Lipid Oxidation in Oil-in-Water Emulsions: Impact of Molecular Environment on Chemical Reactions in Heterogeneous Food Systems

The susceptibility of lipids to oxidation is a major cause of quality deterioration in food emulsions. The reaction mechanism and factors that influence oxidation are appreciably different for emulsified lipids than for bulk lipids. This article reviews the current understanding of the lipid oxidation mechanism in oil‐in‐water emulsions. It also discusses the major factors that influence the rate of lipid oxidation in emulsions, such as antioxidants, chelating agents, ingredient purity, ingredient partitioning, interfacial characteristics, droplet characteristics, and ingredient interactions. This knowledge is then used to define effective strategies for controlling lipid oxidation in food emulsions.     

Characterization of Chemically and Thermally Treated Oil‐in‐Water Heteroaggregates and Comparison to Conventional Emulsions

Heteroaggregated oil‐in‐water (O/W) emulsions formed by targeted combination of oppositely charged emulsion droplets were proposed to be used for the modulation of physical properties of food systems, ideally achieving the formation of a particulate 3‐dimensional network at comparably low‐fat content. In this study, rheological properties of Quillaja saponins (QS), sugar beet pectin (SBP), and whey protein isolate (WPI) stabilized conventional and heteroaggregated O/W emulsions at oil contents of 10% to 60% (w/w) were investigated. Selected systems having an oil content of 30% (w/w) and different particle sizes (d₄₃ ≤ 1.1 or ≥16.7 μm) were additionally subjected to chemical (genipin or glutaraldehyde) and thermal treatments, aiming to increase network stability. Subsequently, their rheological properties and stability were assessed. Yield stresses (τ₀) of both conventional and heteroaggregated O/W emulsions were found to depend on emulsifier type, oil content, and initial droplet size. For conventional emulsions, high yield stresses were only observed for SBP‐based emulsions (τ₀,_SBP approximately 157 Pa). Highest yield stresses of heteroaggregates were observed when using small droplets stabilized by SBP/WPI (approximately 15.4 Pa), being higher than those of QS/WPI (approximately 1.6 Pa). Subsequent treatments led to significant alterations in rheological properties for SBP/WPI systems, with yield stresses increasing 29‐fold (glutaraldehyde) and 2‐fold (thermal treatment) compared to untreated heteroaggregates, thereby surpassing yield stresses of similarly treated conventional SBP emulsions. Genipin‐driven treatments proved to be ineffective. Results should be of interest to food manufacturers wishing to design viscoelastic food emulsion based systems at lower oil droplet contents.     

Stability and Oil Migration of Oil‐in‐Water Emulsions Emulsified by Phase‐Separating Biopolymer Mixtures

Oil‐in‐water (O/W) emulsions with varying concentration of oil phase, medium‐chain triglyceride (MCT), were prepared using phase‐separating gum arabic (GA)/sugar beet pectin (SBP) mixture as an emulsifier. Stability of the emulsions including emulsion phase separation, droplet size change, and oil migration were investigated by means of visual observation, droplet size analysis, oil partition analysis, backscattering of light, and interfacial tension measurement. It was found that in the emulsions prepared with 4.0% GA/1.0% SBP, when the concentration of MCT was greater than 2.0%, emulsion phase separation was not observed and the emulsions were stable with droplet size unchanged during storage. This result proves the emulsification ability of phase‐separating biopolymer mixtures and their potential usage as emulsifiers to prepare O/W emulsion. However, when the concentration of MCT was equal or less than 2.0%, emulsion phase separation occurred after preparation resulting in an upper SBP‐rich phase and a lower GA‐rich phase. The droplet size increased in the upper phase whereas decreased slightly in the lower phase with time, compared to the freshly prepared emulsions. During storage, the oil droplets exhibited a complex migration process: first moving to the SBP‐rich phase, then to the GA‐rich phase and finally gathering at the interface between the two phases. The mechanisms of the emulsion stability and oil migration in the phase‐separated emulsions were discussed.     

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.     

