Influence of sucrose on droplet flocculation in hexadecane oil-in-water emulsions stabilized by beta-lactoglobulin

The influence of sucrose on the flocculation stability of hydrocarbon oil-in-water emulsions stabilized by a globular protein was examined using laser diffraction. Salt (150 mM NaCl) and sucrose (0-40 wt %) were added to n-hexadecane oil-in-water emulsions stabilized by beta-lactoglobulin (beta-Lg, pH 7.0) either before or after isothermal heat treatment (30-95 degrees C for 20 min). When salt was added to emulsions before heat treatment, appreciable droplet flocculation was observed below the thermal denaturation temperature of the adsorbed beta-Lg (T(m) approximately 70 degrees C), and more extensive flocculation was observed above T(m). On the other hand, when salt was added to emulsions after heat treatment, appreciable droplet flocculation still occurred below T(m), but little flocculation was observed above T(m). Addition of sucrose to the emulsions increased T(m) and either promoted or suppressed droplet flocculation depending on whether it was added before or after heat treatment. These results are interpreted in terms of the influence of sucrose on protein conformational stability, protein-protein interactions, and the physiochemical properties of aqueous solutions. This study has important implications for the formulation and production of protein stabilized oil-in-water emulsions.     

Impact of protein surface denaturation on droplet flocculation in hexadecane oil-in-water emulsions stabilized by beta-lactoglobulin

The influence of globular protein denaturation after adsorption to the surface of hydrocarbon droplets on flocculation in oil-in-water emulsions was examined. n-Hexadecane oil-in-water emulsions (pH 7.0) stabilized by beta-lactoglobulin (1-wt % beta-Lg) were prepared by high-pressure valve homogenization. NaCl (0-150 mM) was added to these emulsions immediately after homogenization, and the evolution of the mean particle diameter (d) and particle size distribution (PSD) was measured by laser diffraction during storage at 30 degrees C for 48 h. No change in d or PSD was observed in the absence of added salt, which indicated that these emulsions were stable to flocculation. When 150 mM NaCl was added to emulsions immediately after homogenization, d increased rapidly during the following few hours until it reached a plateau value, while the PSD changed from monomodal to bimodal. Addition of N-ethylmaleimide, a sulfhydryl blocking agent, to the emulsions immediately after homogenization prevented (at 20 mM NaCl) or appreciably retarded (at 150 mM NaCl) droplet flocculation. These data suggests that protein unfolding occurred at the droplet interface, which increased the hydrophobic attraction and disulfide bond formation between droplets. In the absence of added salt, the electrostatic repulsion between droplets was sufficient to prevent flocculation, but in the presence of sufficient salt, the attractive interactions dominated, and flocculation occurred.     

Lipoxygenase and hydroperoxide lyase activities in ripening strawberry fruits

The enzymes lipoxygenase and hydroperoxide lyase have been identified in strawberry (Fragariax ananassa Duch.) var. Camarosa. Their subcellular localization, substrate preference, and product specificity were determined in mature strawberry fruits. The activity of both enzymes was located mainly in the microsomal fraction. Linolenic acid was the preferred substrate for strawberry lipoxygenase, forming 13- and 9-hydroperoxides of this acid in the proportion 70:30. The strawberry hydroperoxide lyase cleaves 13-hydroperoxide of linoleic (13% relative activity) and linolenic (100% relative activity) acids to form hexanal and (3Z)-hexenal, respectively. Both enzyme activities and endogenous content of volatile aldehydes formed by sequential action of lipoxygenase-hydroperoxide lyase were evaluated during strawberry development and ripening. A sequential enzymatic pathway for the formation of green odor compounds in strawberry is proposed.     

Factors affecting lycopene oxidation in oil-in-water emulsions

Evidence that dietary lycopene decreases the risk for a number of health conditions has generated new opportunities for the addition of lycopene to functional foods. This work examined the potential of oil-in-water emulsions as a lycopene delivery system for foods. Oil-in-water emulsions containing lycopene were prepared using different kinds of surfactant (cationic, anionic, and nonionic) and oil types (corn oil, stripped corn oil, and hexadecane). The formation of fatty acid oxidation products and the degradation of lycopene and tocopherol were then monitored. Fatty acids and lycopene had greater stability in oil-in-water emulsions stabilized by cationic dodecyltrimethylammonium bromide (DTAB) or nonionic polyoxyethylene (23) lauryl ether than by anionic sodium dodecyl sulfate (SDS). Oxidative stability in the corn oil-in-water emulsions stabilized by SDS was in the following order: tocopherolhexadecane>tocopherol-stripped corn oil. Lycopene degradation rates were similar in emulsions with and without fatty acids, suggesting that lycopene loss was independent of the presence of fatty acids. These results suggest that the stability of lycopene in oil-in-water emulsions could be inhibited by altering the emulsion droplet interface and by the presence of tocopherols.     

