Oxidative Stability in Oil‐in‐Water Emulsions with Quercetin or Rutin Under Iron Catalysis or Riboflavin Photosensitization

The effects of quercetin and rutin on the oxidative stability of oil‐in‐water (O/W) emulsions were tested under riboflavin (RF) photosensitization in the presence or absence of FeCl₂. The degree of oxidation in O/W emulsions was determined by headspace oxygen content, conjugated dienes, and lipid hydroperoxides. Quercetin chelated more metal than did rutin in iron catalyzed O/W emulsions. Generally, 0.1 mM quercetin and rutin was oxidative while 0.5 and 1.0 mM quercetin and rutin was antioxidative in O/W emulsions under RF photosensitization. Depending on the analysis method, the antioxidants had different strengths. The antioxidative or oxidative properties of quercetin and rutin vary in O/W emulsions and depend the quercetin and rutin concentrations and oxidative forces like transition metals, RF photosensitization, or a combination thereof.     

Effect of proanthocyanidin-rich extracts from Chinese quince (Chaenomeles sinensis) fruit on the physical and oxidative stability of sunflower oil-in-water emulsions

To evaluate the effect of Chinese quince proanthocyanidins (PAs) on the physical and oxidative stability of sunflower oil-in-water (O/W) emulsions during storage, three proanthocyanidin (PA)-rich extracts, namely water extract (WE), ethanol extract (EE), and acetone extract (AE), were prepared. When added to O/W emulsions, all the three extracts inhibited the increase in droplet size and the absolute zeta-potential value during storage (55 °C, 24 days). All three extracts also exhibited superior antioxidative activity in the O/W emulsions. WE showed the highest efficacy in retarding lipid oxidation as proved by its lower conjugated dienes (8.18 ± 0.49 mmol L⁻¹) and thiobarbituric substances values (0.68 ± 0.0025 mg MDA L⁻¹), and such efficacy was similar to that of BHA at the same level. Lower molecular weight and degree of polymerisation have a positive effect on antioxidant activity of PA-rich extracts. According to these results, all three PA-rich extracts are potential natural antioxidants for improving the stability of food-grade emulsions.     

Structure and oxidative stability of oil in water emulsions as affected by rutin and homogenization procedure

The structural properties of oil-in-water (O/W) emulsions, as well as their oxidative stability upon storage at 50 °C, were studied. Eight different formulations were prepared, with the aim of studying the effect of three variables: the composition of the oil phase, the presence of the flavonoid rutin and the homogenization procedure on the structure and the oxidative stability. It was found that high pressure homogenization, through droplet size reduction, stabilized the emulsions both against creaming and oil oxidation. The interfacial protein was also partially replaced by rutin, further improving the stability of the emulsions, whereas purification of the oil phase had hardly any effect. Thus, the structural and oxidative stability of emulsions was controlled by the size of the droplets and improved by the addition of rutin.     

苦荞黄酮的抗脂质过氧化和红细胞保护作用研究

目的:研究苦荞总黄酮的体外抗脂质过氧化和红细胞保护作用,分析其抗氧化的主要成分。方法:将苦荞总黄酮用200～300目硅胶柱层析分离,氯仿-甲醇-水梯度洗脱,紫外检测,得到18个Rf值不同部位;DPPH活性示踪,得到2个活性较强部位(Fr4、Fr9);采用大鼠肝组织脂质过氧化、红细胞溶血模型比较苦荞总黄酮、Fr4、Fr9、槲皮素及芦丁的抗氧化效应;用薄层色谱分析Fr4、Fr9的化学组成。结果:苦荞总黄酮、Fr4、Fr9、槲皮素及芦丁DPPH抑制率(IR)分别为53.13%、66.15%、68.55%、71.99%、63.08%;抑制大鼠肝脏自发性脂质过氧化半抑制浓度(IC50)分别为:27.78、16.05、14.28、8.74和7.4mg/mL;抑制H2O2诱导大鼠肝脂质过氧化IC50分别为:0.37、3.60、0.07、0.07和0.41mg/mL;抑制H2O2诱导大鼠红细胞溶血IC50分别为:13.00、0.48、0.20、0.08和4.10mg/mL。Fr4、Fr9均含有槲皮素,另有3个组分待定。结论:槲皮素是苦荞总黄酮在体外表现抗脂质过氧化和红细胞保护作用主要活性成分之一。     

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.     

