Maillard Reaction Products as Encapsulants for Fish Oil Powders

The use of Maillard reaction products for encapsulation of fish oil was investigated. Fish oil was emulsified with heated aqueous mixtures comprising a protein source (Na caseinate, whey protein isolate, soy protein isolate, or skim milk powder) and carbohydrates (glucose, dried glucose syrup, oligosaccharide) and spray‐dried for the production of 50% oil powders. The extent of the Maillard reaction was monitored using L*, a*, b* values and absorbance at 465 nm. Encapsulation efficiency was gauged by measurement of solvent‐extractable fat and the oxidative stability of the fish oil powder, which was determined by assessment of headspace propanal after storage of powders at 35 °C for 4 wk. Increasing the heat treatment (60 °C to 100 °C for 30 to 90 min) of sodium caseinate‐glucose‐glucose syrup mixtures increased Maillard browning but did not change their encapsulation efficiency. The encapsulation efficiency of all heated sodium caseinate‐glucose‐glucose syrup mixtures was high, as indicated by the low solvent‐extractable fat in powder (<2% powder, w/w). However, increasing the severity of the heat treatment of the sodium caseinate‐glucose‐glucose syrup mixtures reduced the susceptibility of the fish oil powder to oxidation. The increased protection afforded to fish oil in powders by increasing the temperature‐time treatment of protein‐carbohydrate mixtures before emulsification and drying was observed irrespective of the protein (sodium caseinate, whey protein isolate, soy protein isolate, or skim milk powder) and carbohydrate (glucose, glucose/dried glucose syrup, or oligosaccharide/dried glucose syrup) sources used in the formulation. Maillard reaction products produced by heat treatment of aqueous protein‐carbohydrate mixtures were effective for protecting microencapsulated fish oil and other oils (evening primrose oil, milk fat) from oxidation.     

Iron‐mediated lipid oxidation in 70% fish oil‐in‐water emulsions: effect of emulsifier type and pH

The objective of this study was to investigate the protective effect of five different emulsifiers on iron‐mediated lipid oxidation in 70% fish oil‐in‐water emulsions. The emulsifiers were either based on protein (whey protein isolate and sodium caseinate) or based on phospholipid (soy lecithin and two milk phospholipids with different phospholipid contents, MPL20 and MPL75). Lipid oxidation was studied at pH 4.5 and 7.0, and results were compared to lipid oxidation in neat fish oil. Results showed that all emulsions oxidised more than neat oil. Furthermore, emulsions prepared with proteins oxidised more at low pH than at high pH, and casein emulsions oxidised the least (Peroxide value (PV) at day 7 was 0.5–0.7 meq kg^?1). Among emulsions prepared with phospholipids, emulsions with MPL75 were the most oxidised followed by emulsions prepared with lecithin and MPL20. Thus, PV in MPL75 emulsions was 5.0–5.5 meq kg^?1 at day 7 compared with 0.9–1.9 meq kg^?1 in MPL20 emulsions.     

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.     

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.     

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.     

Effect of high‐pressure homogenisation on the retention of selected aroma compounds in model dairy emulsions

The aim of this work was to investigate the effects of high‐pressure homogenisation on the aroma retention of mixed sodium caseinate–whey protein (2% + 2% w/v) emulsions. For this purpose, raw and pasteurised emulsions, with different fat contents (5%, 8% and 15% w/v) and subjected to different homogenisation pressures (0, 18, 100 and 150 MPa), were produced. The retention of seven aroma compounds (hexanal, benzaldehyde, diacetyl, ethyl butyrate, isoamyl acetate, ethyl hexanoate and ethyl octanoate) was evaluated by static headspace gas chromatography. Results showed that aroma release was affected by the presence and the quantity of the lipid phase. As regards homogenisation, an increase in the retention of hexanal with homogenisation pressure was observed and interactions between hexanal and caseinate were suggested. Benzaldehyde showed significant changes in headspace partition with increasing pressure only in the 5% fat content emulsions, whereas no homogenisation effect on aroma retention was observed for diacetyl or esters.     

Comparison of the Emulsifying Properties of Fish Gelatin and Commercial Milk Proteins

ABSTRACT: We have compared the flocculation, coalescence, and creaming properties of oil-in-water emulsions prepared with fish gelatin as sole emulsifying agent with those of emulsions prepared with sodium caseinate and whey protein. Two milk protein samples were selected from 9 commercial protein samples screened in a preliminary study. Emulsions of 20 vol% n -tetradecane or triglyceride oil were made at pH 6.8 and at different protein/oil ratios. Changes in droplet-size distribution were determined after storage and centrifugation and after treatment with excess surfactant. We have demonstrated the superior emulsifying properties of sodium caseinate, the susceptibility of whey protein emulsions to increasing flocculation on storage, and the coalescence of gelatin emulsions following centrifugation.     