Ethylene production and decomposition in soils

Six soils differing in texture and use were investigated for their ability to produce and decompose ethylene. In addition, changes in methane and CO₂ concentrations were monitored. The effects of organic amendments and different water tensions were studied, and a method using low concentrations of acetylene as an inhibitor of ethylene degradation was tested. Possible reduction of acetylene to ethylene was identified by the use of CO or NH₄ ⁺-N, of which the latter turned out to be the more reliable method. This reduction only occurred in a grassland soil. Under aerobic soil conditions, gross ethylene production rates of up to 4.7pmol g^–1 h^–1 could be measured. Highest ethylene production and lowest ethylene decomposition was detected in a spruce forest soil. Fine textured soils produced more ethylene than coarse textured soils. Amended soils produced more ethylene at –100kPa and –5kPa than at 0kPa water tension. Ethylene decomposition was most effective in soils from deciduous woodlands and reached rates of up to 137pmol g^–1 h^–1. Parallels between ethylene and methane decomposition were observed. The addition of 5mgg^–1 glucose and 1mgg^–1 methionine not only promoted ethylene production but also inhibited ethylene decomposition. Received: 4 April 1997     

Use of caseinophosphopeptides as natural antioxidants in oil-in-water emulsions

Chelators are valuable ingredients used to improve the oxidative stability of food emulsions. Caseins and casein peptides have phosphoseryl residues capable of binding transition metals. Thus, the ability of enriched caseinophosphopeptides to inhibit lipid oxidation in corn oil-in-water emulsions was investigated. Enriched caseinophosphopeptides (25 microM) inhibited the formation of lipid oxidation at both pH 3.0 and 7.0 as determined by lipid hydroperoxides and hexanal. Calcium (0-100 mM) had no influence on the antioxidant activity of the enriched caseinophosphopeptides. Casein hydrolysates were more effective inhibitors of lipid oxidation than the enriched caseinophosphopeptides at equal phosphorus content. Thus, antioxidant properties might not be uniquely attributed to chelating metals by phosphoseryl residues but also by scavenging free radicals. Overall, the observed antioxidant activity of casein hydrolysates means they could be utilized to decrease oxidative rancidity in foods.     

Factors influencing the antioxidant and pro-oxidant activity of polyphenols in oil-in-water emulsions

The nonenzymatic oxidation of polyphenols bearing di- and trihydroxyphenol groups results in the generation of hydrogen peroxide (H?O?), a reactive oxygen species that can potentially compromise the oxidative stability of foods and beverages. An investigation of the factors that promote the oxidation of a model polyphenol, (-)-epigallocatechin-3-gallate (EGCG), was undertaken in a model lipid-based food system. Factors affecting oxidative stability, such as exogenous iron chelators (ethylenediaminetetraacetic acid; EDTA and 2,2-bipyridine; BPY) and pH (3 and 7) were evaluated in hexadecane and flaxseed oil-in-water (o/w) emulsions. At neutral pH, H?O? levels were observed to rise rapidly in hexadecane emulsions except for EDTA-containing treatments. However, EDTA-containing samples showed the highest rate of EGCG oxidation, suggesting that H?O? was rapidly reduced to hydroxyl radicals (HO?). Conversely, at pH 3, H?O? concentrations were lower across all treatments. EDTA conferred the highest degree of EGCG stability, with no loss of the catechin over the course of the study. In order to assess whether or not the H?O? production seen in oxidatively stable hexadecane emulsions translated to pro-oxidant activity in an oxidatively labile food lipid system, the effect of EGCG on the stability of flaxseed o/w emulsions was studied. EGCG displayed antioxidant activity at pH 7 throughout the study; however at pH 3, pro-oxidant activity was seen in EGCG-containing emulsions, with and without BPY. This study attempts to provide a mechanistic understanding of the conditions wherein polyphenols simultaneously exert pro-oxidant and antioxidant behavior in lipid dispersions.     

