乳化体系中花生油氧化稳定性的研究

主要探讨花生油乳化体系中乳化剂类型、用量、pH值、EDTA、温度等对花生油氧化稳定性的影响,结果显示:乳化剂种类和pH对于乳状液体系的氧化稳定性有显著影响,阴离子乳化剂SDS稳定的乳化液,pH4.0的氧化速率最快;非离子乳化剂Tween20稳定的乳化液,pH的影响不是很显著;阳离子乳化剂CTAB稳定的乳化液,随着pH的升高,氧化速率变快。乳化液体系中微量金属离子对于体系也有相当大的影响,随着金属离子螯合剂EDTA浓度的增加,其乳化体系中花生油的氧化速率显著降低。乳化剂用量也会影响体系的氧化稳定性,随着乳化剂用量的增加,乳化乳化体系中花生油的氧化稳定性降低。     

Stability of citral in protein- and gum arabic-stabilized oil-in-water emulsions

Citral is a major flavor component of citrus oils that can undergo chemical degradation leading to loss of aroma and formation of off-flavors. Engineering the interface of emulsion droplets with emulsifiers that inhibit chemical reactions could provide a novel technique to stabilize citral. The objective of this study was to determine if citral was more stable in emulsions stabilized with whey protein isolate (WPI) than gum arabic (GA). Degradation of citral was equal to or less in GA- than WPI-stabilized emulsion at pH 3.0 and 7.0. However, formation of the citral oxidation product, p-cymene was greater in the GA- than WPI-stabilized emulsion at pH 3.0 and 7.0. Emulsions stabilized by WPI had a better creaming stability than those stabilized by GA because the protein emulsifier was able to produce smaller lipid droplets during homogenization. These data suggest that WPI was able to inhibit the oxidative deterioration of citral in oil-in-water emulsions. The ability of WPI to decrease oxidative reactions could be due to the formation of a cationic emulsion droplet interface at pH 3.0 which can repel prooxidative metals and/or the ability of amino acids in WPI to scavenge free radical and chelate prooxidative metals.     

EFFECT OF EMULSION DROPLETS ON THE RHEOLOGY OF WHEY PROTEIN ISOLATE GELS

The effects of droplet size and emulsifier type on the rheology of whey protein isolate (WPI) gels containing emulsion droplets was studied. Gels were prepared by dispersing droplets of corn oil (20 wt%, d₃₂= 0.7 – 4 μm) in a 10 wt% WPI solution (pH 7.0, 50 mM NaCl), and heating at 90C for 15 min. Gel strength was determined by measuring the stress of gels at 20% compression using an Instron Universal Testing Machine. Droplets stabilized by WPI increased the gel strength, those stabilized by non-ionic surfactants (Tween 20 and Triton X-100) decreased it slightly, and those stabilized by SDS decreased it drastically. Gel strength increased as the droplet size decreased for droplets stabilized by WPI, but was relatively insensitive to the size of droplets stabilized by the small molecule surfactants. These observations may be explained in terms of the interactions between the emulsifiers and the protein network. Droplets coated with emulsifiers which can be incorporated into the protein network reinforce the structure and so increase gel strength, whereas droplets coated with emulsifiers which cannot be incorporated into the protein network disrupt the three dimensional structure of the gel and decrease its strength.     

Rheology and Oxidative Stability of Whey Protein Isolate-Stabilized Menhaden Oil-in-Water Emulsions as a Function of Heat Treatment

ABSTRACT:  Menhaden oil-in-water emulsions (20%, v/v) were stabilized by 2 wt% whey protein isolate (WPI) with 0.2 wt% xanthan gum (XG) in the presence of 10 mM CaCl₂ and 200 μM EDTA at pH 7. Droplet size, lipid oxidation, and rheological properties of the emulsions were investigated as a function of heating temperature and time. During heating, droplet size reached a maximum at 70 °C and then decreased at 90 °C, which can be attributed to both heating effect on increased hydrophobic attractions and the influence of CaCl₂ on decreased electrostatic repulsions. Combination of effects of EDTA and heat treatment contributed to oxidative stability of the heated emulsions. The rheological data indicate that the WPI/XG-stabilized emulsions undergo a state transition from being viscous like to an elastic like upon substantial thermal treatment. Heating below 70 °C or for less than 10 min at 70 °C favors droplet aggregation while heating at 90 °C or for 15 min or longer at 70 °C facilitates WPI adsorption and rearrangement. WPI adsorption leads to the formation of protein network around the droplet surface, which promotes oxidative stability of menhaden oil. Heating also aggravates thermodynamic incompatibility between XG and WPI, which contributes to droplet aggregation and the accumulation of more WPI around the droplet surfaces as well.     