Interfacial composition and stability of emulsions made with mixtures of commercial sodium caseinate and whey protein concentrate

The interfacial composition and the stability of oil-in-water emulsion droplets (30% soya oil, pH 7.0) made with mixtures of sodium caseinate and whey protein concentrate (WPC) (1:1 by protein weight) at various total protein concentrations were examined. The average volume-surface diameter (d₃₂) and the total surface protein concentration of emulsion droplets were similar to those of emulsions made with both sodium caseinate alone and WPC alone. Whey proteins were adsorbed in preference to caseins at low protein concentrations (<3%), whereas caseins were adsorbed in preference to whey proteins at high protein concentrations. The creaming stability of the emulsions decreased markedly as the total protein concentration of the system was increased above 2% (sodium caseinate >1%). This was attributed to depletion flocculation caused by the sodium caseinate in these emulsions. Whey proteins did not retard this instability in the emulsions made with mixtures of sodium caseinate and WPC.     

Physico‐chemical,organoleptic, antioxidative and release characteristics of flavoured yoghurt enriched with microencapsulated Melissa officinalis essential oil

In this research, Melissa officinalis essential oil was encapsulated through ultrasonication by using different ratios of whey protein isolate/sodium caseinate as coating material. Flavoured yoghurt was generated by adding microcapsules; the release behaviour of the essential oil was characterised over a 21‐day storage period. The released essential oil was quantified by dispersive liquid–liquid microextraction followed by gas chromatography. The results showed that the antioxidative activity of yoghurt samples was increased by the incorporation of encapsulated essential oil. Therefore, the use of microcapsules containing M. officinalis essential oil could be a suitable method for producing nutraceutical foods with antioxidant properties.     

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.     

单、双脂肪酸甘油酯(亚麻酸)乳液的制备及特性研究

针对单、双脂肪酸甘油酯（亚麻酸）极易氧化的特点,该研究以乳清浓缩蛋白（WPC）、大豆分离蛋白（SPI）、酪蛋白酸钠（SC）和吐温80（T80）为乳化剂制备乳液,考察乳化剂类型对乳液的理化性质、氧化稳定性和消化特性的影响。结果表明,乳液均具有较小的粒径（131.97~224.87 nm）,且在两周贮藏期内保持稳定。乳液包载能够提高单、双脂肪酸甘油酯（亚麻酸）的氧化稳定性,相比T80（过氧化值为377.40 mmol/kg）,蛋白质对油脂的氧化保护效果更好,其中SPI稳定的乳液过氧化值最低为197.73 mmol/kg。体外模拟消化试验表明,乳化剂类型对游离脂肪酸的释放影响较小,但蛋白稳定的乳液在胃消化阶段更容易发生液滴聚集;亚麻籽油的脂质水解程度最低为23.93%,而单、双脂肪酸甘油酯（亚麻酸）的初始消化速度更快,最终脂解程度更高（46.33%）。因此,蛋白质乳液能有效提高单、双脂肪酸甘油酯（亚麻酸）的氧化稳定性,且单、双脂肪酸甘油酯（亚麻酸）相比亚麻籽油具有更好的消化效率,有望替代亚麻籽油作为人体亚麻酸的食物来源。     

Influence of Emulsification Technique and Wall Composition on Physicochemical Properties and Oxidative Stability of Fish Oil Microcapsules Produced by Spray Drying

Encapsulation of fish oil is an effective way to protect it against oxidation and masking its fishy odor. One of the possible ways to produce fish oil microcapsules is to produce an oil-in-water (O/W) emulsion followed by spray drying. This study compares the production of the O/W emulsion by mechanical homogenization (rotor–stator) with membrane emulsification and examines the effect of the type and amount of wall material added before drying. The membrane emulsification process selected for the emulsion production is premix membrane emulsification (ME), which consists of the production of a coarse emulsion by mechanical means followed by droplet breakup when the coarse emulsion is forced through a membrane. The emulsions produced had an oil load of 10 and 20 % and were stabilized using whey protein (isolate and hydrolyzate at 1 or 10 %) and sodium caseinate with concentrations of 2 and 10 %. Regarding the material used to build the microcapsule wall, whey protein, maltodextrin, or combinations of them were used at three different oil/wall ratios (1:1, 1:2, 1:3). The results clearly show that premix ME is a suitable technology for producing O/W emulsions stabilized with proteins, which have a smaller droplet size and are more monodisperse than those produced by rotor–stator emulsification. However, protein concentrations of 10 % are required to reduce the droplet size down to 2–3 μm. Small and monodisperse emulsions have been found to produce microcapsules with lower surface oil content, which increases oil encapsulation efficiency and presents lower levels of oxidation during storage at 30 °C. Of all the possible combinations studied, the one with the highest oil encapsulation efficiency is the production of a 20 % O/W emulsion stabilized with 10 % sodium caseinate followed by the addition of 50 % maltodextrin and drying.     

