Effect of sunflower lecithins on the stability of water-in-oil and oil-in-water emulsions

Lecithins are frequently applied in the food industry as emulsifiers, viscosity regulators, and dispersing agents. The main aim of the present work was to study the emulsifying capability of diverse sunflower lecithins so as to evaluate the functionality of these by-products, which are not extensively used at present. The experimental results obtained for water-in-oil (W/O) emulsions showe that dispersions containing levels of 0.1% lecithins were more stable against coalescence than a control system, whereas those with 1% emulsifying agent exhibited the opposite behavior. On the other hand, faster sedimentation kinetics were observed at a concentration of 0.1% than at 1%. Lecithins with high phospholipid content, especially phosphatidylethanolamine and phosphatidylinositol, were found to be the best emulsifying agents for W/O dispersions. In the case of oil-in-water emulsions, it was possible to observe two processes: creaming of emulsions with the addition of 1% of lecithins, and instant creaming followed by coalescence of the cream phase in those cases corresponding to 0.1% added lecithin.     

Fractionation of oligomeric triacylglycerides and the relation to rejection limits for used frying oils

Precipitates enriched in oligomeric triacylglycerides were separated from thermally oxidized olive residue oil, conventional and high-oleic sunflower oils, and soybean oil by solvent fractionation in methanol/acetone at 4–5°C for 16 h. Different fractionation conditions were evaluated in an effort to isolate the oligomeric triacylglycerides (OTG). OTG, formed in frying oils upon heating at low concentations, were not detectable with conventional methods to determine polymeric compounds. The best conditions found from the different assays were the following: (i) weight of oil sample-to-solvent volume ratio of 1∶20; and (ii) solvent system methanol/acetone 10∶90 (vol/vol) for monounsaturated oils and 15∶85 (vol/vol) for polyunsaturated oils. Precipitates, enriched in oligomers, were formed when heated oils and used frying oils contained more than 27% polar compounds, a value which is widely accepted as the upper limit for use of frying oils.     

The behaviour of large gas bubbles at a liquid-liquid interface. Part 2: Liquid entrainment

The roles played by large gas bubbles in the generation and coalescence of liquid drops at a liquid-liquid interface are elucidated. The amount of lower liquid entrained by individual bubbles and the resulting drop size distributions in the upper liquid phase are quantified for the three phase system: sunflower oil + 50 wt % decane, water + 50 wt % sugar, air, and qualitative theoretical models are presented. Drops settling to the interface were found to coalesce rapidly and bubble flux had no apparent effect on the rate of drop coalescence at the liquid-liquid interface.     

Preparation of liposomes using the supercritical anti-solvent (SAS) process and comparison with a conventional method

Two methods to produce liposomes encapsulating a fluorescent marker were compared: the supercritical anti-solvent (SAS) method and a conventional one (Bangham). Liposome size and encapsulation efficiency were measured to assess the methods. Micronized lecithin produced by the SAS process was characterized in terms of particle size, morphology and residual solvent content in order to investigate the influence of experimental parameters (pressure, CO₂/solvent molar ratio and solute concentration). It appears that when the lecithin concentration increases from 15 to 25 wt.%, at 9 MPa and 308 K, larger (20-60 μm) and less aggregated lecithin particles are formed. As concerns liposomes formed from SAS processed lecithin, size distribution curves are mainly bimodal, spreading in the range of 0.1-100 μm. Liposome encapsulation efficiencies are including between 10 and 20%. As concerns the Bangham method, more dispersed liposomes were formed; encapsulation efficiencies were about 20%, and problems of reproducibility have been raised.     