Pro-oxidant activities of carnosine,rutin and quercetin in a beef model system and their effects on the metmyoglobin-reducing activity

The effects of carnosine, rutin and quercetin on oxidative processes and metmyoglobin (MetMb)-reducing activity in a beef model system were investigated. Ground beef was mixed with antioxidant solution at two concentrations. Storage period and antioxidant treatment negatively affected colour, colour stability and thiobarbituric acid-reactive substances values. Carnosine, rutin and to lesser extent quercetin accelerated discolouration, accumulation of MetMb and lipid peroxidation in the meat. The results suggest that these antioxidants acted as a pro-oxidants under the specified experimental conditions. The pro-oxidant activities were in the following order: carnosine>rutin>quercetin. The MetMb-reducing activity was not correlated with storage time, colour parameters, MetMb (%) or lipid oxidation. The MetMb-reducing activity was significantly reduced by 1 mM carnosine. However, there was no association between MetMb-reducing activity and colour stability during post-mortem storage.     

Formulation and Stability Characterization of Rutin-Loaded Oil-in-Water Emulsions

In this work, formulation and characterization of oil-in-water (O/W) emulsions loaded with rutin were successfully overhead. We investigated the effect of homogenization pressure on the mean droplet size, droplet size distribution, physical stability, and rutin retention of these emulsions. O/W emulsions with a mean droplet size (d _3,2) of about 150 nm and a span of nearly the unit were formulated by microfluidization at the homogenization pressure 20–150 MPa. The O/W emulsion droplets loaded with rutin were physically stable in terms of variations of d _3,2 and span during 30 days of storage in the dark condition at 4 and 25 °C. The creaming velocity was characterized using centrifugal method showing a relative good shelf life. HPLC analysis demonstrated that 71–85% of initial rutin was retained in the fresh O/W emulsions and declined to 22–35% (w/w) for 30-day storage at 25 °C. Antioxidant activity assays confirmed that rutin-loaded emulsion participated in the antioxidant activity after encapsulation similarly to pure rutin. These results indicate that O/W emulsion systems can function as potential delivery systems to enhance bioavailability to encapsulate liposoluble antioxidant rutin for potential applications in the food industry.     

Effects of emulsifier charges on the oxidative stability in oil-in-water emulsions under riboflavin photosensitization

The oxidative stability in oil-in-water (O/W) emulsions containing different emulsifier charges was tested under riboflavin photosensitization by analysis of headspace oxygen content and lipid hydroperoxides. Sodium dodecyl sulfate (SDS), Tween 20, and cetyltrimethylammonium bromide (CTAB) were selected as anionic, neutral, and cationic emulsifiers, respectively. The O/W emulsions containing CTAB had lower oxidative stability than those with SDS and Tween 20. The addition of ethylenediaminetetraacetic acid, a well-known metal chelator, increased the oxidative stability in O/W emulsions, irrespective of emulsifier charges. Oxidative stability in Tween 20-stabilized emulsions decreased in FeCl₃ and FeCl₂ concentration-dependent manner. However, oxidative stability in samples containing CTAB increased up to 0.5mM of FeCl₃ and FeCl₂ and then decreased, which implies that CTAB act differently during lipid oxidation compared to SDS and Tween 20.     

Antioxidant and emulsifying properties of potato protein hydrolysate in soybean oil-in-water emulsions

The efficacy of a previously developed antioxidative potato protein hydrolysate (PPH) for the stabilisation of oil droplets and inhibition of lipid oxidation in soybean oil-in-water (O/W) emulsions was investigated. Emulsions (10% lipid, pH 7.0) with PPH-coated oil droplets were less stable than those produced with Tween 20 (P < 0.05). However, the presence of PPH, whether added before or after homogenisation with Tween 20, retarded emulsion oxidation, showing reduced formation of peroxides up to 53.4% and malonaldehyde-equivalent substances up to 70.8% after 7-d storage at 37 °C (P < 0.05), when compared with PPH-free emulsions. In the emulsions stabilised by PPH + Tween 20, 8–15% of PPH was distributed at the interface. Adjustment of the pH from 3 to 7 markedly increased ζ-potential of such emulsions (P < 0.05). Inhibition of lipid oxidation by PPH in soybean O/W emulsions can be attributed to both chemical and physical (shielding) actions.     

Surface properties of phenolic compounds and their influence on the dispersion degree and oxidative stability of olive oil O/W emulsions

The surface and interfacial properties of gallic acid, catechin and quercetin, and their effect on the dispersion degree and the oxidative stability of olive oil oil-in-water (O/W) emulsions prepared using β-lactoglobulin and Tween 20 were studied.Gallic acid showed no effect on the surface properties while catechin was proven to be able to accumulate at the air/water interface, decreasing the surface tension values with increasing its concentration. All the phenolic antioxidants caused a decrease in the interfacial tension at the oil/water interface, even though only catechin and quercetin showed a concentration dependent behaviour.In emulsions, gallic acid did not affect the droplet size of the systems, catechin caused the formation of oil droplets bigger than those of the control, whilst quercetin improved the dispersion state of the emulsions with the increasing of its concentration. Gallic acid, despite its partitioning in the water phase due to its polarity, delayed the formation of both the hydroperoxides and TBARs and limited their accumulation. Catechin did not affect the formation of oxidation products whilst quercetin, among the tested antioxidants, caused the lowest formation of both hydroperoxides and TBARs through 33 days of storage.     