马铃薯蛋白水解物对不同乳化剂制备O/W乳状液氧化稳定性的影响

用Fenton催化氧化体系模拟氧化,催化剂FeCl3,H2O2,VC的浓度分别为5、5、0.1mmol/L,以脂肪氧化产物丙二醛为指标,考察了马铃薯蛋白和不同乳化剂(非离子乳化剂Tween20、阴离子乳化剂卵磷脂和大分子乳化剂酪蛋白酸钠)共乳化制备得到的乳状液的氧化稳定性,并测定了相应乳状液的乳化稳定性。酪蛋白酸钠和马铃薯水解蛋白作为乳化剂得到的乳状液氧化稳定性较好,而Tween20和马铃薯蛋白水解物作为乳化剂得到的乳状液物理稳定性较高。     

Ability of whey protein isolate and/or fish gelatin to inhibit physical separation and lipid oxidation in fish oil-in-water beverage emulsion

The effect of pH on the capability of whey protein isolate (WPI) and fish gelatin (FG), alone and in conjugation, to form and stabilize fish oil-in-water emulsions was examined. Using layer-by-layer interfacial deposition technique for WPI–FG conjugate, a total of 1% protein was used to prepare 10% fish oil emulsions. The droplets size distributions and electrical charge, surface protein concentration, flow and dynamic rheological properties and physiochemical stability of emulsions were characterize at two different pH of 3.4 and 6.8 which were selected based on the ranges of citrus and milk beverages pHs, respectively. Emulsions prepared with WPI–FG conjugate had superior physiochemical stability compare to the emulsions prepared with individual proteins. Higher rate of coalescence was associated with reduction in net charge and consequent decrease of the repulsion between coated oil droplets due to the proximity of pH to the isoelectric point of proteins. The noteworthy shear thinning viscosity, as an indication of flocculation onset, was associated with whey protein stabilized fish oil emulsion prepared at pH of 3.4 and gelatin stabilized fish oil emulsion made at pH of 6.8. At pH 3.4, it appeared that lower surface charge and higher surface area of WPI stabilized emulsions promoted lipid oxidation and production of hexanal.     

Effects of protein concentration and oil-phase volume fraction on the stability and rheology of menhaden oil-in-water emulsions stabilized by whey protein isolate with xanthan gum

The influences of protein concentration (0.2, 1, 2 wt%) and oil-phase volume fraction (5%, 20%, 40% v/v) on emulsion stability and rheological properties were investigated in whey protein isolate (WPI)-stabilized oil-in-water emulsions containing 0.2 wt% xanthan gum (XG). The data of droplet size, surface charge, creaming index, oxidative stability, and emulsion rheology were obtained. The results showed that increasing WPI concentration significantly affected droplet size, surface charge, and oxidative stability, but had little effect on creaming stability and emulsion rheology. At 0.2 wt% WPI, increasing oil-phase volume fraction greatly increased droplet size but no significant effect on surface charge. At 1 or 2 wt% WPI, increasing oil-phase volume fraction had less influence on droplet size but led to surface charge more negative. Increasing oil-phase volume fraction facilitated the inhibition of lipid oxidation. Meanwhile, oil-phase volume fraction played a dominant role in creaming stability and emulsion viscosity. The rheological data indicated the emulsions may undergo a behavior transition from an entropic polymer gel to an enthalpic particle gel when oil-phase volume fraction increased from 20% to 40% v/v.     

Physical Stability of Whey Protein-stabilized Oil-in-water Emulsions at pH 3: Potential ω-3 Fatty Acid Delivery Systems (Part A)

