Olive oil-in-water emulsions stabilized with caseinate: Elucidation of protein–lipid interactions by infrared spectroscopy

This paper reports a FT-IR study for probing lipid and protein structural changes and their interactions in various oil-in-water emulsions. Two different emulsions were prepared using sodium caseinate, as stabilizer system, without and with microbial transglutaminase (MTG), denominated E/SC and E/SC + MTG respectively. Proximate composition, fat and water binding properties and textural characteristics were also evaluated in the emulsions. Penetration force and gel strength values were used to distinguish different (P < 0.05) textural behaviours depending on the formulation of emulsifying system. E/SC + MTG emulsion showed gel textural behaviour while E/SC lack of this property. The spectral results showed frequency upshifting of the amide I band in going from protein stabilizer systems isolate (the solution used as reference) to their corresponding emulsions, what is attributable to greater protein structural order upon emulsion formation. Enzymatic action of MTG in the sodium caseinate stabilizing system induces structural changes, in terms of lipid chain disorder or lipid–protein interactions and protein secondary modifications, which may reflect the formation of a gel structure in the emulsion. These results could help to choose the stabilizing system that is most suitable and effective for its use in the formulation of food products.     

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.     

Impact of surface deposition of lactoferrin on physical and chemical stability of omega-3 rich lipid droplets stabilised by caseinate

There is considerable interest in developing delivery systems to encapsulate and protect chemically labile lipophilic food components, such as omega-3 rich oils. In this study, multilayer emulsion-based delivery systems were prepared consisting of omega-3 rich oil droplets coated by either caseinate (Cas) or lactoferrin–caseinate (LF–Cas). Surface deposition of LF onto Cas-coated oil droplets was confirmed by ζ-potential measurements. Emulsions containing lactoferrin and caseinate had better physical stability to pH changes and salt addition (pH 3–7, 0–50 mM CaCl₂ at pH 7) than those containing only caseinate (pH 5–7, 0–2 mM CaCl₂ at pH 7). The addition of LF also retarded the formation of lipid oxidation markers (hydroperoxides and thiobarbituric acid reactive substances) in the emulsions. The ability of LF to enhance both the physical and chemical stability of protein-stabilised emulsions is useful for the fabrication of delivery systems designed for utilisation within the drug and food industries.     

Diffusion, counter-diffusion and lipid phase changes occurring during oil migration in model confectionery systems

This study investigated the diffusion of peanut oil and counter-diffusion of cocoa butter when cylindrical tempered or untempered samples, composed of cocoa butter with or without addition of cocoa powder, were suspended in peanut oil and stored at 23 °C. Oil migration kinetics was monitored using a novel pipette technique while diffusion and counter-diffusion were measured using gas chromatography. Tempering significantly lowered (p < 0.05) the peanut oil diffusion in the samples but did not influence the counter-diffusion of cocoa butter in peanut oil. Addition of cocoa powder at a volume fraction of 0.45 significantly increased (p < 0.05) peanut oil diffusion and decreased counter-diffusion. Due to the ingress of peanut oil, the solid fat content of tempered and untempered cocoa butter samples dropped from 75% to 59% after 7 weeks and resulted in corresponding dimensional changes in the samples which were also measured using image analysis. Diffusion, counter-diffusion and lipid phase changes were combined to develop a mass balance model to predict the volume changes occurring during oil migration.     

Headspace volatile composition and oxidative storage stability of pressed marama bean (Tylosema esculentum) oil

Marama bean (Tylosema esculentum) is an underutilised legume indigenous to the Kalahari Desert region of southern Africa. The bean has high lipid content and hence is a potential source for production of edible oil. The headspace volatile composition of freshly pressed marama bean oil was explored and the oil was further studied during 7 months of storage under different light and temperature conditions. The oxidative stability of the oil was examined by measuring peroxide value, vitamin E content and FT-IR spectra. Additionally, the headspace volatile composition of the oil was investigated during storage by use of dynamic headspace GC–MS. The results showed that marama oil is highly stable and has good natural antioxidant properties; enzymatic lipid oxidation does not take place in marama oil. Light has a greater effect on the lipid oxidation than has temperature, and hence marama oil should preferably be stored in darkness and rather at 25 °C than 35 °C. Under these conditions, the marama oil has a shelf life of at least 7 months.     

