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。     

Oxidation and oxidative stability in emulsions

Emulsions are implemented in the fabrication of a wide array of foods and therefore are of great importance in food science. However, the application of emulsions in food production is restricted by two main obstacles, that is, physical and oxidative stability. The former has been comprehensively reviewed somewhere else, but our literature review indicated that there is a prominent ground for reviewing the latter across all kinds of emulsions. Therefore, the present study was formulated in order to review oxidation and oxidative stability in emulsions. In doing so, different measures to render oxidative stability to emulsions are reviewed after introducing lipid oxidation reactions and methods to measure lipid oxidation. These strategies are scrutinized in four main categories, namely storage conditions, emulsifiers, optimization of production methods, and antioxidants. Afterward, oxidation in all types of emulsions, including conventional ones (oil-in-water and water-in-oil) and uncommon emulsions in food production (oil-in-oil), is reviewed. Furthermore, the oxidation and oxidative stability of multiple emulsions, nanoemulsions, and Pickering emulsions are taken into account. Finally, oxidative processes across different parent and food emulsions were explained taking a comparative approach.     

Effects of composition and processing variables on the oxidative stability of protein-based and oil-in-water food emulsions

Because many common foods are emulsions (mayonnaise, coffee creamers, salad dressing, etc.), a better understanding of lipid oxidation mechanisms in these systems is crucial for the formulation, production, and storage of the relevant consumer products. A research body has focused on the microstructural and oxidative stability of protein-stabilized oil-in-water emulsions that are structurally similar to innovative products that have been recently developed by the food industry (e.g., non-dairy creams, vegetable fat spreads, etc.) This review presents recent findings about the factors that determine the development of lipid oxidation in emulsions where proteins constitute the stabilizing interface. Emphasis is given to “endogenous” factors, such as those of compositional (e.g., protein/lipid phases, pH, presence of transition metals) or processing (e.g., temperature, droplet size) nature. Improved knowledge of the conditions that favor the oxidative protection of protein in emulsions can lead to their optimized use as food ingredients and thereby improve the organoleptic and nutritional value of the related products.     

Lipid Oxidation in Oil‐in‐Water Emulsions: Involvement of the Interfacial Layer

More polyunsaturated fats in processed foods and fewer additives are a huge demand of public health agencies and consumers. Consequently, although foods have an enhanced tendency to oxidize, the usage of antioxidants, especially synthetic antioxidants, is restrained. An alternate solution is to better control the localization of reactants inside the food matrix to limit oxidation. This review establishes the state‐of‐the‐art on lipid oxidation in oil‐in‐water (O/W) emulsions, with an emphasis on the role of the interfacial region, a critical area in the system in that respect. We first provide a summary on the essential basic knowledge regarding (i) the structure of O/W emulsions and interfaces and (ii) the general mechanisms of lipid oxidation. Then, we discuss the factors involved in the development of lipid oxidation in O/W emulsions with a special focus on the role played by the interfacial region. The multiple effects that can be attributed to emulsifiers according to their chemical structure and their location, and the interrelationships between the parameters that define the physicochemistry and structure of emulsions are highlighted. This work sheds new light on the interpretation of reported results that are sometimes ambiguous or contradictory.     

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.     

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.     

Effects of flavonoids on physical and oxidative stability of soybean oil O/W emulsions

Flavonoids have attracted attention due to pharmacological and antioxidative activities. The effects of flavonoids on the physical and oxidative stabilities of lecithin emulsified soybean oil-in-water (O/W) emulsions were investigated at 25°C during 29 days of storage. Addition of 100 ppm hesperidin, hesperitin, rutin, or quercetin improved the physical stability of O/W emulsions but did not change particle size values, compared to a control with no flavonoids during storage. Quercetin showed the highest antioxidant activity for inhibition of lipid oxidation based on lowered lipid hydroperoxide formation and 2-thiobarbituric acid reactive substances values in emulsions, followed by rutin, hesperitin, and hesperidin. Hesperidin and hesperitin did not affect antioxidative activities in O/W emulsions under metal ion-catalyzed conditions. Addition of hesperidin, hesperitin, rutin, and quercetin to soybean oil O/W emulsions improved the physical and oxidative stability of emulsions lacking added metal ions.     