ABSTRACT: The oxidative stability of polyunsaturated lipids can be improved by incorporating them in oil droplets surrounded by positively charged whey protein isolate (WPI) membranes. This study dealt with the factors that influence the physical properties of WPI-stabilized oil-in-water emulsions at pH 3. Emulsions containing 5 to 50 wt% corn oil and 0.5 to 5.0 wt% WPI (protein-to-oil ratio of 1:10) were prepared at pH 3. The apparent viscosity of the emulsions increased appreciably at oil concentrations ≥ 35 wt%; however, the particle size was relatively independent of oil concentration. The influence of NaCl (0 to 250 m M ) on the physical properties of 28 wt% emulsions was examined. Significant increases in mean particle size, apparent viscosity, and creaming instability occurred at ≥150 m M NaCl, which were attributed to flocculation induced by screening of the electrostatic repulsion between droplets. The influence of heat treatment (30°C to 90°C for 30 min) on 28 wt% emulsions was examined in the absence and presence of salt, respectively. At 0 m M NaCl, heating had little effect on the physical properties of the emulsions, presumably because the electrostatic repulsion between the droplets prevented droplet aggregation. At 150 m M NaCl, the mean particle diameter, apparent viscosity, and creaming instability of the emulsions increased considerably when they were heated above a critical temperature, which was 70°C when salt was added before heating and 90°C when salt was added after heating. These results have important implications for the design of WPI-stabilized emulsions that could be used to incorporate functional lipids that are sensitive to oxidation, for example, ω-3 fatty acids.     

提高大豆油水乳状液氧化稳定性的研究

为满足不同特殊人群的营养需求，可以设计不同的配方奶粉。富含不饱和脂肪酸的配方奶粉由于含有较高的不饱和脂肪酸油脂，容易出现脂肪氧化的质量问题。本文着重考察了配方粉在成粉前，引起乳状液的氧化的一些影响因素。结果表明，在有铁离了共存时，含花生四烯酸的大豆油水乳状液的脂肪氧化与铁离了成正相关，鏊合剂柠檬酸钠可以通过对铁离了的鏊合作用在起始阶段降低乳状液的氧化程度，抗氧化剂抗坏血酸棕榈酸酯抑制脂肪氧化主要体现在贮存后阶段。当二者联合应用时，在液体乳状液和固体粉状时都具有显著的抗氧化效果。     

Antioxidant Activity of Whey in a Salmon Oil Emulsion

The antioxidant capabilities of whey in a Tween 20^TM‐stabilized salmon emulsion were investigated. Whey fractions inhibited formation of thiobarbituric acid reactive substances (TBARS) and lipid peroxides in a 10 % salmon oil emulsion in the order of whey > high‐molecular‐weight (HMW) fraction > low‐molecular‐weight fraction. Heating the HMW fraction exposed sulfhydryls, with optimum exposure at 80 °C. Heating the HMW fraction above 80 °C increased antioxidant activity. The HMW fraction of whey (80 °C) alone, α‐tocopherol (40 ppm) alone, and their combination inhibited TBARS 59,19 and 86%, respectively, at 21 d of storage. Sulfhydryls oxidized before a‐tocopherol, suggesting that sulfhydryls are the primary antioxidant. Results indicate that whey proteins could be useful antioxidants in food emulsions.     

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.     

酯化改性淀粉纳米晶稳定的Pickering乳液及其油脂氧化稳定性

通过辛烯基琥珀酸酐（OSA）与淀粉纳米晶（SNC）的酯化反应获得OSA改性淀粉纳米晶（OSA-SNC）,以OSA-SNC为乳化剂,橄榄油为油相,制备出Pickering乳液,并探讨了OSA-SNC浓度、水相p H对乳液稳定性的影响。此外,通过与Tween-20稳定的乳液进行对比,研究了乳化剂浓度、水相p H对乳液油脂氧化稳定性的影响。研究表明,Pickering乳液的稳定性随着乳化剂浓度或者水相p H的增加而得到提高。OSA-SNC稳定乳液的油脂氧化稳定性显著优于Tween-20稳定的乳液;随着乳化剂浓度的增加,Tween-20稳定乳液的POV升高,而OSA-SNC稳定乳液的POV降低;Tween-20稳定乳液的POV随着水相p H的增大先降低再升高,而OSA-SNC稳定乳液的POV随着水相p H的增大而升高。      

Fractionation and characterisation for antioxidant activity of hydrolysed whey protein