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.     

The essential oil of Glossogyne tenuifolia

Glossogyne tenuifolia (Labill) Cass. (Compositae) is a traditional anti-pyretic and hepatoprotective herb in The Pescadores Islands. The essential oil of the dried herb, from four seasons, was isolated using a simultaneous steam-distillation and solvent-extraction (SDE) apparatus. The essential oil contents were in the range of 0.48–0.77 mg g⁻¹, with an average of 0.66 mg g⁻¹, and declined with the seasons. Generally, the essential oils from four seasons exhibited similar volatile profiles. A total of 62 different compounds were isolated by the SDE method and, among them, 30 compounds were identified, including 13 terpenes, 16 oxygen-containing compounds (eight alcohols, five aldehydes, one ester and two ketones) and one other compound. Terpenes were predominantly present in the essential oil and accounted for 61.3–76.0% of the essential oil with an average of 69.1%. The second most abundant class was alcohols, accounting for 12.4–15.9% of the essential oil, with an average of 14.1%. Consistently for four seasons, the most abundant eight compounds were in the descending order: p-cymene > β-pinene > β-phellandrene > limonene > cryptone > α-pinene > 4-terpineol + γ-muurolene. However, these eight compounds accounted for 71.5% of the average of the essential oil and, in combination, might give rise to the overall citrus-like aroma of the G. tenuifolia.     

Effect of thermal treatments on the properties of coconut milk emulsions prepared with surface-active stabilizers

Previously we have demonstrated improved stability of coconut milk emulsions homogenized with various surface-active stabilizers, i.e., 1 wt% sodium caseinate, whey protein isolate (WPI), sodium dodecyl sulfate (SDS), or polyoxyethylene sorbitan monolaurate (Tween 20) [Tangsuphoom, N., & Coupland, J. N. (2008). Effect of surface-active stabilizers on the microstructure and stability of coconut milk emulsions. Food Hydrocolloids, 22(7), 1233–1242]. This study examines the changes in bulk and microstructural properties of those emulsions following thermal treatments normally used to preserve coconut milk products (i.e., −20 °C, −10 °C, 5 °C, 70 °C, 90 °C, and 120 °C). Calorimetric methods were used to determine the destabilization of emulsions and the denaturation of coconut and surface-active proteins. Homogenized coconut milk prepared without additives was destabilized by freeze–thaw, (−20 °C and −10 °C) but not by chilling (5 °C). Samples homogenized with proteins were not affected by low temperature treatments while those prepared with surfactants were stable to chilling but partially or fully coalesced following freeze–thaw. Homogenized coconut milk prepared without additives coalesced and flocculated after being heated at 90 °C or 120 °C for 1 h in due to the denaturation and subsequent aggregation of coconut proteins. Samples emulsified with caseinate were not affected by heat treatments while those prepared with WPI showed extensive coalescence and phase separation after being treated at 90 °C or 120 °C. Samples prepared with SDS were stable to heating but those prepared with Tween 20 completely destabilized by heating at 120 °C.     

Effects of protein level and fat/oil on emulsion stability,texture, microstructure and color of meat batters

Beef meat batters formulated with increasing protein level (10–15%) and containing 25% beef fat were compared to batters prepared with 25% canola oil. Emulsion stability of the canola oil treatments was higher (less separation during cooking) at the 10–13% protein level compared to the beef fat treatments. However, above 13% protein this was reversed and the canola oil treatments showed high fat and liquid separation, which did not occur at all in the beef fat treatments. This indicates differences in stabilization of fat versus oil in such meat emulsions. Hardness of the cooked meat batters showed significantly (P < 0.05) higher values when the protein level was raised, and was higher in canola oil than in beef fat meat emulsions at similar protein levels. Products’ chewiness were higher in the canola oil treatments compared to the beef fat emulsions. Lightness decreased and redness increased in canola oil batters as the protein level was raised. The micrographs revealed the formation of larger fat globules in the beef fat emulsions compared to the canola oil meat emulsions. The canola oil treatment with 14% protein started to show fat globule coalescence, which could be related to the reduced emulsion stability.     

