volatile compounds in soymilk under light. Hexanal could be formed by singlet oxygen oxidation. Ascorbic acid, a quencher for singlet oxygen and the excited triplet sensitizer, significantly inhibited the formation of hexanal and total volatiles in soymilk under light.     

Photosensitized destruction of Chlorella vulgaris by Methylene Blue or Nuclear Fast Red combined with hydrogen peroxide under visible light irradiation

A considerable number of investigations have started to elucidate the essential roles biological agents play in the biodeterioration of stone. Chemical biocides are becoming increasingly banned because of the environmental and health hazards associated with these toxic substances. The present study reports the photodynamic effect of Methylene Blue (MB) and Nuclear Fast Red (NFR) in the presence of hydrogen peroxide (H2O2) on the destruction of the algae Chlorella vulgaris (C. vulgaris) under irradiation with visible light. Illumination of C. vulgaris in the presence of MB or NFR combined with H2O2 results in the decomposition of both the algal species and the photosensitizer. The photodynamic effect was investigated under aerobic and anaerobic conditions. Differences in mechanism type are reported and are dependent on both the presence and the absence of oxygen. The behavior of each photosensitizer leads to a Type II mechanism and a Type I/Type II combination for MB and NFR, respectively, being concluded. This novel combination could be effective for the remediation of biofilm-colonized stone surfaces.     

食品中脂类物质的1O2氧化及控制方法

脂类食品中存在的天然色素通常是潜在的光敏剂,可以通过光敏反应Type II途径将基态氧激发并转变为单线态氧（singlet oxygen,1O2）。1O2是一种亲电性、非自由基的激发态氧分子,具有活化能低、反应活性高的特点,可以快速引发脂类物质氧化,并最终导致其氧化劣变。本文查阅并分析了国内外本领域的最新研究成果,对脂类食品中1O2的形成途径、光敏氧化机理及甘油三酯和植物甾醇等常见脂类物质的光敏氧化进行了深入阐述,并从光敏剂和三线态氧的脱除与控制、1O2淬灭、光源选择等方面总结了食品中脂类物质光敏氧化控制的最新研究进展,以期为深入研究食品中脂类物质的光敏氧化及抑制技术提供理论依据。     

Patterning cultured cells by visible light illumination with photosensitizers

We showed that PC12 cells and 3T3 cells cultured in dishes were killed by illumination with visible white light from a halogen lamp at 7 x 10(4) lx for 5 min in the presence of either 10 microM hematoporphyrin or 2 microM methylene blue as a photosensitizer. This simple technique, based on the photodynamic reaction via generation of reactive oxygen species can be applicable for patterning cultured cells.     

Quenching Mechanisms and Kinetics of α-Tocopherol and β-Carotene on the Photosensitizing Effect of Synthetic Food Colorant FD&C Red No. 3

ABSTRACT: Effects of FD&C Red No. 40, Red No. 3, Yellow No. 5, Yellow No. 6, Green No. 3, Blue No. 1 and Blue No. 2 on 0.03M soybean oil oxidation in acetone at 25 °C under light were studied by measuring headspace oxygen depletion. As Red No. 3 increased from 0 to 5, 20, 100 and 200 ppm, the headspace oxygen was reduced by 2 to 70, 73, 77 and 77%, respectively, for 4 h. Only Red No. 3 acted as a photosensitizer to produce singlet oxygen in the oil. The quenching rates of α-tocopherol and β-carotene for the singlet oxygen by Red No.3 were 4.1 × 10⁷ M⁻¹s⁻¹ and 7.3 × 10⁹ M⁻¹s⁻¹, respectively. When β-carotene was below 1.86 × 10⁻⁶ M, β-carotene quenched singlet oxygen, but it quenched both singlet oxygen and Red No. 3 at or above 3.72 × 10⁻⁶ M. However, α-tocopherol quenched singlet oxygen only.     

