Improved oil solubilization in oil/water food grade microemulsions in the presence of polyols and ethanol

Microemulsions based on five-component mixtures for food applications and improved oil solubilization have been studied. The compositions included water, oil phase [such as R(+)-limonene and medium-chain triglycerides (MCT)], short-chain alcohols (such as ethanol), polyols (propylene glycol and glycerol), and several surfactants and their corresponding mixtures (nonionic, such as ethoxylated sorbitan esters, polyglycerol esters, sugar ester, and anionic, such as phosphatidylcholine). The phase behavior of these systems is discussed with respect to the influence of polyols and short-chain alcohols on the degree of solubilization of oils in the aqueous phase. The alcohol and polyols modify the interfacial spontaneous curvature and the flexibility of the surfactant film, enhancing the oil solubilization capacity of the microemulsions. The solubilization of R(+)-limonene was dramatically improved in the presence of the alcohol and polyols, whereas the improvement of solubilization for triglycerides containing MCT was less pronounced. In some systems high oil solubilization was achieved, and some of them can be easily diluted to infinity both with the aqueous phase and with the oil phase. Viscosity measurements along selected dilution lines [characterized by a single continuous microemulsion region starting from a pseudo binary solution (surfactant/oil phase) to the microemulsion (water/polyol corner)] indicate that at a certain composition the system inverts from a W/O to an O/W microemulsion.     

Solubilization patterns of lutein and lutein esters in food grade nonionic microemulsions

Lutein, a naturally occurring carotenoid, is widely distributed in fruits and vegetables and is particularly concentrated in the Tagetes erecta flower. Epidemiological studies suggest that a high lutein intake (6 mg/day) increases serum levels that are associated with a lower risk of cataract and age-related macular degeneration. Lutein can either be free or esterified (myristate, palmitate, or stearate). Both are practically insoluble in aqueous systems, and their solubility in food grade solvents (oils) is very limited, resulting is low bioavailability. To improve its solubility and bioavailability, lutein was solubilized in U-type food grade microemulsions based on ethoxylated sorbitan fatty acid esters, glycerol, R-(+)-limonene, and ethanol. Some of the main findings are as follows: (1) reverse micellar and W/O compositions solubilized both luteins better than an O/W microemulsion, and maximum solubilization is obtained within the bicontinuous phase; (2) free lutein is solubilized better than the esterified one, in the W/O microemulsions, whereas the esterified lutein is better accommodated within the O/W microemulsion; (3) vegetable oils decrease the solubilization of free lutein; (4) glycerol and alcohol enhance the solubilization of both luteins; (5) solubilization is surfactant-dependent in all mesophase structures, but its strongest effect is in the bicontinuous phase.     

Self-diffusion nuclear magnetic resonance,microstructure transitions,and solubilization capacity of phytosterols and cholesterol in Winsor IV food-grade microemulsions

Microemulsions are of growing interest to the food industry as vehicles for delivering and enhancing solubilization of natural food supplements with nutritional and health benefits. The incorporation of molecular phytosterols, cholesterol-lowering agents, in food products is of great interest to the food industry. In this work is demonstrated the use of water dilutable food-grade microemulsions consisting of ethoxylated sorbitan ester (Tween 60), water, R-(+)-limonene, ethanol, and propylene glycol as vehicles for enhancing the phytosterols solubilization. Phytosterols were solubilized up to 12 times more than the dissolution capacity of the oil [R-(+)-limonene] for the same compounds. The solubilization capacity of phytosterols and cholesterol along a dilution line in a pseudo-ternary phase diagram [on this dilution line the weight ratio of R-(+)-limonene/ethanol/Tween 60 is constant at 1:1:3] was correlated to the microstructure transitions along the dilution line. Structural aspects were studied by self-diffusion NMR spectroscopy. The ability of phytosterols to compete with cholesterol for penetration into bile salt micelles in the gut may be limited to rich aqueous systems (O/W microemulsion).     