Stabilization of Fish Oil‐in‐Water Emulsions with Oleosin Extracted from Canola Meal

International dietary guidelines advocate replacement of saturated and trans fat in food with unsaturated oils. Also, there is growing interest in incorporating highly unsaturated omega‐3 oils in to food products due to beneficial health effects. A major obstacle to incorporating highly unsaturated oils in to food products is the extreme susceptibility to oxidative deterioration. Oil bodies were prepared from tuna oil, oleosin, and phospholipid mimicking natural oil bodies within oilseed. Oleosin was extracted from canola (Brassica napus) meal by solubilization in aqueous sodium hydroxide (pH 12) and subsequent precipitation at its isoelectric point of pH 6.5. The tuna oil artificial oil bodies (AOBs) readily dispersed in water to produce oil‐in‐water (o/w) emulsions, which did not coalesce on storage and were amenable to pasteurization using standard conditions. Accelerated oxidation studies showed that these AOB emulsions were substantially more resistant to lipid oxidation than o/w emulsions prepared from tuna oil using Tween40, sodium caseinate, and commercial canola protein isolate, respectively. There is potential to use commercial canola meal, which is cheap and abundant, as a natural source of oleosin for the preparation of physically and oxidatively stable food emulsions containing highly unsaturated oils.     

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.     

辐照及贮藏条件对食品脂肪氧化影响的研究

^60Coγ射线辐照能加速食品脂肪氧化,辐照食品在贮藏的前期,其脂肪氧化速度与对照相比无明显区别,随着贮藏时间的延长,其脂肪氧化速度明显加快;不同辐照食品的脂肪氧化速度不同;贮藏温度对辐照食品脂肪氧化的影响较大,贮藏温度越高,脂肪氧化速度越快,但温度对不同辐照食品脂肪氧化的影响程度有所差别;抗氧化剂可明显地抑制吃一堑照对食品脂肪氧化的影响和贮藏温度对辐照食品脂肪氧化的影响。     

Antioxidant Properties of Aqueous Extract of Roasted Hulled Barley in Bulk Oil or Oil‐in‐Water Emulsion Matrix

Antioxidant properties of the aqueous extracts of hulled barley (Hordeum vulgare L.) that had been roasted at 210 °C for 20 min were determined in bulk oil and oil‐in‐water (O/W) emulsions. Bulk oils were heated at 60, 100, and 180 °C, and O/W emulsions were oxidized under riboflavin photosensitization. The content of phenolic compounds was analyzed by high‐performance liquid chromatography, and in vitro antioxidant assays were also conducted. The major phenolics contained in the aqueous extract of roasted hulled barley (AERB) were p‐coumaric, ferulic, protocatechuic, chlorogenic, 4‐hydroxybenzoic, and vanillic acids. Depending on the concentration and oxidation temperature, AERB had antioxidant or prooxidant properties in bulk oil. At 60 °C, AERB at a concentration of 0.5% acted as a prooxidant, whereas at 1.0% it acted as an antioxidant. At 100 °C, AERB acted as an antioxidant irrespective of concentration. In 180 °C conditions, 0.5% AERB acted as a prooxidant, whereas other concentrations of AERB acted as antioxidants. In the case of riboflavin photosensitized O/W emulsions, AERB showed antioxidant properties irrespective of concentration. Antioxidant abilities of AERB are affected by the food matrix, including bulk oil and O/W emulsions, and concentrations of AERB, even though diverse phenolic compounds may display high antioxidant properties in in vitro assays.     

The Effect of Buckwheat Hull Extract on Lipid Oxidation in Frozen‐Stored Meat Products

This study investigated the effect of antioxidants on lipid stability of frozen‐stored meat products. Buckwheat hull extract was used to enrich fried meatballs made from ground pork. During 180‐d storage of meat products, lipid oxidation (peroxide and 2‐thiobarbituric acid reactive substances [TBARS] value) was periodically monitored. The results were compared with butylated hydroxytoluene (BHT). The addition of antioxidants decreased lipid oxidation in stored meatballs. The highest ability to control peroxide and TBARS values was demonstrated for buckwheat hull extract. Moreover, buckwheat hull extract showed a higher 2,2‐diphenyl‐1‐picrylhydrazyl free radical scavenging activity as well as higher Fe(II) ion chelating ability, as compared with BHT. The total content of phenolic compounds are highly correlated to the individual polyphenols in extract of buckwheat hull, among which the following were assayed: 3,4‐dihydroxybenzoic acid, 4‐hydroxybenzoic acid, gallic acid, isovanillic acid and p‐coumaric acid, and flavonoids: isoorientin, quercetin, quercetin 3‐d ‐glucoside, rutin, and vitexin. These results indicate that plant extracts can be used to prolong shelf life of products by protecting them against lipid oxidation and deterioration of their nutritional quality.     