冷等离子体技术对食品组分的影响及其作用机制

冷等离子体作为一种新型的非热加工技术,因其具有安全、绿色、能耗低等优点,在食品加工领域受到广泛关注。冷等离子体使用的气体在电离过程中产生的紫外线、活性物质（如活性氧、活性氮、羟自由基和离子）等会通过辐射/修饰作用使生物大分子发生刻蚀及交联,或对食品组分（脂质、蛋白质、淀粉等）的表面结构和官能团进行修饰,使组分结构发生变化,从而影响食品的品质、功能特性等。本文综述了冷等离子体作用对食品主要组分（蛋白质、脂质、淀粉）、维生素和多酚的影响及其可能的作用机制,并讨论了该技术存在的问题和未来发展的方向,以期为冷等离子体在食品工业的应用提供参考。     

Stability and Photochemistry of Vitamin D2 in Model System

Oxidation of vitamin D₂ in a model system of 12% water and 88% acetone in the presence of 15 ppm riboflavin under light and dark was studied by measuring the depleted headspace oxygen. Riboflavin accelerated the oxidation of vitamin D₂ by singlet oxygen under light, but did not affect the vitamin D₂ oxidation under dark. The effect of 0 and 15 ppm riboflavin on the stability of vitamin D₂ during storage at 25 and 60°C was studied by measuring the contents of vitamin D₂ during 48h. Results indicated that photosensitized singlet oxygen oxidation of vitamin D₂ under light was temperature-independent, and triplet oxygen oxidation of vitamin D₂ both under light and in the dark was temperature-dependent.     

Wavelength-tailored light-emitting diodes reduce damage to sensory properties of light-exposed milk

Photooxidation has long been affecting nutrient and sensory quality of fluid milk. Light oxidation starts from the activation of photosensitive compounds, followed by generation of singlet oxygen that reacts with vitamins, proteins, and lipids in milk. It is hypothesized that wavelength-tailored light schemes possessing spectral properties capable of avoiding excitation maxima of common photosensitizers in milk could slow the chemical degradation of light-exposed milk and thus preserve consumer acceptability. A series of 6 consumer tests with sample sizes from 95 to 119 participants tested hedonic responses to fluid milk samples exposed to light of varying wavelength spectra. For milk in clear plastic bottles (polyethylene terephthalate or high-density polyethylene), consumer panels generally liked milk exposed to light-emitting diodes eliminating wavelengths below 520 or 560 nm more than standard white light, or those eliminating other wavelength bands. This higher degree of liking coincided with panelists citing fewer off-flavors or aromas from these samples. Taken together, these observations suggest such light schemes can protect milk from light damage to some extent. Wavelength-tailored light schemes used in this study did not offer effective protection for milk in glass bottles. Dissolved oxygen, color, riboflavin loss, and hexanal content were instrumentally evaluated, but results failed to indicate significant signatures of light damage in milk compared with sensory measures. The appearance of milk bottles illuminated by the slightly greenish or yellowish light were less liked by consumers, suggesting further efforts on consumer education may be necessary if these light schemes were to be installed in retail dairy coolers.     

核黄素介导的光动力技术的研究进展

核黄素是一类B族维生素,它少部分存在于人体内,广泛的存在于食物中。核黄素对于人体的新生代谢以及生长发育具有良好的促进作用。光动力技术是一种新型、环保、高效的控制手段,光敏剂是光动力技术的关键要素,以核黄素光敏剂介导的光动力技术在肿瘤、皮肤病、病虫害等领域均已有广泛的应用。然而,大量研究表明核黄素的光敏特性对人体健康及食品稳定性仍存在一定的影响。因此,本文综述了核黄素的功能特性,并总结了核黄素作为光敏剂介导的光动力技术在治疗疾病与控制病虫害等过程中的应用,以及对人体健康及食品稳定性产生的可能影响,旨在为其进一步开发提供参考依据。     

Reactive Oxygen Species,Aging, and Antioxidative Nutraceuticals

The important roles of reactive oxygen species in diseases related to aging and the necessity and benefits of antioxidative nutraceuticals in the prevention of diseases and promotion of healthy aging have been extensively reported in recent years. Oxygen is an essential component of living organisms. The generation of reactive oxygen species such as superoxide anion, hydrogen peroxide, hydroxyl radicals, and singlet oxygen is inevitable in aerobic metabolism of the body. Reactive oxygen species cause lipid oxidation, protein oxidation, DNA strand break and base modification, and modulation of gene expression. In the past several years, unprecedented progress has been made in the recognition and understanding of roles of reactive oxygen species in many diseases. These include atherosclerosis, vasospasms, cancers, trauma, stroke, asthma, hyperoxia, arthritis, heart attack, age pigments, dermatitis, cataractogenesis, retinal damage, hepatitis, liver injury, and periodontis, which are age‐related. The body protects itself from the potential damages of reactive oxygen species. Its first line of defense is superoxide dismutases, glutathione peroxidases, and catalase. Scientists have indicated that antioxidant nutraceuticals supplied from daily diets quench the reactive oxygen species or are required as cofactors for antioxidant enzymes. Nutraceuticals play significant roles in the prevention of a number of age‐related diseases and are essential for healthy aging. Epidemiological studies also reported the relevance of antioxidative nutraceuticals to health issues and the prevention of age‐related diseases. Health‐conscious consumers have made antioxidative nutraceuticals the leading trend in the food industry worldwide in recent years.     