Phospholipid-based microemulsions suitable for use in foods

The preparation of nonaqueous microemulsions using food-acceptable components is reported. The effect of oil on the formation of microemulsions stabilized by lecithin (Epikuron 200) and containing propylene glycol as immiscible solvent was investigated. When the triglycerides were used as oil, three types of phase behavior were noted, namely, a two-phase cloudy region (occurring at low lecithin concentrations), a liquid crystalline (LC) phase (occurring at high surfactant and low oil concentrations), and a clear monophasic microemulsion region. The extent of this clear one-phase region was found to be dependent upon the molecular volume of the oil being solubilized. Large molecular volume oils, such as soybean and sunflower oils, produced a small microemulsion region, whereas the smallest molecular volume triglyceride, tributyrin, produced a large, clear monophasic region. Use of the ethyl ester, ethyl oleate, as oil produced a clear, monophasic region of a size comparable to that seen with tributyrin. Substitution of some of the propylene glycol with water greatly reduced the extent of the clear one-phase region and increased the extent of the liquid crystalline region. In contrast, ethanol enhanced the clear, monophasic region by decreasing the LC phase. Replacement of some of the lecithin with the micelle-forming nonionic surfactant Tween 80 to produce mixed lecithin/Tween 80 mixtures of weight ratios (Km) 1:2 and 1:3 did not significantly alter the phase behavior, although there was a marginal increase in the area of the two-phase, cloudy region of the phase diagram. The use of the lower phosphatidylcholine content lecithin, Epikuron 170, in place of Epikuron 200 resulted in a reduction in the LC region for all of the systems investigated. In conclusion, these studies show that it is possible to prepare one-phase, clear lecithin-based microemulsions over a wide range of compositions using components that are food-acceptable.     

Solubilization of acyl heterogeneous triacylglycerol in phosphatidylcholine vesicles

The amount of acyl heterogeneous triacylglycerol (TG(HET)) solubilized by phosphatidylcholine (PC) vesicles, prepared by co-sonication of egg PC and small amounts (<6% w/w) of TG(HET), was determined using (13)C nuclear magnetic resonance (NMR). The acyl chains of TG(HET) were predominantly 16 or 18 carbons in length, 50% saturated, and approximately 21.7% (13)C isotopically enriched at the carbonyl carbon. The (13)C NMR spectra revealed two carbonyl resonances at chemical shift values between PC carbonyls and oil-phase TG carbonyls, confirming the presence of TG(HET) solubilized in PC vesicles. Oil-phase TG carbonyl peaks were present only in spectra of vesicles containing >3 wt % TG(HET). Integration of TG(HET) carbonyl resonances determined that PC vesicles solubilized 3.8 wt % of TG(HET), compared to 2.8 wt % of acyl homogeneous triolein. The difference between the maximum solubility of TG(HET) and that of homogeneous TG (TG(HOM)) with similar acyl chain lengths provides evidence that specific acyl composition, in addition to the acyl chain length of triacylglycerols, affects the solubility of TG in PC vesicles and TG-rich lipoprotein surfaces. Thus, TG(HET) may innately be a better model substrate than TG(HOM) for determination of substrate availability of TG at lipoprotein surfaces.     

Formation of flavor oil microemulsions, nanoemulsions and emulsions: influence of composition and preparation method

This study aimed to establish conditions where stable microemulsions, nanoemulsions or emulsions could be fabricated from a nonionic surfactant (Tween 80) and flavor oil (lemon oil). Different colloidal dispersions could be formed by simple heat treatment (90 °C, 30 min) depending on the surfactant-to-oil ratio (SOR): emulsions (r > 100 nm) at SOR < 1; nanoemulsions (r < 100 nm) at 1 < SOR < 2; microemulsions (r < 10 nm) at SOR > 2. Turbidity, electrical conductivity, shear rheology, and DSC measurements suggested there was a kinetic energy barrier in the oil-water-surfactant systems at ambient temperature that prevented them from forming metastable emulsion/nanoemulsion or thermodynamically stable microemulsion systems. High energy homogenization (high pressure or ultrasonic homogenizer) or low energy homogenization (heating) could be used to form emulsions or nanoemulsions at low or intermediate SOR values; whereas only heating was necessary to form stable microemulsions at high SOR values.     