Lipid hydroperoxide induced oxidative stress damage and antioxidant enzyme response in Caco-2 human colon cells

It has been demonstrated that reactive oxygen species, free radicals, and oxidative products, such as lipid hydroperoxides, participate in tissue injuries and in the onset and progression of degenerative diseases in humans. Studies were conducted using Caco-2 colon carcinoma cells to evaluate cellular damage caused by exposing cells for 30 min to oleic acid hydroperoxides (OAHPx) at concentrations varying from 0 to 25 microM. Cell membrane damage and DNA damage were significantly high even at the lowest concentration of 2.5 microM OAHPx compared to the control. Cell lipid peroxidation, indicated by conjugated diene concentration, increased exponentially with increasing OAHPx concentration. Antioxidant mechanisms in Caco-2 cells were evaluated by measuring catalase, superoxide dismutase (SOD), and glutathione peroxidase (GPx) activities. Cellular catalase and GPx activities were not significantly different from each other at 0 to 25 microM OAHPx concentrations. SOD activity decreased with increasing OAHPx concentration. These results show that existing enzymatic antioxidant mechanisms are not sufficient for complete detoxification of 5-25 microM lipid hydroperoxides.     

Stability of citral in emulsions coated with cationic biopolymer layers

Multilayer emulsions containing citral were prepared by the layer-by-layer deposition technique based on the electrostatic interaction between negatively charged emulsion droplets and two positively charged biopolymer coatings, chitosan (CS) and ε-polylysine (EPL). The optimum concentrations of both CS and EPL were determined through the ζ-potential and particle size measurements and were found to be 1.5 mg/mL for CS and 6 mg/mL for EPL. Quartz crystal microbalance with dissipation monitoring (QCM-D) was conducted to monitor the binding between emulsion droplets and cationic polymers, and our results proved the existence of strong interactions between emulsions and the cationic polymer coatings. The stability of citral and the production of the off-flavor compounds were analyzed by solid-phase microextraction gas chromatography (SPME-GC). The results suggested that the addition of the cationic CS interfacial layer was effective in improving the stability of citral during storage.     

Lipid hydroperoxide determination in dark chicken meat through a ferrous oxidation-xylenol orange method

A ferrous oxidation-xylenol orange (FOX) method was adapted to measure lipid hydroperoxides (LHP) in raw and cooked dark chicken meat. Its applicability was evaluated using samples with different alpha-tocopherol contents or unsaturation degrees (both modulated by dietary supplementation). The FOX assay can work as an induced method because there is some oxidation of the sample extract during the incubation of the reaction. Consequently, it allows assessment of sample susceptibility to oxidation (response after some hours of incubation) and comparison of samples that are highly oxidized or readily susceptible to oxidation through their absorbance after 30 min of incubation. It is highly specific for LHP and showed a linear relationship between volume of meat extract and absorbance. However, the most suitable volume of extract and incubation time must be studied for each kind of sample. The use of butylated hydroxytoluene during this incubation is strongly discouraged because it attenuated the reaction by radical stabilization, thus diminishing Fe(III) formation and leading to a lower response.     

Density and microviscosity studies of palm oil/water emulsions

Electron paramagnetic resonance (EPR) and densitometry were used to measure the temperature- and rate-dependent formation of fat crystals in emulsion droplets in hardened palm kernel oil in water emulsions. The solid fat content in emulsions can be critical for the functionality of the emulsions in a wide variety of applications. Therefore, new and accessible methods are needed to monitor solid fat content in order to control the functional properties of these emulsions. EPR measurements showed that the microviscosity within the oil droplets could be measured as a function of temperature and that the storage temperature below the main fat melting point is crucial for an increase in the microviscosity, due to fat solidification. The microviscosity of the oil droplets could be an important parameter for defining functional performance (e.g., rheology and partial coalescence). Density measurements provided a simple and accurate method for monitoring changes in phase state of the oil. The phase behavior agreed well with the EPR results, demonstrating that accurate density measurements could prove to be a valuable tool for monitoring fat crystallization processes.     