Quantitative analysis of volatiles in transesterified coconut oil by headspace-solid-phase microextraction-gas chromatography–mass spectrometry

A simple and fast headspace-solid-phase microextraction (HS-SPME) method coupled with gas chromatography–mass spectrometry (GC–MS) was developed for the analysis of volatile compounds in transesterified coconut oil by applying solvent dilution. Solvent dilution conditions (solvent type and solvent amount) and HS-SPME sampling parameters (adsorption temperature and time) were optimised through monitoring the adsorption result of the selected volatiles (octanoic acid esters) in transesterified coconut oil samples. The incubation of methanol (800 μl)-diluted oil (200 μl) sample at 60 °C for 30 min led to the best result. The method was further validated by determining the calibration linear range, correlation coefficient (R²), accuracy, precision, limit of detection and limit of quantification through spiking standards into the blank matrix consisting of coconut oil and methanol. This method may also be applicable for detection and determination of volatile compounds in other transesterified oil samples.     

Emulsification enhances the retention of esters and aldehydes to a greater extent than changes in the droplet size distribution of the emulsion

The physicochemical and organoleptic properties of an emulsion depend on the way the constituents interact with one another to form emulsion droplets, interfacial region and continuous phase. The objective of this work was to evaluate the respective impact of both the emulsification and the modification of the properties of an emulsion, such as the droplet size distribution, on the partition of aroma compounds. The emulsions were prepared with sodium caseinate and the low melting point fraction of anhydrous milk fat (Φ = 0.3). Their volume-surface mean droplet size ranged from 1.8 to 0.3 μm. Results showed that the measured partition coefficients of ethyl pentanoate, isoamyl acetate, hexanal and t-2-hexenal were lower than the calculated ones from values measured separately over continuous and dispersed phases. The droplet size distribution had no significant impact on the partition coefficient of the three esters whereas, for a volume-surface mean diameter below 0.5 μm, the partition coefficients of the two aldehydes were drastically reduced. The greater retention is not related to the sodium caseinate remaining in the continuous phase of the emulsion. The formation of an interfacial area seems to govern the partition of aroma compounds in emulsions.     

Scaled-up production of zero-trans margarine fat using pine nut oil and palm stearin

An interesterified structured lipid was produced with a lipid mixture (600 g) of pine nut oil (PN) and palm stearin (PS) at two weight ratios (PN:PS 40:60 and 30:70) using lipase (Lipozyme TL IM, 30 wt.%) as a catalyst at 65 ^°C for 24 h. Major fatty acids in the interesterified products were palmitic (35.1–40.4%), oleic (29.5%), and pinolenic acid (cis-5, cis-9, cis-12 18:3; 4.2–5.9%). α-Tocopherol (1.1–1.3 mg/100 g) and γ-tocopherol (0.3–0.4 mg/100 g) were detected in the interesterified products. Total phytosterols (campesterol, stigmasterol, and β-sitosterol) in the interesterified products (PN:PS 40:60 and 30:70) were 63.2 and 49.6 mg/100 g, respectively. Solid fat contents at 25 ^°C were 23.6% (PN:PS 40:60) and 36.2% (PN:PS 30:70). Mostly β′ crystal form was found in the interesterified products. Zero-trans margarine fat stock with desirable properties could be successfully produced from pine nut oil and palm stearin.     