Emulsifying Properties of Different Modified Sunflower Lecithins

Lecithins are a mixture of acetone-insoluble phospholipids and other minor substances (triglycerides, carbohydrates, etc.). The most commonly processes used for lecithin modification are: fractionation by deoiling to separate oil from phospholipids, fractionation with solvents to produce fractions enriched in specific phospholipids, and introduction of enzymatic and chemical changes in phospholipid molecules. The aim of this work was to evaluate the emulsifying properties of different modified sunflower lecithins in oil-in-water (O/W) emulsions. In this study, five modified sunflower lecithins were assessed, which were obtained by deoiling (deoiled lecithin), fractionation with absolute ethanol (PC and PI enriched fractions), and enzymatic hydrolysis with phospholipase A₂ from pancreatic porcine and microbial sources (hydrolyzed lecithins). Modified lecithins were applied as an emulsifying agent in O/W emulsions (30:70 wt/wt), ranging 0.1–2.0% (wt/wt). Stability of different emulsions was evaluated through the evolution of backscattering profiles (%BS), particle size distribution, and mean particle diameters (D [3, 4], D [3, 2]). PC enriched fraction and both hydrolyzed lecithins presented the best emulsifying properties against the main destabilization processes (creaming and coalescence) for the analyzed emulsions. These modified lecithins represent a good alternative for the production of new bioactive agents.     

Lecithin gum rheology and processing implications

The rheology of canola, sunflower, and soybean lecithin gum was examined by studying samples of different moisture contents produced in a batch evaporator (70°C, 0.1 atm). Soybean lecithin was found to have the lowest viscosity, approximately 10 poise (100 s⁻¹, 70°C), compared to canola and sunflower lecithin with viscosities of approximately 90 and 90,000 poise, respectively. The high sunflower viscosity was attributed to the presence of long-chain waxes. Lecithin gum was shown to change from a Bingham (water continuous phase) to a pseudoplastic (oil continuous phase) type fluid as the moisture content of the lecithin gum decreased. The viscosity maxima occurred between 6.9 and 19.3% moisture content (100 s⁻¹), with the variation found to be related to the oil/water ratio of the system. Rheological results indicated that vertical scraped surface evaporator design could be optimized through the addition fluidizing of agents prior to the evaporator and/or increased heating at the evaporator outlet.     

A first pilot study to produce a food antioxidant from sunflower seed shells (Helianthus annuus)

This article explains a laboratory procedure to produce an antioxidant from grinded, dehulled and partially defatted sunflower seeds. Initially, a solvent suitable to extract phenols was searched among different solutions of water mixed with ethanol, methanol and acetone at 40% (vol/vol) (each tested at pH 5, 7 and 9). Both the ethanol/water 60:40 (vol/vol) and the acetone/water 60:40 (vol/vol) mixtures proved to be suitable for the dephenolization of sunflower seed shells, but in the next steps of this research, the mixture ethanol/water 60:40 (vol/vol) at pH 5 was used. Secondly, the procedure to obtain the antioxidant product was defined, which consisted in hydrolysis of sunflower seed phenols with 1.25 N NaOH at room temperature for 60 min and finally the recovery of caffeic acid formed from chlorogenic acid with ethyl acetate. From 25 g of partially defatted sunflower shells, around 90 mg of powdery antioxidant product, consisting of 58% caffeic acid, was obtained. The antioxidant product, the caffeic acid standard and propyl gallate were added to different edible fats at the same dose of 240 AU (antioxidant units) per kg fat. A Rancimat test, at 130 °C and an air flow of 20 L h^?1, demonstrated that the effectiveness of the sunflower antioxidant product was essentially similar to that of the caffeic acid standard, but 15–20% lower than that of propyl gallate. In conclusion, dephenolization of sunflower seeds could be economically convenient, not only because a useful antioxidant can be produced, but also because the raw material composition can be improved for other uses.     

Flocculation and Separation of Oil Droplets in Ultrasonic Standing Wave Field

A new method for breaking oil in water emulsion based on flocculation of droplets in high intensity ultrasonic standing wave field was developed in this study and the effect of initial droplets size, type of disperse phase as well as the time of sonication and the height of emulsion in the chamber on the extent of interdroplet interactions were investigated. The results showed that type of disperse phase affects the efficiency of separation process through controlling the initial size of droplets. For the two types of disperse phase in question the efficiency of separation was calculated to be 42.7% for canola oil/water emulsion and 37% for sunflower oil/water emulsion. The time of sonication was found to have a positive contribution to the percent of flocculation and coalescence, so that the largest aggregates were formed after 30 minutes treatment. Also, the optimum height of emulsion in the treatment chamber was determined to be λ/4 at which the strongest flocculation and highest percent of coalescence took place. Increasing the height of emulsion did not significantly influence the course of aggregation and separation.     