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.     

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.     

Physical and Oxidative Stabilities of O/W Emulsions Formed with Rice Dreg Protein Hydrolysate: Effect of Xanthan Gum Rheology

The shortening of shelf-life of food emulsions is frequently due to poor creaming and lipid oxidation stability. The lipid oxidation of O/W emulsions can be inhibited by rice dreg protein hydrolysate (RDPH); however, emulsions were stabilized by Tween-20. Polysaccharides can control the rheology and network structure of the aqueous continuous phase by increasing viscosity and yield stress, hence retarding phase separation and gravity-induced creaming, especially for xanthan gum. The objective of this research was to evaluate whether emulsions formed with 2 wt% RDPH and stabilized by xanthan gum (0–0.5 wt%) could produce 20 % (v/v) soybean oil-in-water emulsions that had good physical and oxidative stability. The degree of flocculation of droplets as a function of xanthan gum concentration was assessed by the microstructure, rheology, and the creaming index of emulsions. Addition of xanthan gum prior to homogenization had no significant effect on the mean droplet diameter in all emulsions studied. Increase in xanthan gum concentration led to the increase in creaming stability of emulsions, due to an increase in viscosity of the continuous phase and/or the formation of a droplet network with a yield stress, as well as the enhanced steric and electrostatic repulsion between the droplets. Lipid oxidation of the emulsions was significantly inhibited at xanthan gum concentrations of 0.12 wt% or above with RDPH, which could due to the fact that xanthan gum increases the viscosity of the aqueous phase and hindered the diffusion of oxidants to the oil droplet surface area, synergistic effect between RDPH and xanthan gum to suppress oil peroxidation, and metal ion chelation capability of xanthan gum. Thus, stable protein hydrolyzates-type emulsions could be obtained with increasing concentration of xanthan gum.     

Impact of iron encapsulation within the interior aqueous phase of water-in-oil-in-water emulsions on lipid oxidation

Iron (Fe³⁺) was encapsulated within the internal aqueous phase of water-in-oil-in-water (W/O/W) emulsions, and then the impact of this iron on the oxidative stability of fish oil droplets was examined. There was no significant change in lipid droplet diameter in the W/O/W emulsions during 7 days storage, suggesting that the emulsions were stable to lipid droplet flocculation and coalescence, and internal water diffusion/expulsion. The initial iron encapsulation (4 mg/100 g emulsion) within the internal aqueous phase of the water-in-oil (W/O) emulsions was high (>99.75%), although, a small amount leaked out over 7 days storage (≈10 μg/100 g emulsion). When W/O/W emulsions were mixed with fish oil droplets the thiobarbituric acid-reactive substances (TBARS) formed decreased (compared to fish oil droplets alone) by an amount that depended on iron concentration and location, i.e., no added iron < iron in external aqueous phase < iron in internal aqueous phase. These differences were attributed to the impact of W/O droplets on the concentration and location of iron and lipid oxidation reaction products within the system.     

水包油乳液中油脂氧化稳定性的研究进展

随着消费者对不饱和脂肪酸及其产品营养价值越来越重视,不饱和脂肪酸富集食品已经成为食品工业发展的趋势。水包油(oil-in-water,O/W)乳液是食品油脂最常见的存在形式,也是必需脂肪酸、脂溶性营养素和风味物质的有效载体。然而,富含不饱和脂肪酸的O/W乳液食品在加工和贮藏过程中极易氧化,引起风味恶化、营养损失,甚至形成威胁人类健康的有毒化合物。因此,如何提高乳液中油脂的氧化稳定性是食品工业中亟待解决的问题。然而,消费者对天然食品需求的提高,又限制了合成抗氧化剂和氢化等传统抗氧化方法的使用。本文综述了O/W乳液中油脂氧化的机制、影响因素和调控机制,重点概述了食品分散体中油-水界面的理化性质如何影响油脂氧化稳定性这一基础研究,为高稳定性乳液体系和新型功能食品的开发提供新思路和理论支持。     

Antioxidant properties of caseins and whey proteins in model oil-in-water emulsions

The oxidative stabilities of both wheyproteinisolate (WPI)- and sodiumcaseinate-stabilized linoleic acid emulsions with different droplet sizes, protein concentrations and protein concentrations in the continuous phase were examined by determining lipid hydroperoxide and hexanal in the headspace. Emulsions with small droplet size had greater oxidative stability than emulsions with large droplet size in both WPI and sodiumcaseinate-stabilized emulsions. Lipid oxidation was in general lowered by an increase in the protein concentration. At high protein concentrations, the antioxidative effect of the protein in the emulsions appeared to offset the effects of emulsion droplet size and protein type. Replacing the unadsorbed protein in the continuous phase with water markedly decreased the oxidative stability of the emulsions. In contrast, the oxidative stability of the emulsions increased with increasing protein concentration in the continuous phase. This suggests that the antioxidative mechanism of protein in the interfacial region, such as binding trace metal ions from the lipid phase and free-radical-scavenging activity, may involve a dynamic exchange process with protein molecules from the continuous phase.     