Antioxidant activity of selected Spanish wines in corn oil emulsions

Wines contain phenolic compounds that may be useful for preventing lipid oxidation as dietary antioxidants. This study was aimed at evaluating the antioxidant activity in corn oil emulsions of seventeen selected Spanish wines and two California wines. The inhibition of hydroperoxide formation at 10 microM gallic acid equivalents (GAE) varied from 8.4% to 40.2% with the red wines, from 20.9% to 45.8% with the rosé wines, and from 6.5% to 47.0% with the white wines. The inhibition of hydroperoxide formation at 20 microM GAE varied from 11.9% to 34.1% with the red wines, from 0.1% to 34. 5% with the rosé wines, and from 3.3% to 37.2% with the white wines. The inhibition of hexanal formation at 10 microM GAE varied from 23. 6% to 64.4% with the red wines, from 42.7% to 68.5% with the rosé wines, and from 28.4% to 68.8% with the white wines. The inhibition of hexanal formation at 20 microM GAE varied from 33.0% to 46.3% with the red wines, from 11.3% to 66.5% with the rosé wines, and from -16.7% to +21.0% with the white wines. The antioxidant effect decreased with increasing concentration. This antioxidant activity was related to the five main groups of phenolic compounds identified in wines by HPLC. The relative antioxidant activity correlated positively with the total phenol content of wines (by the Folin-Ciocalteu method and by HPLC), benzoic acids, anthocyanins, flavan-3-ols, and flavonols, for the inhibition of hydroperoxides and hexanal at 10 and 20 microM GAE.     

Titrimetric determination of nonesterified fatty acids in intravenous fat emulsions

A titrimetric method, suitable for use at a limit of 5 mEq/L, has been developed for the determination of total nonesterified fatty acids in intravenous fat emulsion preparations. The method differentiates titrant consumed by the nonesterified fatty acids from that consumed by egg yolk phospholipids, usually present as an emulsifying agent. The total nonesterified fatty acids in 8 products from 4 manufacturers were in the range from 0.4 to 3.8 mEq/L. The mean standard deviation of the method is 0.09 mEq/L.     

Color changes in hydrocarbon oil-in-water emulsions caused by Ostwald ripening

The influence of Ostwald ripening on the optical properties of hydrocarbon oil-in-water emulsions stabilized by sodium dodecyl sulfate was investigated. The droplet size, spectral reflectance, and tristimulus color coordinates (L, a, and b) of a series of n-hexadecane and n-octadecane oil-in-water emulsions were measured in the presence and absence of a water-soluble red dye (FD&C Red No. 40). The droplets grew more rapidly in the emulsion containing n-hexadecane than in the emulsion containing n-octadecane because of the higher solubility of n-hexadecane molecules in the aqueous phase. Ostwald ripening caused appreciable changes in n-hexadecane emulsion spectral reflectance and color L, a, and b values due to the growth of emulsion droplets. L, a, and b color values and spectral reflectances of n-octadecane emulsions did not significantly change during the course of the experiment. The results were explained in terms of Ostwald ripening theory and a previously described light scattering theory. The model enables emulsion manufacturers to predict color changes in oil-in-water emulsions that exhibit transcondensational ripening.     

Role of hydrocolloids in the creaming of oil in water emulsions

The influence of guar gum and xanthan gum on the creaming of 10% oil in water emulsions has been investigated. The presence of very low concentrations of the polysaccharides (typically < approximately 0.075%) was found to induce depletion flocculation of the emulsion droplets and increased the rate of creaming. However, at higher polysaccharide concentrations (typically > approximately 0.1%) the creaming rate was reduced due to the increased viscosity of the aqueous phase. For most systems a delay period was noted before creaming started, which was found to be dependent on the zero shear viscosity of the continuous phase and independent of polysaccharide type. The delay period increased significantly at zero shear viscosities approaching 1 Pa s. A mathematical model has been used to fit the creaming rate profiles and a simple exponential relationship obtained between delay time and polysaccharide concentration.     

Lentil and chickpea protein-stabilized emulsions: optimization of emulsion formulation

Chickpea and lentil protein-stabilized emulsions were optimized with regard to pH (3.0-8.0), protein concentration (1.1-4.1% w/w), and oil content (20-40%) for their ability to form and stabilize oil-in-water emulsions using response surface methodology. Specifically, creaming stability, droplet size, and droplet charge were assessed. Optimum conditions for minimal creaming (no serum separation after 24 h), small droplet size (<2 μm), and high net droplet charge (absolute value of ZP > 40 mV) were identified as 4.1% protein, 40% oil, and pH 3.0 or 8.0, regardless of the plant protein used for emulsion preparation.     

