Effects of enzymatically modified starch on the encapsulation efficiency and stability of water-in-oil-in-water emulsions

The present study was performed to investigate the possibility of using 4-α-glucanotransferase (4αGTase)-treated starch in W/O/W emulsions to increase their encapsulation efficiency (EE) and stability. Emulsions were prepared using soybean oil, polyglycerol polyricinoleate (PGPR), 4αGTase-treated starch and Tween 20. The mean diameter of W/O/W droplets ranged from 4 to 10 μm depending on the sonication time. When the dye was loaded in the internal water phase, the emulsion prepared by sonication for 1 and 2 min showed a high EE of the dye (>90%). The W/O/W emulsion prepared by sonication for 3 min showed an EE of <90%, but this EE was improved by adding 4αGTase-treated starch to the internal water phase. 4αGTase-treated starch was added to the internal water phase of W/O/W emulsions prepared with a low concentration of PGPR, and the PGPR concentration required to maintain an EE >90% was reduced. W/O/W emulsions containing 4αGTase-treated starch also showed better stability against heating and shearing stresses. These results indicated that 4αGTase-treated starch could be used in the preparation of W/O/W emulsions, which would allow the formulation of W/O/W emulsions with a reduced surfactant concentration.     

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.     

Water soluble inner aqueous phase markers as indicators of the encapsulation properties of water-in-oil-in-water emulsions stabilized with sodium caseinate

The aim of this study was to evaluate the suitability of Methylene Blue (MB) and Vitamin B₁₂ (Vit-B₁₂) as water soluble inner aqueous phase (W₁) markers for measuring the encapsulation efficiency and stability of water-in-oil-in-water (W₁/O/W₂) double emulsions stabilized by sodium caseinate (NaCN). The encapsulation efficiency and stability were determined by centrifugation of the double emulsion to separate the cream phase (W₁/O) and the outer aqueous phase (W₂) and measuring the concentration of marker in W₂ by absorbance spectrophotometry. To validate this method the marker concentration measurable and the stability of the marker in W₂ were measured. Both markers could be accurately measured in W₂ and there was no change in the concentration of marker on storage of a W₂ solution for 7 days at 45 °C. The recovery yields of MB and Vit-B₁₂ in the recovered W₂ of an oil-in-water (O/W₂) emulsion, determined using the procedure normally used for measuring encapsulation efficiency and stability, were 78% and 99%, respectively, and 52 and 100%, respectively. Double emulsions had encapsulation efficiency of 61.9 ± 21.4% and 16.6 ± 1.1% and encapsulation stability of 62.0 ± 22.6% and 10.7 ± 0.7% for MB and Vit-B₁₂, respectively. Recovery yield and encapsulation efficiency/stability data for MB indicate that it is not a suitable marker for measuring the encapsulation properties of NaCN stabilized double emulsions while similar data for Vit-B₁₂ indicate that it is a suitable marker for studying the encapsulation properties of double emulsions stabilized with NaCN. Methods used in other studies to measure encapsulation properties of double emulsions are discussed in light of the results obtained in this study.     

The influence of different stabilizers and salt addition on the stability of model emulsions containing olive or sesame oil

Stabilizers are widely used in low-fat emulsion production. However, food industry pays attention to ingredients, such as resistant starch (RS) that also present substantial benefits to human health. Low-fat model emulsions of either olive or sesame oil that also contained xanthan gum (XG), whey protein concentrate (WPC), and undigested (resistant) starch (RS) were produced and stored at 5 °C. Salt was added in selected samples. A multiple light scattering technique was applied for investigating destabilization phenomena. Microscopic observations and droplet size measurements took place. Rheological properties performing a heating–cooling cycle experiment (5–25–5 °C) were measured. Olive oil emulsions presented the greatest stability and the lowest droplet size. RS plays the role of solid particle stabilizer, mainly entrapped in the matrix of the continuous phase. By salt addition stability was significantly improved, whereas droplet size was decreased. Those samples had a more pronounced elastic character and significantly greater viscosity values than their counterparts without salt.     