Oil-in-Water Emulsions Stabilized by Sodium Caseinate or Whey Protein Isolate as influenced by Glycerol Monostearate

Competitive adsorption between glycerol monostearate (GMS) and whey protein isolate (WPI) or sodium caseinate was studied in oil-in-water emulsions (20 wt % soya oil, deionized water, pH 7). Addition of GMS resulted in partial displacement of WPI or sodium caseinate from the emulsion interface. SDS-PAGE showed that GMS altered the adsorbed layer composition in sodium caseinate stabilized emulsions containing < 1.0 wt % protein. Predominance of β-casein at the interface in the absence of surfactant was reduced in the presence of GMS. The distribution of α-lactalbumin and β-lactoglobulin between the aqueous bulk phase and the fat surface in emulsions stabilized with WPI was independent of the concentration of added protein or surfactant.     

Retention of propanal in protein-stabilised tuna oil-in-water emulsions

Propanal concentrations in the static headspace (HS) above water, aqueous protein solutions and freshly made tuna oil-in-water emulsions spiked with propanal (an indicator of omega-3 fatty acid oxidation) were compared. In the presence of proteins, HS propanal concentration was reduced and its decrease above aqueous hydrolysed whey protein isolate (HWPI) solutions was significantly greater than that above whey protein isolate (WPI) solutions. Similar trends were found for emulsions stabilised by HWPI and WPI. The results suggested that there was stronger binding of propanal to HWPI compared to WPI. Emulsification decreased the HS propanal concentration even further for both the WPI and HWPI matrices, but its effect was less in comparison to the protein type. Phosphate buffer decreased the HS propanal concentration, but this effect was minor. The difference in the release of propanal from protein stabilised tuna oil-in-water emulsions was interpreted in terms of the chemical interaction between propanal and protein.     

Monitoring air/liquid partition of mastic gum oil volatiles in model alcoholic beverage emulsions: Effect of emulsion composition and oil droplet size

The purpose of this work was to study the impact of the structure and composition of hydroalcoholic emulsions on the air–liquid partition of aroma compounds of the essential oil of Pistacia lentiscus var. chia, commonly known as mastic gum oil (mainly consists of terpenes). Oil-in-water emulsions (φ = 0.17), containing 15% (v/v) ethanol, stabilized by three different emulsifiers (sodium caseinate, whey protein isolate and Tween 40), were prepared by using two different lipid phases (sunflower oil and anhydrous butter fat). The homogenization conditions were varied to obtain emulsions with different volume–surface mean diameters. The partition of the volatile compounds between air phase and emulsions at three different temperatures (25, 37 and 50 °C) was monitored by applying the Headspace Solid Phase Microextraction technique, followed by gas chromatography–mass spectrometry (GC–MS) analysis. In general, the results obtained showed that sodium caseinate was the most effective in retaining mastic aroma compounds, while WPI was the least effective. This could partly be explained by the different structure of the two proteins which, when adsorbed at the interface, form a membrane that acts as a barrier and influences the partition of the aroma compounds between the air and the liquid. At the same time interactions of aroma compounds with the two proteins in the bulk phase may also play a role. The retention of the aroma compounds depended on the oil droplet size only in the case of sodium caseinate containing emulsions at 37 and 50 °C. This behaviour could be due to the substantial increase in the thickness of the adsorbed casein layer when moving from a fine sized emulsion to one with a much larger size as well as to differences in the ratio of free to adsorbed emulsifier. The composition of the lipid phase also appeared to have a significant impact on the concentration of volatile compounds in the headspace of mastic gum oil containing emulsions stabilized by proteins. This was lower in the case of butter fat probably due to differences in composition with regard to fatty acid degree of saturation as well as to volatile absorption by the liquid lipid at 40 °C and subsequent entrapment in the semisolid fat at 25 °C.     