光动力杀菌机制及在食品应用中的优势与不足

有害微生物是引起食品安全问题的重要原因之一。广谱抗生素的使用虽然有效地抑制了有害微生物,但耐药性导致其无法得到有效控制,这加重了食品安全隐患,同时造成更严重的经济损失。因此,迫切需要开发其它替代杀菌技术,这也是保护食品安全的重要挑战。光动力杀菌技术是通过光激发光敏剂后,产生的活性氧物质破坏致病菌的形态结构、细胞膜、核酸和蛋白质等,同时触发多种细菌难以抵消的死亡机制,此机制不易造成细菌耐受性。光动力杀菌技术杀菌效果佳,但此杀菌技术对食品营养成分及品质的影响关注较少,限制了其在食品领域中的推广和应用。本文系统综述了光动力杀菌技术的杀菌机制及影响因素,并且介绍了光动力杀菌在食品中的研究应用,就杀菌技术在食品应用中的优势和不足提出新见解,以期为我国光动力杀菌技术的工业化应用提供参考。     

Fullerol-sensitized production of reactive oxygen species in aqueous solution

The relative production rate of reactive oxygen in aqueous solution sensitized by fullerol (a polyhydroxylated, water-soluble form of the fullerene C60) was measured and compared to known reactive oxygen sensitizers using an oxygen consumption method. The solutions were irradiated by polychromatic visible and ultraviolet light. Reactive oxygen species were generated under both visible and ultraviolet light sources. The greatest rates of oxygen consumption were observed at acidic pH. We show for the first time evidence of both singlet oxygen and superoxide production by fullerol under both UV and polychromatic light sources.     

Effects of Chlorophyll and β-Carotene on the Oxidation Stability of Olive Oil

Virgin olive oil was purified by silicic acid column chromatography to remove non-triglyceride components. The effects of chlorophyll and β-carotene on the oxidation stability of purified olive oil were studied by a combination of measuring peroxide value and oxygen disappearance in the headspace of sample bottles by gas chromatography. Chlorophyll in the purified oil acted as a photosensitizer for singlet oxygen formation under light. β-carotene minimized lipid oxidation of purified oil under light storage by its light-filtering effect. Experiments clearly suggested that singlet oxygen was mainly responsible for the photooxidation of the oil containing chlorophyll.     

Singlet Oxygen Quenching Effects of Phosphatidylcholine in Emulsion Containing Sunflower Oil

ABSTRACT:  Effects of phosphatidylcholine (PC) on the oxidation of oil by singlet oxygen in a W/O microemulsion and an emulsion food model containing tocopherol-stripped sunflower oil (TSSO) have been studied. The W/O microemulsion consisted of methylene chloride, butanol, and sodium dodecyl sulfate with PC (0, 250, 1000 ppm) and TSSO (0, 3.3, 16.5, 33 mg/mL). Production of singlet oxygen in the microemulsion was done chemically with hydrogen peroxide in the presence of sodium molybdate, and indirectly evaluated by rubrene oxidation at A₅₂₉. The emulsion food model consisted of TSSO, distilled water, and xanthan gum with addition of 250 ppm PC and 4 ppm chlorophyll b, and was placed at 25 °C under fluorescent lights (1700 lux) for 24 h. The oxidation of TSSO was determined by thin-layer chromatography and values of conjugated dienoic acid (CDA) and peroxides (POV). PC significantly decreased the oxidation of rubrene and TSSO in the W/O microemulsion, but its content was decreased to approximately one-half by a 20-min reaction, indicating its degradation. This clearly shows that PC acted as an antioxidant via chemical quenching of singlet oxygen in the W/O microemulsion. A possible synergism between PC and TSSO was observed in singlet oxygen quenching in the microemulsion. PC also significantly decreased the chlorophyll-photosensitized oxidation of TSSO in the emulsion food model, possibly by singlet oxygen quenching. This study clearly suggested that PC be used as an antioxidant to improve the lipid oxidative stability of an emulsion food containing chlorophyll under light.