Model studies on the release of aroma compounds from structured and nonstructured oil systems using proton-transfer reaction mass spectrometry

Relative retention, volatility, and temporal release of volatile compounds taken from aldehyde, ester, and alcohol chemical classes were studied at 70 degrees C in model systems using equilibrium static headspace analysis and real time dynamic headspace analysis. These systems were medium-chain triglycerides (MCT), sunflower oil, and two structured systems, i.e., water-in-oil emulsion and L2 phase (water-in-oil microemulsion). Hydrophilic domains of the emulsion type media retained specifically the hydrophilic compounds and alcohols. Four kinetic parameters characterizing the concentration- and time-dependent releases were extracted from the aroma release curves. Most of the kinetic parameter values were higher in structured systems than in oils particularly when using MCT. The oil nature was found to better control the dynamic release profiles than the system structures. The release parameters were well-related (i) to the volatile hydrophobicity as a function of the oil used and (ii) to the retention data in the specific case of the L2 phase due to a specific release behavior of alcohols.     

Use of SMS as a Compost Matrix to Degrade Pesticide Residuals

Pesticide rinsates have been found to be one source of surface water and groundwater contamination. Practical waste treatment methods that achieve environmental protection standards applicable to pesticide rinsates are limited (Kuo, 1993). The research to be presented was conducted to investigate the feasibility of using SMS as an adsorption medium and as a microorganism source to remediate synthetic technical grade rinsate solutions containing up to 30 mg/L of three carbamate insecticides, namely, carbaryl, carbofuran and aldicarb. All experiments were conducted in the laboratory using bench scale complete mixing batch reactors (CMBR) at 25°C.

The results indicated that the SMS was able to adsorb the candidate pesticide from aqueous solution. The process was found to exhibit nonlinear “favorable” adsorption behavior which was characterized by the Freundlich isotherm model. Rates were enhanced by the increase of organic contents in the SMS.

The SMS microorganisms were found to be more adapted to detoxifying the carbamate solutions than seed derived from domestic wastewater activated sludge. Inhibition of the SMS cultures by the insecticides was not indicated. The degradation rates were described by the Monod model, with carbaryl and carbofuran rated “readily” biodegradable, while aldicarb rated “hardly” biodegradable.

Future research needs to address other classes of pesticides, including organophosphates; pilot-scale studies using commercial grade formulations; and fundamental research dealing with identifying the unique microbial consortium found in SMS.     

Food-grade microemulsions based on nonionic emulsifiers: media to enhance lycopene solubilization

Water-dilutable food-grade microemulsions consisting of ethoxylated sorbitan esters, and in some cases blended with other emulsifiers, water, (R)-(+)-limonene, ethanol, and propylene glycol, have been prepared. These microemulsions are of growing interest to the food industry as vehicles for delivering and enhancing solubilization of natural food supplements with nutritional and health benefits. Lycopene, an active natural lipophilic antioxidant from tomato, has solubilized in water-in-oil, bicontinuous, and oil-in-water types of microemulsions up to 10 times the oil [(R)-(+)-limonene] dissolution capacity. The effects of aqueous-phase dilution, nature of surfactant (hydrophilic-lypophilic balance), and mixed surfactant on solubilization capacity and solubilization efficiency were studied. Structural aspects studied by self-diffusion NMR were correlated to the solubilization capacity, and transformational structural changes were identified.     

Effect of chitosan and chitin on the separation of membranes from proteins solubilized by pH shifts using cod (Gadus morhua)

Studies with isolated membranes and isolated membranes suspended in muscle proteins solubilized at pH 3 showed that mixing chitosan and membranes at this low pH followed by a pH adjustment to 10.5 could sediment membranes effectively at 4000 g. In the solubilized muscle homogenate, the effectiveness of membrane removal by chitosan at 4000 g for 15 min was molecular weight dependent. About 80% of the phospholipids and 28% of proteins were sedimented from solubilized muscle homogenate by mixing muscle homogenate (10 g of muscle tissue homogenized with 90 mL of distilled water) with 10 mL of MW 310-375 k chitosan (10 mg/mL in 0.1 N HCl) before solubilizing it at pH 10.5, whereas 55% of the phospholipids and 12% of proteins were sedimented by mixing muscle homogenate with the MW 310-375 k chitosan before solubilizing the homogenate at pH 3. Low molecular weight chitosans (at MW 1k or 33k) showed little effect on membrane sedimentation under the same conditions. Chitin was not useful for removing membranes at either pH 3 or 10.5, whether added before or after pH adjustment.     