Lipid oxidation in n-3 fatty acid enriched Dutch style fermented sausages

Dutch style fermented sausages were manufactured with a substitution of 10%, 15% and 20% of pork backfat by flaxseed oil and canola oil, pre-emulsified with soy protein isolate. The 15% and 20% substitution were also reached by adding encapsulated flaxseed oil and encapsulated fish oil and by adding flaxseed oil, pre-emulsified with sodium caseinate, respectively. The products were sliced, packaged in an oxygen-enriched atmosphere and stored in the dark for 12 weeks at 7°C. No differences were detected in moisture, protein and fat content between control and modified sausages, with the exception of the formulation with sodium caseinate. The PUFA/SFA ratio increased from 0.30 in the control to 0.42-0.48 in the sausages with canola oil and to 0.49-0.71 in the sausages with flaxseed oil. The n-6/n-3 ratio decreased from 11.20 in the control to 6.94-5.12 in the sausages with canola oil and to 1.93-1.05 in the sausages with flaxseed oil. The addition of canola oil and encapsulated flaxseed oil resulted in a comparable shelf life as the control in terms of lipid oxidation. In the samples with addition of pre-emulsified flaxseed oil, especially with sodium caseinate, lipid oxidation clearly increased during storage. Physical and sensory analysis showed that the sausages with encapsulated fish oil and flaxseed oil resembled the control most.     

Effect of composition and antioxidants on the oxidative stability of fluid milk supplemented with an algae oil emulsion

The oxidative stability of an algal oil emulsion dispersed in water, or fluid milk of varying fat contents, was assessed from measurements of lipid hydroperoxide and propanal concentration. All of the milk samples, independent of their milk fat content, were stable compared to the aqueous samples. The extent of oxidation was unaffected when sodium azide (200 ppm) was added to inhibit microbial growth. Added iron (100 ppm) accelerated the oxidation rate in the aqueous samples, but had no effect on the milk samples. The antioxidant properties of milk were ascribed to the iron binding of casein. Added protein antioxidants (0.8 wt%) [i.e. sodium caseinate, whey protein isolate (WPI) and thermally denatured WPI] had minimal effects whereas EDTA and ascorbic acid (160 ppm) were effective antioxidants.     

Low-fat frankfurters formulated with a healthier lipid combination as functional ingredient: microstructure, lipid oxidation, nitrite content, microbiological changes and biogenic amine formation

Oil (healthier lipid combination of olive, linseed and fish oils)-in-water emulsions stabilized with different protein systems (prepared with sodium caseinate (SC), soy protein isolate (SPI), and microbial transglutaminase (MTG)) were used as pork backfat replacers in low-fat frankfurters. Microstructure, lipid oxidation, nitrite content, microbiological changes and biogenic amine formation of frankfurters were analyzed and found to be affected by the type of oil-in-water emulsion and by chilling storage (2° C, 41 days). Although the lipid oxidation levels attained were low, replacement of animal fat by healthier oil combinations in frankfurter formulation did promote a slight increase in lipid oxidation. Residual nitrite was affected (P < 0.05) by formulation and storage. Only 51-61% of the added nitrite was detectable in the product after processing and 17-46% at the end of storage. The microbial population was low in all formulations during chilling storage. Spermine was the most abundant amine (19-20 mg/kg), but similar in level to all samples.     

Oxidatively Derived Volatile Compounds in Microencapsulated Fish Oil Monitored by Solid-phase Microextraction (SPME)

The stability of microencapsulated fish oil was studied during storage at 4 °C for up to 20 wk. Different coating mixtures consisting of gelatin or caseinate in blends with carbohydrates (sucrose, lactose, maltodextrin) were investigated. Oxidative stability of the microencapsulated fish oil was monitored by analysis of volatile compounds using gas chromatography olfactometry (GC‐O) or GC flame ionization (GC‐FID) (SPME‐HS‐GC/O or GC/ FID and HS‐GC/MS), Oxipres test, thiobarbituric acid‐reactive substances (TBARS), and sensory analysis. Coating mixture of caseinate and lactose showed slightly better stability than the sucrose and maltodextrin caseinate mixtures. Combination of fish gelatin and maltodextrin did not show as good oxidative stability as the coating blend of caseinate, lactose, and lecithin. Hexanal, 2‐nonenal and 2,4‐decadienals were selected as quality indicators to monitor the lipid oxidation during storage of the samples. SPME‐GC‐O analysis of these indicators showed that they were representative for the oxidation occurring in the microencapsulated fish oil. SPME‐GC‐FID analysis was sensitive enough to detect oxidative changes during storage. Oxidative stability test, TBARS results, and sensory analysis were in agreement with the SPME, indicating that SPME (polydimethylsiloxane/divinylbenzene [PDMS/ DVB] fiber) can be a useful tool for rapid analysis of lipid oxidation in microencapsulated fish oil.     

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.