Distribution of hydroxytyrosol and hydroxytyrosol acetate in olive oil emulsions and their antioxidant efficiency

We employed a kinetic method to determine the distributions of the antioxidants hydroxytyrosol (HT) and hydroxytyrosol acetate (HTA) between the oil, aqueous, and interfacial regions of a model food emulsion composed of stripped olive oil, acidic water, and a blend of Tween 80 and Span 80 [hydrophilic–lipophilic balance (HLB) = 8.05] as an emulsifier. HT is oil-insoluble, but HTA is both oil- and water-soluble (partition constant P(O)(W) = 0.61). Results indicate that, at a given emulsifier volume fraction Φ(I), the fraction of HTA in the interfacial region is higher than that of HT. The percentage of both antioxidants increases with an increasing Φ(I), so that % HT > 40% at Φ(I) = 0.005 and % HT > 80% at Φ(I) = 0.04. HTA appears to be a better antioxidant than HT, as shown by an accelerated oxidative test (Schaal oven method). A correlation between their distribution in the emulsion and their efficiency was established.     

Delayed volatile compound release properties of self-assembly structures in emulsions

Temporal release and retention of aroma compounds from structured emulsions (where unsaturated monoglycerides are added to the oil) and conventional oil-in-water emulsions were studied using in vitro dynamic headspace analysis by proton-transfer reaction mass spectrometry and static headspace analysis by gas chromatography-mass spectrometry. Under dynamic conditions, the structured emulsion exhibited delayed release compared to the oil-in-water emulsion containing the same lipid content of 5%. The time to maximum concentration T max of amphiphilic and lipophilic aroma compounds increased by a factor of 1.2 (for 3 E-hexenal) to 1.9 (for octanal). The aroma release profile of the 5% lipid structured emulsion was close to that obtained for the oil-in-water emulsion containing 10% lipid. Under static conditions, the 5% lipid structured emulsion retained more of the most lipophilic aroma compounds than its counterpart 5% oil-in-water nonstructured emulsion. The present study provides potential solutions for modulating aroma release profiles of reduced-fat foods by self-assembly structures.     

大豆油体乳液稳定性和流变性分析

研究大豆油体乳液的基本物理化学性质,将为其工业应用提供参考。以水为介质提取大豆油体,方法无毒,利于食用。对其在不同pH值（pH值2～8）、NaCl浓度（0～250?mmol/L）和加热处理（30～90℃,30?min）条件下的Zeta电位、平均粒径和乳析稳定性进行测定,并对其流变性进行考察。大豆油体乳液的Zeta电位为+20?mV～-40?mV（pH值2～8）,等电点约为4.5。在pH值≤3和pH值≥6条件下,平均粒径均为0.4?μm左右;而在3＜pH＜6时,产生了乳析现象。在较高NaCl浓度下（＞25?mmol/L）,粒径较大和发生了乳析现象。大豆油体乳液在30～90℃加热处理时较稳定。大豆油体乳液呈现出弱凝胶的性质,其黏度随着油质量分数的降低而降低。研究表明,大豆油体乳液在一定的环境条件下是稳定的。     

Hydroxymethanesulphinate salts and related decomposition products in wastewater

Hydroxymethanesulphinate (HMS) and its decomposition products such as HCHO, Zn and sulphites can be determined quantitatively in each other's presence by a polarographic method. In the alkaline medium it is possible to have well defined and separated waves relative to the oxidation of HMS ion and to the reduction of HCHO and zincate ion. The quantitative determination of these compounds is carried out with standard addition methods since the concentration-current relationship is linear. The SO₂ is determined in HClO₄ 0.1 M and in the same sample it is possible to determine even HMS, HCHO and Zn after addition of NaOH up to 0.1 M. Moreover, a method of indirect determination of HMS is herein described. This is based on the determination of HCHO released by means of a weak oxidation of HMS which is stoichiometrically proportional to the total HMS. The method is sensitive and is made specific for such types of wastewater which come from textile industries.