Influence of heat processing and calcium ions on the ability of EDTA to inhibit lipid oxidation in oil-in-water emulsions containing omega-3 fatty acids

The nutritional benefits of ω-3 fatty acids make them excellent candidates as functional food ingredients if problems with oxidative rancidity can be overcome. Oil-in-water emulsions were prepared with 2% salmon oil, stabilized by 0.2% Brij 35 at pH 7. To determine the effects of heating (50–90 °C), ethylenediaminetetraacetic acid (EDTA), and calcium on the oxidative and physical stability of salmon oil-in-water emulsions, particle size, thiobarbituric acid reactive substances (TBARS), and lipid hydroperoxides were measured. The heat-processed emulsions showed no significant difference, in particle size, TBARS or hydroperoxides during storage, from unheated emulsions. Above 2.5 μM, EDTA dramatically decreased lipid oxidation in all samples. Addition of calcium to emulsions containing 7.5 μM EDTA significantly increased both TBARS and hydroperoxide formation when calcium concentrations were 2-fold greater than EDTA concentrations. These results indicate that heat-processed salmon oil-in-water emulsions with high physical and oxidative stability could be produced in the presence of EDTA.     

Stability of Bisphenol A (BPA) in Oil-In Water Emulsions under Riboflavin Photosensitization

Effects of riboflavin photosensitization on the degradation of bisphenol A (BPA) were determined in oil-in-water (O/W) emulsions containing ethylenediaminetetraacetic acid (EDTA) or sodium azide, which are a metal chelator or a singlet oxygen quencher, respectively. Also, the distribution of BPA between the continuous and dispersed phases in O/W emulsions was analyzed by high-performance liquid chromatography (HPLC). The concentration of BPA in O/W emulsions significantly decreased by 38.6% after 2 h under visible light irradiation and in the presence of riboflavin (P < 0.05). Addition of EDTA and sodium azide protected the decomposition of BPA significantly in a concentration dependent manner (P < 0.05), which implies both transition metals and singlet oxygen accelerate the photodegradation of BPA in O/W emulsions. Approximately 21.7% of the BPA was distributed in the 2.5% (w/v) dispersed lipid particles and 78.3% was in the continuous aqueous phase of the emulsions. The amount of BPA in aqueous phase decreased faster than the amount of BPA in the lipid phase during riboflavin photosensitization (P < 0.05). Thus, the BPA in the aqueous phase was the major target of riboflavin photodegradation in O/W emulsions. Practical Application: Concentration of BPA, an endocrine disrupting chemical, was decreased significantly in oil-in-water emulsions under riboflavin and visible light irradiation. BPA in continuous aqueous phase was major target of riboflavin photosensitization. However, BPA was distributed more densely in lipid phase and more protected from riboflavin photosensitized O/W emulsions. This study can help to decrease the level of BPA in foods made of O/W emulsions containing riboflavin, which could be displayed under visible light irradiation.     

Antiradical action of flavonoid-ascorbate mixtures

Flavonoids and ascorbic acid are antioxidants usually consumed together in foods, taking this into account, the antiradical capacity of mixtures of ascorbic acid with some representative flavonoids (flavanones, chalcones and flavonols) against the 2,2-diphenyl-1-picrylhydrazyl radical (DPPH) was evaluated. Antiradical capacities of naringin, naringenin, hesperidin, hesperetin, naringin chalcone, naringin dihydrochalcone, rutin and quercetin were measured alone and in different combinations with ascorbic acid. Experimental and theoretical values of antiradical activities for these mixtures as well as the values obtained in sequential reactions were compared in order to determine synergistic or antagonistic effects. Among the different ascorbic acid-flavonoid combinations analyzed only the mixture with naringin or quercetin exhibited synergistic effects, the mixture activity being 33 and 18% higher than the theoretical value, respectively. On the contrary, antagonistic effects were found in the cases of rutin, hesperidin, naringin chalcone, naringin dihydrochalcone and naringenin. Moreover, only hesperetin showed an additive effect. These behaviours were ascribed to the regeneration of the oxidized species on the basis of the structural features of each flavonoid and their different reactivity against DPPH These results show that the antiradical activity can be modified by the interaction among the mixture constituents and this may be considered to improve antioxidant formulations.     

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.