Whey protein isolate (WPI) was hydrolysed for 1 h using Alcalase, Protamex and Flavourzyme. Native WPI, hydrolysed WPI and two commercial WPI hydrolysates were subjected to fractionation by size exclusion chromatography. Antioxidant activity of WPI fractions was measured with a liposome‐oxidising system (50 µM FeCl₃/0.1 µM ascorbate, pH 7.0). Lipid oxidation was measured as thiobarbituric acid‐reactive substances (TBARS). Gel electrophoresis and amino acid analysis were run to identify the peptide composition. The influence of amino acid composition on antioxidant activity was evaluated using multivariate analysis methods (correlation analysis, principal component analysis, multiple linear regression and discriminant analysis). TBARS assays indicated the presence of antioxidant activity in all protein fractions, including non‐hydrolysed WPI. For native and hydrolysed WPI samples the first fraction (> 45 kDa) showed a higher TBARS inhibition effect (24–27%) when compared with lower‐molecular‐weight fractions and hydrolysate mixtures. In contrast, for commercial WPI hydrolysates a higher inhibitory effect was found in most of the lower‐molecular‐weight fractions (30–55%). The ability of WPI fractions to delay lipid oxidation was found to be related to the prevalence of histidine and hydrophobic amino acids. Copyright © 2004 Society of Chemical Industry     

Influence of chitosan and NaCl on physicochemical properties of low-acid tuna oil-in-water emulsions stabilized by non-ionic surfactant

An influence of low molecular weight (LMW) chitosan on physicochemical properties and stability of low-acid (pH 6) tuna oil-in-water emulsion stabilized by non-ionic surfactant (Tween 80) was studied. The mean droplet diameter, droplet charge (ζ-potential), creaming stability and microstructure of emulsions (5 wt% oil) were evaluated. The added chitosan was adsorbed on the surface of oil droplets stabilized by Tween 80 through electrostatic interactions. Such addition of chitosan at different concentrations (0–10 wt%) to emulsions showed slight effect on the mean droplet diameter. However, the degree of flocculation was a function of chitosan concentration assessed by emulsions' microstructure and creaming index. The impact of chitosan on the strength of the colloidal interaction between the emulsion droplets increased with increasing chitosan concentration. The mean diameter of droplet in emulsions increased with increasing NaCl because of the electrostatic screening effect. The addition of LMW chitosan could be performed to create tuna oil emulsions with low-acid to neutral character, as well as various physicochemical and stability properties suitable for health food products.     

Comparison of Gum Arabic, Modified Starch, and Whey Protein Isolate as Emulsifiers: Influence of pH, CaCl2 and Temperature

ABSTRACT: The particle size and zeta potential of model beverage emulsions (0.01 wt% soybean oil-in-water emulsions, d ≅ 1 mm) stabilized by gum arabic, modified starch, or whey protein isolate (WPI) were studied with varying pH (3 to 9), CaCl₂ concentration (0 to 25 mM), and temperature (30 °C to 90 °C). Temperature, pH, CaCl₂ strongly influenced emulsions stabilized by WPI because its stabilizing mechanism was mainly electrostatic repulsion, but not those stabilized by gum arabic or modified starch because their stabilizing modes of action were mainly steric repulsion. This study may have important implications for the application of WPI as an emulsifier in beverage emulsions.     

Microstructural design to reduce lipid oxidation in oil-inwater emulsions

The influence of emulsifier type (Tween 20 and sodium caseinate (CAS)) and oil phase volume fraction (5% and 30%) on emulsion oxidative stability was investigated. The primary and secondary lipid oxidation products of emulsions stored at 40 °C were measured over 7 days. The results indicated that the oxidative stability of samples stabilised with CAS was significantly higher compared with emulsions stabilised with Tween 20. We propose that this is due to iron binding ability of CAS. Moreover, the impacts of Pickering emulsions (Silica particles) on lipid oxidation were studied and compared with Tween 20 stabilised emulsions. The results showed that silica particles could increase the oxidative stability of 20% sunflower oil-in-water emulsions by acting as a physical barrier between pro-oxidants located in continuous phase and hydroperxide at droplet interface.     

Effect of antioxidants on stabilization of meat products fortified with n-3 fatty acids