Effect of lipid type on water‐in‐oil‐emulsions stabilized by phosphatidylcholine‐depleted lecithin and polyglycerol polyricinoleate

Water‐in‐oil (W/O, 30:70) emulsions were prepared with phosphatidylcholine‐depleted lecithin [PC/(PI,PE) = 0.16] or polyglycerol polyricinoleate (PGPR) as emulsifying agents by means of pressure homogenization. The effect of lipid type (medium‐chain triacylglycerols, sunflower, olive, butter oil, or MCT‐oil/vegetable fat blends) was investigated in relation to particle size distribution, coalescence stability and the sedimentation of the water droplets. A significant correlation (p <0.05) was observed between the interfacial pressure caused by the addition of lecithin to the pure lipids and the specific surface area of the emulsion droplets (r_s = 0.700), and between the viscosity of the lipids used as the continuous phase (reflecting the fatty acid composition) and the specific surface area of the emulsion droplets (r_s = 0.8459) on the other hand. Blends of vegetable fat and MCT‐oil led to reduced coalescence stability due to the attachment of fat crystals to the emulsion droplets. Lecithin‐stabilized W/O emulsions showed significantly higher viscosities compared to those stabilized with PGPR. It was possible to adjust the rheological properties of lecithin‐stabilized emulsions by varying the lipid phase.     

Stability of Oil-in-Water Emulsions with Sunflower (Helianthus annuus L.) and Chia (Salvia hispanica L.) By-Products

Emulsifiers and stabilizers play an important role in emulsion stability. Optical characterization and droplet size distribution of oil‐in‐water emulsions formulated with different types and concentrations of modified sunflower lecithin [phosphatidylcholine (PC) enriched lecithin and deoiled sunflower lecithin], with or without chia mucilage (0.75 % wt/wt), have been evaluated as a function of storage time at 4 ± 1 °C. Emulsions with PC‐enriched lecithin (without chia mucilage) exhibited the highest stability at the different concentrations because of the high PC/phosphatidylethanolamine ratio in comparison to Control lecithin. The addition of 0.75 % wt/wt mucilage contributed to obtain stable emulsions for all type and concentrations of emulsifiers studied, mainly with PC‐enriched lecithin due to the reduction of the mobility of oil particles by the formation of a tridimensional network.     

Laboratory Studies on Membrane Deoiling of Lecithin

Deoiling of lecithin using a nonporous membrane was examined in a favorable solvent (hexane) medium with soy and rice bran lecithins. During the membrane process, the acetone insoluble (AI) content of soy lecithin increased from 63.2 to 81.0% in a single step batch operation. The membrane exhibited an excellent selectivity since phospholipid (PL) reverse micelles formed in the system were rejected almost completely due to low solubility probably aided synergistically by size exclusion. Diafiltration achieved greater oil removal from lecithin as reflected in terms of higher AI and PL contents in the deoiled lecithin. In discontinuous diafiltration, the PL content increased from 33.3 to 85.5% in rice bran lecithin (150% dilution to feed) and 56.6 to 85.7% in soy lecithin (200% dilution), respectively. The simulated continuous diafiltration run showed slightly greater PL content in soy lecithin (91.3%) compared to discontinuous diafiltration (89.7%) besides offering higher productivity. The membrane showed a color reduction of ~60% in soy lecithin but there was no improvement in rice bran lecithin due to the retention of degradation products. The proposed integrated membrane process with nonporous (deoiling) and nanofiltration (solvent recovery) membranes could be an attractive preposition besides being an acetone free process.     