菌糠等物料施入风沙土对其溶解性有机质组分的动态变化影响

采用室内培养试验研究菌糠等不同物料对风沙土溶解性有机质组分的动态变化的影响。结果表明:菌糠施入土壤后,其溶解性有机质组分水溶性碳(WSOC)、热水溶性碳(HWSOC)、溶解性酚酸(DP)、可溶性糖(DS)含量均比对照增加,以施入时间1个月内增加效果明显,针对菌糠以调节C/N比值效果好。与玉米秸秆比较,菌糠施入土壤后,土壤的溶解性有机质组分水溶性碳(WSOC)、热水溶性碳(HWSOC)、溶解性酚酸(DP)均比玉米秸秆处理含量高,而可溶性糖(DS)含量前3d较高,后期低于玉米秸秆。与麦麸比较,菌糠施入土壤前1周溶解性有机质组分水溶性碳(WSOC)比麦麸含量高,而热水溶性碳(HWSOC)、溶解性酚酸(DP)、可溶性糖(DS)含量均低于麦麸处理,1周后麦麸可溶性糖(DS)含量均高于菌糠,在整个试验培养期间,麦麸溶解性酚酸(DP)含量均高于菌糠。生产实践中,麦麸被认为是目前较好的微生物载体,以热水溶性碳(HWSOC)、溶解性酚酸(DP)、可溶性糖(DS)含量评定微生物载体的质量标准,以木屑生产的食用菌菌糠作为生物载体不及麦麸。     

Phase transitions of pea starch over a wide range of water content

The phase transitions of pea starch over a wide range of water content were investigated by differential scanning calorimetry (DSC). Swelling of starch granules increased progressively with increasing water content. The main endotherm G broadened progressively with increasing water content up to 94.5 wt % (water:starch ratio 15:1), above which it became too broad to define. The corresponding peak and conclusion temperatures and enthalpy change increased with increasing water content. Scanning electron microscopy (SEM) showed that, at a water:starch ratio of 2:1 (water content of 70.7 wt %), starch granules only swelled partially with discernible granular contours still clearly evident. The results of swelling power tests and SEM images revealed that the endotherm G obtained at a water:starch ratio of 2:1 represented only partial swelling of starch granules. The transition from a narrow to broad endotherm G was interpreted to reflect the thermal transition behavior progressing from limited swelling to maximum swelling and then partial dissolution and leaching of starch polymers from the granules.     

Comparative evaluation of the emulsifying properties of phosphatidylcholine after enzymatic acyl modification

The ability of enzymatically synthesized structured phosphatidylcholine (PC) containing caprylic acid to form and stabilize oil-in-water emulsions prepared with different triglycerides [medium chain triglycerides (MCT), soybean oil, and enzymatically synthesized structured lipids] was examined and compared with natural soybean PC and deoiled lecithin. Emulsions were prepared with varying oil and emulsifier concentrations. The particle size distribution, creaming stability, and viscosity were measured for the evaluation of the emulsifying properties. With an increase in the oil concentration, there was an increase in particle size, viscosity, and creaming layer. With an increase in the phospholipid (PL) concentration, there was usually a decrease in particle size and an increase in viscosity, where the emulsion stability was increased. General emulsions prepared with structured lipids resulted in smaller particle sizes as compared to MCT and soybean oil. Deoiled lecithin was able to increase the viscosity more significantly and give smaller particle sizes as compared to the other emulsifiers, thus producing more stable emulsions. However, in certain cases, structured PC was superior to deoiled lecithin and soybean PC. This observation was made for emulsions prepared with soybean oil or structured lipid at an oil/water ratio of 10:90. At an oil/water ratio of 30:70, the deoiled lecithin performed better as compared to the other PLs with all oil types. However, structured PC produced more stable emulsions as compared to natural soybean PC in MCT and soybean oil.     