Impact of free fatty acid concentration and structure on lipid oxidation in oil-in-water emulsions

Free fatty acids are strong prooxidants in both bulk and emulsified oils. Addition of oleic acid to an oil-in-water emulsions increased lipid hydroperoxide and hexanal formation at free fatty acid concentrations as low as 0.1% of the lipid. The prooxidant effect of free fatty acids was dependent on fatty acid type with lipid oxidation rates being in the order of linolenic < linoleic < oleic. There were no significant differences in lipid oxidation rates when free fatty acid isomers with cis or trans double bonds were compared. The prooxidant activity of the free fatty acids was postulated to be due to their ability to attract prooxidant metals as well as co-oxidise the triacylglycerol in the oil. Overall, these results show that the oxidative stability of oil-in-water emulsions is strongly linked to both the concentration and type of free fatty acids present.     

The choice of homogenisation equipment affects lipid oxidation in emulsions

Milk proteins are often used by the food industry because of their good emulsifying properties. In addition, they can also provide oxidative stability to foods. However, different milk proteins or protein components have been shown to differ in their antioxidative properties, and their localisation in emulsions has been shown to be affected by the emulsification conditions. The objective of this study was to investigate the influence of homogenisation equipment (microfluidizer vs. two-stage valve homogeniser) on lipid oxidation in 10% fish oil-in-water emulsions prepared with two different milk proteins. Emulsions were prepared at pH 7 with similar droplet sizes. Results showed that the oxidative stability of emulsions prepared with sodium caseinate was not influenced by the type of homogeniser used. In contrast, the type of homogenisation equipment significantly influenced lipid oxidation when whey protein was used as emulsifier, with the microfluidizer resulting in lower levels of oxidation.     

Oil-in-water emulsions as a delivery system for n-3 fatty acids in meat products

The oxidative and physical stabilities of oil-in-water emulsions containing n-3 fatty acids (25 wt.% oil, 2.5 wt.% whey protein, pH 3.0 or pH 6.0), and their subsequent incorporation into meat products were investigated. The physical stability of fish oil emulsions was excellent and neither coalescence nor aggregation occurred during storage. Oxidative stability was better at pH 6.0 compared to pH 3.0 likely due to antioxidative continuous phase proteins. Incorporation of fish oil emulsions into pork sausages led to an increase in oxidation compared to sausages without the added fish oil emulsion. Confocal microscopy of pork sausages with fish oil emulsions revealed that droplets had coalesced in the meat matrix over time which may have contributed to the decreased oxidative stability. Results demonstrate that although interfacial engineering of n-3 fatty acids containing oil-in-water emulsions provides physical and oxidative stability of the base-emulsion, their incorporation into complex meat matrices is a non-trivial undertaking and products may incur changes in quality over time.     

Inhibition of lipid oxidation by encapsulation of emulsion droplets within hydrogel microspheres

The purpose of this study was to assess whether the oxidation of polyunsaturated lipids could be inhibited by encapsulating them within protein-rich hydrogel microspheres (size range 1-100 μm). Filled hydrogel microspheres were fabricated as follows: (i) high methoxy pectin, sodium caseinate, and casein-coated lipid droplets were mixed at pH 7, (ii) the mixture was acidified (pH 5), (iii) casein was cross-linked using transglutaminase, (iv) the pH was adjusted to pH 7. Samples were stored in the dark at 55 °C and were monitored for lipid hydroperoxide formation and headspace propanal. Oxidation of fish oil (1% vol/vol) in the microspheres was compared with that in oil-in-water emulsions stabilised by either sodium caseinate or Tween 20. Emulsions stabilised by Tween 20 oxidised faster than either microspheres or emulsions stabilised by casein, while microspheres and the casein stabilised emulsion showed similar oxidation rates. Results highlight the natural antioxidant properties of food proteins.     