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.     

脂肪氧化诱导鱼蛋白聚集变性研究进展

综述鱼脂肪氧化、鱼蛋白质变性以及脂肪氧化对蛋白质影响等方面的研究进展.明确提出鱼品质的下降的一个重要原因是由脂肪氧化诱导引起蛋白质劣变,下一步研究重点是探索脂肪氧化诱导蛋白质变性的机理.     

薄层色谱画像解析法快速判定鱼肉的脂质氧化度

为了快速判定鱼肉的脂质氧化度,建立薄层色谱画像(thin layer chromatography image,TLC-i)解析法快速测定鱼类氧化生成的极性化合物含量。取黄鳍金枪鱼油0.5μL点样于硅胶板上,用正己烷-乙醚-醋酸(30∶70∶1,V/V)的混合液展开12 min后,3%醋酸铜磷酸溶液喷雾显色,150℃加热15 min后,将氧化生成的极性化合物通过面积分析软件进行半定量分析。结果表明,此方法测得的极性化合物含量与常用的过氧化值(peroxide value,POV)、羰基值(carbonyl value,CV)相比,具有较好的相关性,相关系数分别为0.993 8和0.972 5。将此方法用于判定远东多线咸鱼在4℃贮藏期间的脂质氧化情况,发现极性化合物含量与POV具有较好的正相关性(R~2=0.962 5)。将此方法用于判定盐渍红鲑在-5℃贮藏期间的脂质氧化情况,发现极性化合物含量与a*值具有较好的负相关性(R~2=-0.822 9)。结果表明,该方法具有简单化、快速化、微量化、可视化的优点,且不需要昂贵的设备,适合鱼肉脂质氧化度的快速评价。     

Antioxidative Effects of a Glucose‐Cysteine Maillard Reaction Product on the Oxidative Stability of a Structured Lipid in a Complex Food Emulsion

A glucose‐cysteine Maillard reaction product (MRP) was produced and its antioxidant effects on lipid oxidation were determined for a structured‐lipid enriched with polyunsaturated fatty acids in a complex emulsion. Trolox equivalent antioxidant capacities (TEAC) were determined for MRP heating intervals of 2, 4, and 6 h and were compared to α‐tocopherol (TOC), MRP with TOC (TOC‐MRP), and TOC with ascorbyl palmitate (TOC‐AP). Emulsions were produced with total antioxidant additions of 0.02% of the oil, and lipid oxidation was monitored by peroxide and p‐anisidine values over 56 d. Positive correlations between browning and heating time as well as TEAC were observed. Total TEAC values for the MRP at 6 h, TOC, TOC with the MRP at 6 h, and TOC‐AP were 2.51, 3.87, 2.68, and 2.76 mg trolox eq/g, respectively. Oxidation results indicated a possible antioxidant effect for the MRP at 6 h on secondary oxidation for days 14 to 28. These results suggest that the MRP at 6 h could be useful in inhibiting secondary oxidation in complex emulsions.     

中式香肠中脂肪氧化对蛋白质氧化的影响

以中式香肠为研究对象,通过对加工、储藏过程中包装、温度、光照以及抗氧化剂的不同处理,建立中式香肠的脂肪氧化模型,结合对其蛋白质氧化的跟踪检测,分析了中式香肠中脂肪氧化与蛋白质氧化之间的相关性。结果表明:对于脂肪氧化的抑制作用,有效抑制了蛋白质氧化形成羰基类物质,且与脂肪氧化初级和次级产物均表现较好的相关性;脂肪氧化对于蛋白质游离硫醇基流失的促进作用是由脂肪氧化次级产物挥发性醛类物质引起的。