Prediction of average droplet size in flowing immiscible polymer blends

The paper is focused on calculation of the average droplet size in immiscible blends during their steady flow. Available theoretical and experimental results of studies of the droplet breakup and coalescence are utilized to derive the equations describing dynamic equilibrium between the droplet breakup and coalescence. New expression for the coalescence efficiency, reliably reflecting recent theoretical results, is proposed. The equation for the average steady droplet size, controlled by the stepwise breakup mechanism and coalescence of droplets with not very different sizes, is derived for blends containing up to 10–20 vol % of the droplets. For blends with above approximate 20 vol % of the droplets, the breakup by the Tomotika mechanism and coalescence in highly polydisperse system is modeled. Results of the derived equations are compared with experimental data; qualitative agreement is found for the dependence of the droplet size on the amount of the dispersed phase. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45250.     

Characterizing Lecithin Interactions in Chocolate Using Interfacial Properties and Rheology

The functionality of chocolate is based on specific properties including how it flows. Cocoa butter and lecithin are two ingredients that help to control the flow properties of melted chocolate. Lecithin is an emulsifier that has been the preferred method of providing yield stress and viscosity control while reducing production costs by decreasing the amount of cocoa butter needed to achieve similar flow results. In this industrially oriented study, soy, sunflower, and dairy lecithin were compared by quantifying interfacial and rheological properties of lecithin in dark chocolate. Each lecithin source was added up to the 1.0% limit, which is the emulsifier maximum set forth by the Code of Federal Regulations. The compositions of each lecithin source were analyzed for total phospholipid composition, which were used to normalize data based on the total added phosphatides added for all samples. Differences in both phosphatide composition and fatty acid composition were found. Both interfacial tension between oil and water phases and contact angle between a cocoa butter drop and flat sucrose crystal surface decreased as the phosphatide concentration increased for each lecithin source. In terms of rheology, the yield stress first decreased with increasing lecithin content and then began to increase, whereas plastic viscosity continually decreased with addition of lecithin. Significant differences were seen for the different lecithin sources, even when compared on an equivalent phosphatide content. No correlations were found between interfacial properties and yield stress; however, direct correlations were found between both interfacial measures and plastic viscosity.     

Stability determination of soy lecithin-based emulsions by Fourier transform infrared spectroscopy

The stability of soy lecithin-stabilized emulsions was determined by Fourier transform infrared spectroscopy. Oilin-water (o/w) emulsions were prepared with 6% (vol/vol) medium-chain triglycerides (MCT), 94% (vol/vol) water, and 4% (wt/vol) Lecigran and Lecimulthin soy lecithin. There were little or no differences between the 4% Lecigran and 4% Lecimulthin emulsions for all vibrational regions studied (OH at 3348 cm⁻¹, C=O at 1741 cm⁻¹, PO and C−O−C at 1157 cm⁻¹, and P−O−C at 1101 cm⁻¹), but the control emulsion, without emulsifier, had increased vibrations as the emulsion separated. The weaker vibrations of the more stable emulsions were probably due to reduced molecular interaction at the interface. However, added magnesium or calcium chloride enhanced the vibration of these groups, probably by disrupting the lecithin interaction at the emulsion interface.     

Ethanol extraction of polyphenols in an immersion extractor. Effect of pulsing flow

A comparative study on polyphenol extraction from sunflower press cake in a semicontinuous pulsed-flow immersion extractor and in a conventional laboratory immersion extractor was developed. The solvent was 96% (vol/vol) ethanol. No difference in the residual polyphenol content in the cake was observed at short times, but after 10 h, the pulsed extractor showed a higher polyphenol concentration in the outlet miscella. In addition, the effective diffusivity of polyphenols in sunflower press cake was estimated.     