Comparison of lipid and protein oxidation,total iron content and fatty acid profile of conventional and organic pork

The aim of the research was to compare differences in lipid and protein oxidation, total iron content and fatty acid profile in pork loin obtained from organic and conventionally reared pigs. The samples of organic meat were taken from breeding certified by the polish certifying body according to the Council Regulation (EC) no 834/2007 on organic production and labelling of organic products. The meat samples were examined at the following times post‐mortem: 2, 4, 7 days. Measurements of lipid oxidation showed that the organic meat samples were characterised by lower TBARS values during whole storage period (0.78–0.81 mg kg^?1) compared with those of conventional system production (0.95–0.99 mg kg^?1). Results of protein oxidation measurements of the organic meat sample were significantly lower (0.43 nmol mg^?1 protein) at the beginning of experiment than those for the conventional meat sample (0.66 nmol mg^?1 protein). It was also indicated that the production system had no effect on iron content and myoglobin oxidation during storage. In conclusion, obtained results pointed out that the organic pig meat was characterised by higher lipid stability during the whole storage time compared with meat from conventional production system.     

Protein-stabilized emulsions containing beta-carotene produced by premix membrane emulsification

Protein-stabilized O/W emulsions containing beta-carotene were produced by premix membrane emulsification (ME) using polymeric microfiltration membranes. Bovine serum albumin (BSA) and a whey protein concentrate (WPC) were used as protein emulsifiers while a nonionic small-molecule surfactant, Tween 20, was used both as a control and co-emulsifier. Membrane fouling caused by WPC reduced more significantly transmembrane flux than that by BSA. Mixtures of WPC or BSA with Tween 20 reduced protein membrane fouling and, simultaneously, decreased the mean droplet size. WPC/Tween 20 mixtures enable to produce emulsions with low polydispersion (span < 1) but with a significant membrane fouling while BSA/Tween 20 mixtures led to higher transmembrane fluxes although polydisperse emulsions (span = 7). During storage at 22 and 35 °C, the chemical degradation rate of emulsions with WPC/Tween 20 was slower than those with BSA/Tween 20 whereas Tween 20-stabilized emulsions led to the highest rate of beta-carotene reduction during storage at 35 °C.     

Oxidative stability of oil-in-water emulsions containing iron chelates: Transfer of iron from chelates to milk proteins at interface

Iron supplementation can promote oxidation of food matrices as well as cell lipids. The oxidative stability of oil/water emulsions stabilised by β-lactoglobulin (BLG) or sodium caseinate (SC) was studied in the presence of Fe-bisglycinate, NaFe-EDTA or FeSO₄. Lipid oxidation was evaluated by following the peroxide value (PV) and the thiobarbituric acid reactive substances (TBARS) over 7 days. At pH 6.5, for Fe-bisglycinate iron complement, the oxidation kinetics was more reduced with BLG than with SC. Contrarily to BLG, SC possesses phosphate groups that have more affinity for iron ions than carboxylate residues. Both BLG and SC stabilised emulsions were more oxidised with Fe-bisglycinate or FeSO₄ than with NaFe-EDTA. At pH 3.5, lipid oxidation was higher compared to pH 6.5. These results indicate that the competition for iron complexation between functional groups of protein and salt counter-ions (glycinate, sulphate or EDTA) appear as a key factor in oxidation.     

Reduction in lipid oxidation by incorporation of encapsulated sodium tripolyphosphate in ground turkey

Ground turkey, with 1% NaCl, was incorporated with no sodium tripolyphosphate (control, nSTP), unencapsulated STP (uSTP; 0.3% or 0.5%), encapsulated STP (eSTP; 0.3% or 0.5% active, phosphate basis), or a blend (0.3% uSTP plus 0.2% eSTP). Encapsulate (hydrogenated vegetable oil) was designed to melt at 74 °C. Treatments were stored (4, 24 h at 3 °C) before being cooked to two different endpoints (EPT; 74, 79 °C) followed by post-cooked storage (0, 5, 10 days). An improvement of 77% (0.3% eSTP) and 80% (0.5% eSTP) in the reduction of TBARS was found in comparison to corresponding uSTP. The blend produced a 62% improvement compared to uSTP (0.5%) while maintaining cook yield. CIE a* values were highest at both EPT and post-cooked storage times beyond 0 day for eSTP. Meat manufacturing procedures that entail a delayed thermal processing step will benefit by an improvement in lipid oxidation control through the use of encapsulated phosphates.     