The effects of an n-3 oil emulsion, with and without added antioxidants, on lipid oxidation in n-3 polyunsaturated fatty acid (PUFA)-fortified meat products were studied. An emulsion of n-3 PUFAs was prepared (25% algal oil, 2.5% whey protein isolates, 10mM sodium citrate, 0.2% potassium sorbate, 500ppm of 70% mixed tocopherols, 100μM EDTA, pH 3, pasteurized at 75°C for 30min) and incorporated into fresh ground turkey, and fresh pork sausage (20% fat) to achieve a concentration of 500mg n-3 PUFA/110g meat. An antioxidant combination containing rosemary (0.2% w/w; radical quencher), citrate (0.5% w/w; sequestrant) and erythorbate (1g/kg product; reductant) was prepared and incorporated into ground turkey patties (5cm dia, 1.5cm thick) or fresh pork sausages (5cm dia, 1.5cm thick). Meat products were stored at 4°C or -18°C and analyzed for color (L*, a*, b* values), lipid oxidation (TBARS and lipid hydroperoxides) and n-3 PUFA profile. a* Values of refrigerated ground turkey patties decreased with storage, and an antioxidant combination effect was observed after 4 days (P<0.05). For fresh pork sausages at 4°C, control+antioxidant (CON+ANTI), and n-3+antioxidant (n-3+ANTI) groups showed greater a* values than controls (CON) indicating that the antioxidant combination stabilized meat color. TBARS and lipid hydroperoxides of both n-3 PUFA-enhanced meat products increased with storage (P<0.05); there were no significant changes in TBARS or lipid hydroperoxides for treatments containing the antioxidant combination (P<0.05). The actual level of n-3 PUFA incorporation in both meat products was greater than 87%; n-3 PUFA concentrations did not change within any treatment during storage (P>0.05). These results provide support for including antioxidant protection in n-3 PUFA fortified meat products.     

腐植酸钠在复杂体系中抗氧化作用的研究

用偶氮氧化物AAPH热分解生成的自由基引发脂质氧化,通过硫氰酸铁法和硫代巴比妥酸反应物法检测脂质的氧化进程,研究腐植酸钠在用非离子表面活性剂Tween 20稳定的葵花油水包油乳状液模拟非均相食品体系和用大豆磷脂脂质体模拟非均相生物体系中的抗氧化活性。结果表明:在葵花油乳状液中0.20、0.50、1.00 mg/mL腐植酸钠和在大豆磷脂脂质体中0.016、0.040、0.080 mg/mL的腐植酸钠均具有抗氧化活性。     

Physical characteristics of submicron emulsions upon partial displacement of whey protein by a small molecular weight surfactant and pectin addition

O/W emulsions (6 wt.% olive oil) were prepared at pH 3.3 using different WPI:Tween 20 weight ratios (1:0, 3:1, 1:1, 1:3, 0:1) at 1 wt.% total concentration. The emulsion droplet size was found to decrease with an increase in Tween 20. A minimum droplet size of d_3,2 300 nm was found for Tween systems alone, similar to that found (360 nm) for a 1:1 WPI:Tween 20 combination (p < 0.05). This specific composition showed a value for the interfacial tension close to that of Tween 20 alone. However, the emulsions presented low stability regardless of the WPI:Tween 20 ratio. To increase their stability, pectin was added, in various concentrations (0.2, 0.4 and 0.6 wt.%), using the Layer by Layer technique. In the presence of pectin, the ζ-potential of the oil droplets became negative; indicating that negatively charged pectin was absorbed onto the positively-charged droplet surface forming a secondary layer. The additional layer resulted in a wide range of emulsion stability. For all pectin concentrations, the 1:1 ratio of WPI:Tween 20 showed the highest stability. In most emulsions, extensive aggregation of oil droplets was observed, and their viscosity increased. Insufficient amounts of pectin to form the secondary layers led to bridging flocculation phenomena of oppositely charged pectin and proteins, leading to aggregation of the oil droplets. The higher the concentration of pectin, the greater the stability of the emulsion due to higher viscosity. All in all, the addition of a second layer consisting of pectin can be used to increase the stability of an emulsion containing emulsion droplets in the sub-micron range.     

界面组成对乳化颗粒填充乳清蛋白凝胶强度及持水性的影响

考察了p H（3、7）、氯化钠浓度（50、200mmol/L）以及热处理（90℃、30min）对不同乳化剂（乳清分离蛋白、Tween20、Tween20+马铃薯蛋白水解物）制备O/W乳状液分层稳定性的影响。并以凝胶持水性和凝胶强度为指标,考察了p H和氯化钠浓度对上述不同界面组成的乳化颗粒填充乳清蛋白热诱导凝胶性质的影响。结果表明,以乳状液为溶剂制备的凝胶持水性与凝胶强度高于以水为溶剂制备的凝胶。加入一定量的氯化钠有助于乳状液凝胶持水性与凝胶强度的增加。研究表明,p H和盐浓度对乳状液填充凝胶强度均有影响,乳状液性质对乳状液填充凝胶强度和持水性有一定影响。