Oxidative stability of oil-in-water emulsions stabilised with protein or surfactant emulsifiers in various oxidation conditions

Many studies have investigated the effect of emulsifiers on the oxidative stability of oil-in-water (O/W) emulsions. A better oxidative stability of surfactant-stabilised O/W emulsions as compared to protein-stabilised emulsions has been recently shown in conditions when the major part of the emulsifier is adsorbed at the oil-water interface and oxidation is induced by iron−ethylenediaminetetraacetic acid (EDTA) complex. In this work, the contribution of the interfacial layer to the oxidation of emulsified lipids is investigated under various incubation conditions, involving different oxidation mechanisms. O/W emulsions were formulated at pH 6.7 with limited amounts of emulsifiers in the aqueous phase. Emulsions were incubated either at 33 °C without initiator at 25 °C in the presence of iron/ascorbate, metmyoglobin or 2,2′-azobis(2-amidinopropane)-dihydrochloride (AAPH). Oxygen uptake and volatile compound formation confirmed that protein-stabilised emulsions are less oxidatively stable than Tween 20-stabilised ones. This work also shows complex oxidative interrelationships between oxidation initiator and certain proteins, such as β-casein and bovine serum albumin.     

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.     

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.     

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 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.     

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.     

Review on the Stability Mechanism and Application of Water‐in‐Oil Emulsions Encapsulating Various Additives

Water‐in‐oil (W/O) emulsions can be used to encapsulate and control the release of bioactive compounds for nutrition fortification in fat‐based food products. However, long‐term stabilization of W/O emulsions remains a challenging task in food science and thereby limits their potential application in the food industry. To develop high‐quality emulsion‐based food products, it is essential to better understand the factors that affect the emulsions’ stability. In real food system, the stability situation of W/O emulsions is more complicated by the fact that various additives are contained in the products, such as NaCl, sugar, and other large molecular additives. The potential stability issues of W/O emulsions caused by these encapsulated additives are a current concern, and special attention should be given to the relevant theoretical knowledge. This article presents several commonly used methods for the preparation of W/O emulsions, and the roles of different additives (water‐ and oil‐soluble types) in stabilizing W/O emulsions are mainly discussed and illustrated to gain new insights into the stability mechanism of emulsion systems. In addition, the review provides a comprehensive and state‐of‐art overview of the potential applications of W/O emulsions in food systems, for example, as fat replacers, controlled‐release platforms of nutrients, and delivery carrier systems of water‐soluble bioactive compounds. The information may be useful for optimizing the formulation of W/O emulsions for utilization in commercial functional food products.     

Grape skin extracts as a sustainable source of antioxidants in an oil-in-water emulsion: an alternate natural approach to synthetic antioxidants using principal component analysis

Grape (Kyoho) skin, used to retard lipid oxidation in edible oil foods, was investigated to reduce lipid oxidation in an oil-in-water (O/W) emulsion during 20 day of storage. The antioxidant efficacy of Kyoho skin extracts in O/W emulsions was determined by the measurement of secondary oxidation products. Moreover, principal component analysis (PCA) was conducted to determine similarities between emulsions treated with or without Kyoho skin extracts and standards. The data revealed that Kyoho skin extracts exhibited >93% inhibition and reported a similar p-anisidine (4.30–20.71) and TBARS (6.08–11.15 mg MDA L⁻¹) values over the standards during 20 day of storage. PCA (PCs 1 (51.83%) and 2 (18.85%)) demonstrated a similarity in the contribution of Kyoho skin extracts over the synthetic antioxidants in O/W emulsion. Overall, these findings highlighted the possibility of using Kyoho skin extracts as natural antioxidants to decrease oxidative rancidity in foods.     