Estimation of the oil water partition coefficient,experimental and theoretical approaches related to volatile behaviour in milk

Oil/water partition coefficients (K_ow) of 20 volatile compounds in model or milk-based emulsions were determined experimentally using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS). The K_ow values were estimated by comparing the headspace concentration of volatiles above solutions with different lipid content (2, 7, 12, 27, 62 and 102 g/L). This involved curve fitting of a series of the six experimental values to an equation describing the expected behaviour of volatiles in lipid containing systems. Alternatively, a simpler experimental method based on the comparison of only two samples was used. Overall, the K_ow values determined in the milk-based emulsion were the same as those found in simple model emulsions, suggesting that the partitioning behaviour of volatiles between air and the two emulsion systems was the same. The Log P values of the 20 volatile compounds were calculated using four software programmes, the Log P values from EPI Suite™ were found to correlate best with experimental Log K_ow values.     

Oxidative and thermal stabilities of genetically modified high oleic sunflower oil

The oxidative and thermal stabilities of genetically modified high oleic sunflower oil (87% oleic acid) were compared with those of regular sunflower (17% oleic acid), soybean, corn, and peanut oils during storage at 55 °C and simulated deep fat frying at 185 °C. Oxidative stability was evaluated by measuring the oxygen content and volatile compounds in the sample bottle headspace and peroxide value. The coefficient variations (CVs) for volatile compound, headspace oxygen, and peroxide value analyses were 2.02%, 1.41%, and 3.18%, respectively. The oxidative stability of high oleic sunflower oil was greater than those of regular sunflower and soybean oil (P < 0.05) and as good as those of corn and peanut oils (P > 0.05). The thermal stabilities of oils during deep fat frying were evaluated by measuring the infrared absorption at 2.9 μm and conjugated diene content. The CV of conjugated diene content was 1.07%. Infrared and conjugated diene results showed that the high oleic sunflower oil had greater thermal stability than had regular sunflower, soybean, corn, and peanut oils (P < 0.05). The genetically modified high oleic sunflower oil, with 5.5% linoleic acid, had better oxidative and thermal stabilities than had the regular sunflower oil with 71.6% linoleic acid.     

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.     

Co-encapsulation of fish oil with phytosterol esters and limonene by milk proteins

Co-encapsulated microcapsules containing three lipophilic bioactive components (LBCs) including fish oil, phytosterols and limonene were studied and compared with those containing only fish oil. Milk proteins (whey protein isolate and sodium caseinate in a ratio of 4:1) were used as wall materials. Results show that good quality microcapsules can be obtained at inlet temperature of 170 °C and outlet temperature of 70 °C, with the wall to core ratio of 4:1. There was no significant different (p > 0.05) in the microencapsulation efficiency and the oxidation indicators (PV and AV) after the accelerated storage for both types of microcapsules. However, the retention of EPA and DHA in the LBCs-microcapsules was significantly higher (p < 0.05) than the fish oil microcapsules. The phytosterols content was unchanged but loss of limonene occurred after storage. The LBCs-microcapsules had better flavor/odour profile than the fish oil microcapsules after drying and storage.     

Sodium caseinate/carboxymethylcellulose interactions at oil–water interface: Relationship to emulsion stability

The effect of carboxymethylcellulose (CMC) on the properties of oil-in-water emulsions prepared with sodium caseinate (CN) was studied at different pHs (4–7). At pH 7, the surface protein coverage increased gradually with increasing CMC concentration, followed by a preferential adsorption of β-casein. While at pH 4, a sharp decrease in surface protein coverage was noted between 0 and 0.3 wt.% CMC, and no obvious difference in protein composition was observed. ζ-Potential measurements indicated that CMC adsorbed onto the CN-coated droplets at pH 4–5, but not at pH 6–7. As a result, the excess of non-adsorbed CMC induced depletion flocculation in the neutral emulsions. However, the acidic emulsions containing high levels of CMC (>0.3 wt.%) remained stable after 60 days of storage due to the formation of multilayer structures. At pH 4, CMC desorbed from the droplet surfaces at high NaCl concentrations, leading to lower emulsion stability.     