Physicochemical and sensory properties of milk fortified with iron microcapsules prepared with water‐in‐oil‐in‐water emulsion during storage

This study investigated the possibility of fortifying iron microcapsule powder into milk and the effects of the fortification on the physicochemical and sensory properties of the products during storage. The iron microcapsules were prepared by the water‐in‐oil‐in‐water (W/O/W) emulsion technique. Fortifying the lower concentrations (0.1–0.3%, w/v) of iron microcapsules into the milk samples did not significantly change thiobarbituric acid values. The L‐values for the milk samples were not significantly influenced by fortifying iron microcapsules (0.1–0.7%, w/v). The overall acceptability scores were not affected when the lowest concentration of iron microcapsules (0.1%, w/v) was fortified into the milk.     

Design of interfacial films to control lipid oxidation in oil-in-water emulsions

In oil-in-water (O/W) emulsions, the droplets covered by native proteins are more prone to oxidation than droplets covered by surfactants. We attempted in this work to improve the barrier properties of protein-stabilized interfacial layers by controlled modifications of their composition and structure. Native bovine β-lactoglobulin (BLG) or β-casein (BCN), partially aggregated BLG and mixtures of the proteins with dilauroyl phosphatidylcholine (DLPC) were used to prepare emulsions and reconstituted Langmuir–Blodgett films. Lipid oxidation in the emulsions, as evaluated from oxygen uptake and formation of conjugated dienes, propanal and hexanal was roughly unmodified with aggregated BLG and DLPC–BLG mixtures and even favored with DLPC–BCN mixtures. The reconstituted phospholipid/protein interfacial layers presented interfacial heterogeneity evidenced by atomic force microscopy (AFM). This indicates that the structural homogeneity of the interface could be a key factor in controlling lipid oxidation.     

水相大豆分离蛋白质对油包水乳液稳定性影响

以富含多不饱和脂肪酸的核桃油为油相,于水相添加大豆分离蛋白(SPI),采用超高压微射流均质机制备油包水(W/O)乳液,乳液于45 ℃避光保存,每隔1 d测定乳液的平均粒径及粒径分布等物理特性,同时检测乳液初级及其次级氧化产物—脂质氢过氧化物与己醛,探究SPI对W/O乳液稳定性影响。结果表明,SPI应用于W/O乳液,乳液水滴粒径降低,乳液物理稳定性增大,SPI同时具有抗氧化活性。0.1%～0.4% SPI,蛋白质浓度的增大对乳液物理稳定性无显著性影响;SPI浓度增大(0.1%～0.2%)延长了脂质氢过氧化物与己醛形成延迟期,而浓度进一步增大(0.4%)乳液脂质氧化稳定性影响不显著。乳液水相pH对SPI抗氧化活性有显著影响,水相pH7.0,SPI抗氧化活性高于水相pH3.0。研究同时表明,水相钙离子强度0～200 mM CaCl₂,钙离子引入提高了乳液物理稳定性;乳液水相钙离子强度较低时(≤10 mMCaCl₂),离子强度的增大降低了SPI抗氧化活性,较高离子强度(100～200 mM CaCl₂)加速了乳液脂质氧化。     

脂质氧化产物-蛋白质相互作用研究进展

富含不饱和脂质的食品及其原料在加工和储存过程中易受多种因素影响而发生氧化。在此过程中生成的过氧化自由基和其他次级氧化产物能够使得蛋白质发生复杂变化。脂质氧化产物与蛋白质相互作用可以诱发蛋白质的交联、聚合,导致蛋白质共价结构变化、功能特性下降、风味恶化及营养损失,甚至产生有毒有害物质。研究表明,脂质氧化产物诱导的蛋白质氧化会造成色氨酸、精氨酸、酪氨酸等氨基酸含量减少;巯基含量增加、可溶性蛋白质的表面疏水性降低;α-螺旋、β-折叠增加;蛋白质聚集形成粒径较大的高分子聚集体。本文综述了脂质氧化产物-蛋白质相互作用及其对蛋白质结构和功能特性的影响,对于揭示脂质氧化产物与蛋白质的互作机制具有一定的指导意义。     

Preparation and impact of multiple (water-in-oil-in-water) emulsions in meat systems