Quantitative Analysis of Sunflower Lecithin Adulteration with Soy Species by NMR Spectroscopy and PLS Regression

NMR spectroscopy was used to distinguish pure sunflower lecithin from that blended with soy species, and to quantify the degree of such adulteration. Sample preparation included liquid extraction of lecithin blends and measurement of polar and non‐polar fractions using ³¹P and ¹H NMR spectrometry. Several phospholipid species, linolenic acid and stachyose were found to be characteristic for sunflower lecithin authentication. For quantitative analysis, partial least squares regression (PLS) was utilized for modeling NMR data of authentic lecithin samples and in‐house prepared blends (n = 80). The models based on phospholipid, fatty acid and saccharide distributions were validated using independent test sets. PLS based on saccharide composition is able to estimate lecithin falsification regarding its vegetable origin with the sensitivity and root mean square error of validation below 1 % w/w and 3.5 % w/w, respectively. Prediction error was improved by modeling the whole lecithin profile (phospholipids, fatty acids, and saccharides). Repeatability and precision expressed in coefficients of variations was estimated to be below 8 %. The developed approach allowed the evaluation of the composition of lecithin blends of unknown soy and sunflower content on the basis of multiple chemical components.     

Heterogeneous hydrodynamic coagulator-coalescer devices

The kinetics of heterogeneous hydrodynamic coagulation and coalescence of motor oil droplets 0.4–1.5 μm in size with a concentration of 0.15–0.5 vol % is investigated in a convoluted tube, a centrifugal pump, and their combination. Kinetic parameters of the coagulation-coalescence process, which proceeds hundreds times faster than sedimentation, are determined.     

Coalescence behaviour of gas bubbles in aqueous solutions of n-alcohols and fatty acids

Coalescence frequency and coalescence times of bubble pairs formed on two adjacent capillary tubes were determined in aqueous solutions of n-alcoho and fatty acids. The results show, that coalescence times of bubbles are proportional to the surface excess concentration of the solute. Coalescence ti increase with the polarity of the hydrophilic group of the solute, its chain length and the bubble size. Coalescence frequency decrease drastically fro 100% to 0% at a distinct solute concentration. The transition in coalescence behaviour occurs, if the coalescence times becomes greater than the availa contact times of the bubbles. The transition concentration therefore decreases with increasing rate of bubble formation.     

Coalescence behaviour of water droplets in water‐oil interface under pulsatile electric fields

In this research, the deformation of water droplets in sunflower oil-interface under pulsatile electric field was studied experimentally. Three types of coalescence were observed:(i) complete coalescence, (ii) incomplete coalescence and (iii) no-coalescence. The first type is desirable because of leaving no secondary droplets. The second type that produced secondary droplets which caused by necking process, due to extreme elongation of droplets (mostly small droplets), was undesirable; because the small droplets were more difficult to coalesce and remove. The no-coalescence was caused by very fast coalescence and extensive pushing of droplet into the continuous phase. In this work the process was operated with the utilization of a batch cylindrical separator with high voltage system. The lower part of the cylinder was filled with the aqueous phase and its top part was filled with sunflower oil to form an interface between the two phases. The effects of electric field strength, frequency, and waveform types were investigated. It was found that, the ramp-ac waveform was the best waveform, avoiding the production of secondary droplets and in this case the frequency also played an important role.     

A study on polymer blending microrheology: Part IV. The influence of coalescence on blend morphology origination

The influence of shear induced coalescence on the origination of morphologies in polymer blending processes is investigated both theoretically and experimentally. In the theoretical part a route is proposed to estimate the fraction of collisions between disperse phase domains in simple shear flow that result in an actual coalescence. It was shown that under polymer blending conditions this “coalescence probability” is only substantial if the polymer/polymer interfaces exhibit a high degree of mobility. In the experimental part, the phenomenon of gravity induced droplet/planar interface coalescence is utilized to show the high degree of mobility of molten polymer interfaces. Seoul experiments on the relation between domain size and disperse phase concentration in polymer blends prepared on a single screw extruder were carried out. For extremely low concentration (<½ %) the domain size could be predicted satisfactorily by means of Taylor's classical criterion for Newtonian liquids, while at higher concentration coalescence increased the average domain size manifold.