Potential implications of oxidative modification on dietary protein nutritional value: A review

During food processing and storage, proteins are sensitive to oxidative modification, changing the structural characteristics and functional properties. Recently, the impact of dietary protein oxidation on body health has drawn increasing attention. However, few reviews summarized and highlighted the impact of oxidative modification on the nutritional value of dietary proteins and related mechanisms. Therefore, this review seeks to give an updated discussion of the effects of oxidative modification on the structural characteristics and nutritional value of dietary proteins, and elucidate the interaction with gut microbiota, intestinal tissues, and organs. Additionally, the specific mechanisms related to pathological conditions are also characterized. Dietary protein oxidation during food processing and storage change protein structure, which further influences the in vitro digestion properties of proteins. In vivo research demonstrates that oxidized dietary proteins threaten body health via complicated pathways and affect the intestinal microenvironment via gut microbiota, metabolites, and intestinal morphology. This review highlights the influence of oxidative modification on the nutritional value of dietary proteins based on organs and the intestinal tract, and illustrates the necessity of appropriate experimental design for comprehensively exploring the health consequences of oxidized dietary proteins.     

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.     

Release rate profiles of magnesium from multiple W/O/W emulsions

Water-in-oil-in-water (W/O/W) emulsions were formulated based on rapeseed oil, olive oil, olein and miglyol. Polyglycerol polyricinoleate and sodium caseinate were used as lipophilic and hydrophilic emulsifiers, respectively. Magnesium was encapsulated in the inner aqueous droplets. Emulsion stability was assayed through particle sizing and magnesium release at two storage temperatures (4 and 25 °C) over 1 month. Irrespective of the oil nature, both the primary W/O and W/O/W emulsions were quite stable regarding the size parameters, with 10-μm fat globules and 1-μm internal water droplets. Magnesium leakage from W/O/W emulsions was influenced by the oil type used in the formulation: the higher leakage values were obtained for the oils characterized by the lower viscosity and the higher proportion of saturated fatty acids. Magnesium release was not due to droplet–globule coalescence but rather to diffusion and/or permeation mechanisms with a characteristic rate that varied over time. In addition, W/O/W emulsions were resistant to various thermal treatments that mimicked that used in pasteurization processes. Finally, when W/O/W emulsions were placed in the presence of pancreatic lipase, the emulsion triglycerides were hydrolysed by the enzyme. These results indicated a possible use of W/O/W emulsions loaded with magnesium ions in food applications.     

Processing and storage effects on the oxidative stability of hemp (Cannabis sativa L.) oil‐in‐water emulsions

Hempseed oil was used to form oil‐in‐water emulsions, and the effect of heating, storage and light on the oxidative stability of the dispersed phase was investigated. Lipid oxidation rate increased following thermal processing and light exposure, whereas oxidation markers remained relatively unaffected during emulsions storage at 4 °C for 10 days. Induction times of the emulsions were reduced up to 26% and the concentration of thiobarbituric acid reactive substances increased up to 4.5‐fold, depending on the processing conditions. Selected berries as potential sources of natural antioxidants were screened for polyphenol and anthocyanin content in order to investigate their ability to retard lipid oxidation in comparison with a commercially available synthetic counterpart. Raspberry powder extract significantly improved the oxidative stability of hemp‐based emulsion compared with the control and was even more effective compared to a synthetic antioxidant when samples were subjected to heat treatment.     

Emulsifying Properties of Proteins Isolated from Various Rice Cultivars

The emulsifying properties of rice proteins isolated from various non-waxy and waxy rice cultivars were studied to evaluate their potential application as oil-in-water (O/W) emulsifier and to compare the emulsifying properties of the rice proteins isolated from various rice cultivars. The solubility of the rice proteins was measured at different pHs (2–10), and O/W emulsions were prepared with the proteins at pH 2, 7, and 10. The rice protein-stabilized O/W emulsions were analyzed by measurement of particle size and zeta-potential, and observation under an optical microscope. The results indicated the potential of the rice proteins as emulsifiers at low and high pH values, and that, in particular, rice proteins isolated from waxy-rice cultivars could form stable emulsions even at neutral pH. The information obtained in this study may be useful for development of emulsion-based food products using rice protein isolate.