Furfural-cysteine model reaction in food grade nonionic oil/water microemulsions for selective flavor formation

The thermal reaction between cysteine and furfural was investigated at 65 degrees C in five-component food grade oil/water (O/W) microemulsions of R-(+)-limonene/ethanol, EtOH/water/propylene glycol, PG/Tween 60 as apart of a systematic study on the generation of aroma compounds by utilizing structured W/O and O/W fluids. The furfural-cysteine reaction led to the formation of unique aroma compounds such as 2-furfurylthiol (FFT), 2-(2-furanyl)thiazolidine (main reaction product), 2-(2-furanyl)thiazoline, and N-(2-mercaptovinyl)-2-(2-furanyl)thiazolidine. These products were determined and characterized by GC-MS. Enhancement in flavor formation is termed "microemulsion catalysis". The chemical reaction occurs preferably at the interfacial film, and therefore a pseudophase model was assumed to explain the enhanced flavor formation. The product internal composition is dictated by process conditions such as temperature, time, pH, and mainly the nature of the interface. Increasing water/PG ratio leads to a dramatic increase in the initial reaction rate (V(0)). V(0) increased linearly as a function of the aqueous phase content, which could be due to the increase in the interfacial concentration of furfural. Microemulsions offer a new reaction medium to produce selective aroma compounds and to optimize their formation.     

Use of Spent Mushroom Substrate (SMS) for Corn (Maize) Production and its Effect on Surface Water Quality

Mushroom farmers have large quantities of spent mushroom substrate after their crops are harvested. This material is used for a variety of purposes including the growth of field crops. SMS was incorporated into a poor quality soil before planting 90-day corn. Field plots were established where spent mushroom substrate (SMS) was incorporated at 22.5, 45.0 or 90.0 kg m^?1, plus an untreated control on each of three years. Analysis of SMS indicates its nutrient level was 0.9-0.6-1.0 (N-P-K). Starter fertilizer was applied at planting along with an insecticide, but no herbicide. No additional fertilizer was used. Corn yields were significantly higher in SMS amended plots and the nitrogen content of both grain and stover was significantly higher than the control. Surface runoff water quality values from SMS amended soil were in the same range as those from the control treatments, the plots that received no SMS. Annual incorporation of up to 90 kg m^?2 of SMS into land planted to corn did not degrade the quality of surface water. Nutrients were retained in the SMS soil matrix and were, apparently, used as nutrients by the corn plants. Surface runoff was very low in ammonia nitrogen, CBOD, and chlorides. Use of SMS as an exclusive soil nutrient/soil ameliorant in corn production resulted is exceptionally good yields and quality.     

Changes in Soil Aggregate-Associated Organic Carbon and Nitrogen after Ten Years under Different Land-Use and Soil-Management Systems in Indo-Gangetic Sodic Soil

A study was conducted to evaluate the effects of different land uses and soil-management systems (LU and SMS) on key soil physicochemical indicators [aggregate stability, distribution of soil organic carbon (SOC), and nitrogen (N) in aggregate fractions] and to interpret significance of long-term cultivation of agroforestry plantations [Prosopis juliflora L. (AFP) and Casuarina equisetifolia L. (AFC)], horticultural plantations [(Tamarindus indica (HI) and Syzygium cumini (HJ)], and rice–wheat system (RW) in sodic soil of the Indo-Gangetic plain. Soil samples collected from the different LU and SMS plots were analyzed. The barren sodic soil (BSS) exhibited the least mean weight aggregate diameter (0.21), whereas AFP recorded the greatest (0.59). Total N content in surface soil under RW system was about the same as AFP, AFC, HI, and HJ and significantly greater than BSS. Across the LU and SMS except BSS, microaggregates recorded a narrower C/N ratio than macro- and mesoaggregates.     