Physicochemical characterisation and oxidative stability of fish oil and fish oil–extra virgin olive oil microencapsulated by sugar beet pectin

Spray-dried microcapsules were prepared at 25% and 50% w/w oil load from sugar beet pectin-stabilised emulsions (pH 3) containing fish oil, and a blend of fish oil and with extra virgin olive oil (1:1 w/w). Microencapsulation efficiencies were high (≥90%). However, deterioration in microcapsule wall integrity and an increase in oil droplet size were observed during storage (25 °C, 0–3 months). Lipid oxidation increased with both increased oil load (P < 0.05) and storage duration (P < 0.05), but was independent of oil composition (P > 0.05). These results suggest that sugar beet pectin functions poorly as a wall material and its residual metal ions exacerbate omega-3 oxidation, despite the presence of endogenous antioxidants found in extra virgin olive oil. Interestingly, under accelerated storage conditions (OxiPres® at 80 °C, 0.5 bar oxygen pressure), microcapsules containing the oil blend showed the best oxidative stability (P < 0.05), irrespective of oil load. A possible explanation for the superior oxidative stability of the microencapsulated oil blend at high storage temperature is discussed.     

Influence of temperature and NaCl on the release in aqueous liquid media of aroma compounds encapsulated in edible films

This work analyses the release of n-hexanal and d-limonene from edible films, previously encapsulated in the iota-carrageenan matrix (with and without lipid). Both volatile compounds have different physico-chemical properties. The effect of temperature (25 °C and 37 °C) and dissolution medium (water and 0.9% NaCl) on the release and retention of aroma compounds were studied. Hydrophobicity and wettability properties of active iota-carrageenan films were also studied and they were related with the internal and surface microstructure of films. Results highlight that d-limonene is encapsulated in the lipid phase of the films decreasing the release in the salt medium. d-limonene, the most hydrophobic, was more sensitive to the temperature changes than hexanal. Thus, this work gives an idea of the release of aroma compounds encapsulated in iota-carrageenan films in aqueous media.     

The effect of butter grains on physical properties of butter-like emulsions

Milk fat exists as globules in its natural state in milk. The potential of using globular fat to modulate the rheological properties and crystallization behavior in butter-like emulsions was studied in the present work. We conducted a comparative study of butter-like emulsions, with a fat phase consisting of 0, 10, 25, 50, or 100% anhydrous milk fat (AMF), the remaining fat being butter grains, and all samples containing 20% water, to obtain systematic variation in the ratio of globular fat. All emulsions were studied over 4 wk of storage at 5°C. By combining small and large deformation rheology, we conducted a detailed characterization of the rheological behavior of butter-like emulsions. We applied differential scanning calorimetry to monitor thermal behavior, confocal laser scanning microscopy for microstructural analysis, and low-field pulsed nuclear magnetic resonance spectrometry to measure solid fat content. By combining these techniques, we determined that increasing the fraction of globular fat (by mixing with butter grains) decreases the hardness of butter-like emulsions up to an order of magnitude at d 1. However, no difference was observed in thermal behavior as a function of butter grain content, as all emulsions containing butter grains revealed 2 endothermal peaks corresponding to the high (32.7°C ± 0.6) and medium (14.6°C ± 0.1) melting fractions of fatty acids. In terms of microstructure, decreasing the amount of butter grains in the emulsions resulted in formation of a denser fat crystal network, corresponding to increased hardness. Moreover, microstructural analysis revealed that the presence of butter grains resulted in faster formation of a continuous fat crystal network compared with the 100% AMF sample, which was dominated by crystal clusters surrounded by liquid oil. During storage, hardness remained stable and no changes in thermal behavior were observed, despite an increase in solid fat content of up to 5%. After 28 d of storage, we observed no difference in either microstructural or rheological properties, indicating that formation of primary bonds occurs primarily within the first day of storage. The rheological behavior of butter-like emulsions is not determined solely by hardness, but also by stiffness related to secondary bonds within the fat crystal network. The complex rheological behavior of milk fat-based emulsions is better characterized using multiple parameters.