The aim of this paper was to prepare and characterise multiple emulsions and assess their utility as pork backfat replacers in meat gel/emulsion model systems. In order to improve the fat content (in quantitative and qualitative terms) pork backfat was replaced by a water-in-oil-in-water emulsion (W₁/O/W₂) prepared with olive oil (as lipid phase), polyglycerol ester of polyricinoleic acid (PGPR) as a lipophilic emulsifier, and sodium caseinate (SC) and whey protein concentrate (WP) as hydrophilic emulsifiers. The emulsion properties (particle size and distribution, stability, microstructure) and meat model system characteristics (composition, texture, fat and water binding properties, and colour) of the W₁/O/W₂, as affected by reformulation, were evaluated. Multiple emulsions showed a well-defined monomodal distribution. Freshly prepared multiple emulsions showed good thermal stability (better using SC) with no creaming. The meat systems had good water and fat binding properties irrespective of formulation. The effect on texture by replacement of pork backfat by W₁/O/W₂ emulsions generally depends on the type of double emulsion (associated with the hydrophilic emulsifier used in its formulation) and the fat level in the meat system.     

State of dispersed lipid carrier and interface composition as determinants of beta-carotene stability in oil-in-water emulsions

Abstract: Liposoluble bioactive compounds are often included in foods in emulsified lipid carriers. In the present study, the impact of the physical state of the lipid carrier and the interfacial composition of oil‐in‐water emulsions on the stability of β‐carotene was studied. Emulsions with hydrogenated palm kernel oil (HPKO) concentration of 10% (w/w) dispersing 0.05% (w/w) β‐carotene, and a water phase at pH 7 containing 30% (w/w) sucrose, were stabilized by 1%, 1.5%, 2%, and 3% (w/w) whey protein isolate (WPI). Crystallization and melting behavior of emulsified and bulk HPKO were studied by differential scanning calorimetry. The hysteresis of emulsified HPKO crystallization (onset approximately 10 °C; endset approximately 6 °C) and melting (onset approximately 17 °C; endset approximately 45 °C) allowed us to operate at 15 °C on systems with identical compositions but different physical states of the same lipid phase. Surface protein coverage of emulsions was calculated and size of the dispersed particles was characterized by dynamic light scattering. β‐Carotene contents of the emulsions during storage at 15 °C was analyzed spectrophotometerically. Results highlighted an impact of the phase of the lipid carrier and of the concentration of WPI on β‐carotene degradation. β‐Carotene loss showed zero‐order kinetics. A liquid dispersed phase resulted in a low degradation rate but a high concentration of protein on a solid lipid carrier was likewise effective for β‐carotene protection. Practical Application: The inclusion of lipophilic bioactive compounds, such as carotenoids, is a current trend in the production of functional foods aiming to enhance health and well‐being. However, the use of functional ingredients in food products is complicated because of the sensitivity of the active molecules to physical and chemical factors to which they are exposed during processing, storage, and consumption. The present work gives indications of the influence of the lipid carrier physical state and surface structure on ß‐carotene stability in formulated oil‐in‐water liquid food models, suggesting possible strategies for an enhanced stabilization of lipophilic labile compounds.     

米糠蛋白O/W及W/O/W乳液制备及界面稳定性

为对比不同米糠蛋白质量浓度下O/W及W/O/W乳液的稳定性,以米糠蛋白作为基料,采用双乳化法制备O/W及W/O/W乳液,考察不同米糠蛋白质量浓度下乳液的微观形态和稳定性并探究其界面稳定机理。结果表明：W/O/W乳液的贮存稳定性显著优于O/W乳液;与相同蛋白含量的O/W乳液相比,W/O/W乳液的黏度显著提高;当米糠蛋白质量浓度为0.4 g/100 mL时,W/O/W乳液的稳定性较O/W乳液提高了1 倍以上;乳液内部包裹更多的W/O液滴,W/O/W乳液的粒径较大;而此时静电斥力也较大,起到稳定乳液的目的。同时,米糠蛋白质量浓度不小于0.4 g/100 mL时,O/W及W/O/W乳液中蛋白质的吸附率较高,达到78%以上。本研究为天然米糠蛋白质在食品级乳液中的开发提供参考,为粮食副产物的综合利用提供了新思路。