Extraction of proteins with low fluoride level from Antarctic krill (Euphausia superba) and their composition analysis

The extraction of proteins with low fluoride level (LFP) from Antarctic krill (Euphausia superba) was investigated in this work. The optimal conditions for protein solubilization were determined to be pH 11.5 and 4 °C. The proteins were solubilized two times; a water/krill ratio (mL/g) of 6 and a time of 30 min were used for the first step, whereas the second used a water/krill residue ratio (mL/g) of 3 and a time of 30 min. The optimum pH for protein precipitation was 4.6. A LFP with fluoride content of 9.86 mg/kg (dry weight) was finally obtained through a fluoride removal program. The protein yield of LFP was 52.68%. Composition analysis of LFP indicated it was composed of 66.96% of crude proteins (dry weight) and 33.01% of total lipids (dry weight),, and all nine essential amino acids were in sufficient amounts to meet FAO/WHO/UNU requirements for adults and infants. In addition, LFP could be taken as a good source of EPA and DHA for consideration of use as a food item for human consumption.     

Influence of flavor solvent on flavor release and perception in sugar-free chewing gum

The influence of flavor solvent [triacetin (TA), propylene glycol (PG), medium chained triglycerides (MCT), or no flavor solvent (NFS)] on the flavor release profile, the textural properties, and the sensory perception of a sugar-free chewing gum was investigated. Time course analysis of the exhaled breath and saliva during chewing gum mastication indicated that flavor solvent addition or type did not influence the aroma release profile; however, the sorbitol release rate was statistically lower for the TA formulated sample in comparison to those with PG, MCT, or NFS. Sensory time-intensity analysis also indicated that the TA formulated sample was statistically lower in perceived sweetness intensity, in comparison with the other chewing gum samples, and also had lower cinnamon-like aroma intensity, presumably due to an interaction between sweetness intensity on aroma perception. Measurement of the chewing gum macroscopic texture by compression analysis during consumption was not correlated to the unique flavor release properties of the TA-chewing gum. However, a relationship between gum base plasticity and retention of sugar alcohol during mastication was proposed to explain the different flavor properties of the TA sample.     

Model studies on the influence of matrix type and storage environment on the stability of a model aroma mixture during storage

The objective of this study was to investigate the effect of oxygen in the storage atmosphere on the degradation of model compounds when present in water or a medium chain triglyceride (MCT) matrix. A model aroma compound mixture was prepared in oil (MCT) or water, and it was then stored under either an ambient air or argon atmosphere containing respectively ca. 20% and <0.5% residual oxygen. Samples were analyzed by SPME-GC/MS to determine the relative stability over time of different classes of aroma compounds. The low-oxygen atmosphere appeared to have a significant protective effect on sulfur compounds, aldehydes, and ketones in oil but a detrimental influence on pyrroles. Data showed little influence of the atmosphere for these compounds in water. In addition, the type of matrix had a significant effect (P < 0.05) on the stability of aldehydic, ester, and pyrrole compounds. These compounds were more stable in MCT than in water.     

The Use of Spent Mushroom Substrate (SMS) as an Organic Manure and Plant Substrate Component

The effect of the addition of SMS to soil on the growth of perennial ryegrass was studied in a pot experiment. SMS raised the analyzed levels of P, K, Mg and Electrical Conductivity (EC) but not the level of NO₃-N. At the first harvest, there was a positive response of growth up to a rate equivalent to 50 t/ha but above this growth declined. By the final harvest, there was a positive response of dry matter production up to the highest rate, 400 t/ha. The calculated nitrogen efficiency of dry matter production for SMS averaged 3.1 as against 21.1 for calcium ammonium nitrate. Leaching an SMS/peat column with distilled water at 10 day intervals over a 60 day period recovered 94 percent of the K in the leachate, 33 percent of the P and only 15 percent of the N. In SMS/peat mixes, early growth of tomato seedlings did not respond to rates above five percent of SMS by volume and was reduced when the SMS rate was above 20 percent. When the plants were grown on to a more mature stage, there was a response up to 20 percent SMS. In three experiments, SMS was used as a single nutrient source to supply N, P and K respectively. When used as a source of P and K, there was little benefit from increasing the rate of SMS above five percent. However, when used as a source of N, plant growth increased up to a rate of 25 percent SMS. There was no response to the addition of trace elements to SMS/peat substrates. When an SMS/peat substrate, containing five percent SMS by volume was supplemented with extra N, plant performance was as good as in a peat substrate with inorganic fertilizers.