Preparation of Margarine Stock Rich in Naturally Bioactive Components by Enzymatic Interesterification.

Fully hydrogenated expanded press soybean oil (FHEPSO) rich in naturally bioactive components was prepared using Palladium on Carbon (Pd/C) catalyst. Interesterified fat was prepared from binary blends of FHEPSO and cold press corn oil (CPCO) with FHEPSO/CPCO mass ratios of 50:50, 40:60 and 30:70. Lipozyme RM IM (6 wt% of total substrate) was used in a supercritical CO2 system to catalyze the transesterification. The fatty acid compositions had no significant changes in the fats before and after interesterification, and trans-fatty acid (TFA) was not detected. The fatty acid compositions within triacylglycerol (TAG) were rearranged, and the amounts of trisaturated and triunsaturated TAG decreased, whereas that of mixed TAG increased as a result of interesterification. The enzymatic interesterified fats (EIEF) had a lower solid fat content (SFC), broader melting and plasticity ranges compared to the noninteresterified blend (NIB). According to X-ray diffraction (XRD), the predominant crystal form had changed from ß to ß'. EIEF contained 0.33-0.51 g/100 g phospholipids, 88.6-105.6 mg/100 g total tocopherols, and 916-1053 mg/100 g total phytosterols, which could confer health benefits. The results indicated that EIEF may have a potential use in trans-free margarine stock preparation.

Mesoporous SBA-15 Silica-supported Diisopropylguanidine: an Efficient Solid Catalyst for Interesterification of Soybean Oil with Methyl Octanoate or Methyl Decanoate.

The organosilane agent, namely 3-(N,N'-diisopropylguanidine)-propyltriethoxysilane, was firstly prepared by the reaction of diisopropylcarbodimide with (3-aminopropyl)triethoxysilane, and then employed for grafting guanidine base onto the surface of the mesoporous SBA-15 silica to afford an organic-inorganic hybrid catalyst. The prepared solid catalyst was fully characterized by various techniques such as small-angle X-ray power diffraction, Fourier transform infrared spectra, scanning electron microscopy, transmission electron microscopy, nitrogen adsorption-desorption and elemental analysis techniques. The obtained results showed that the guanidine base was successfully tethered onto the SBA-15 silica and the ordered mesoporous structure of the SBA-15 material remained almost unchangeable after the orgnofunctionalization. The solid catalyst was found to have appreciable catalytic activities to the interesterification of soybean oil with methyl octanoate or methyl decanoate under solvent-free conditions. Influence of various reaction parameters, such as the substrate molar ratio, reaction temperature, catalyst loading and reaction time, on the catalytic interesterification was investigated to optimize the interesterification condition for the production of structured lipids containing medium-chain fatty acids. The hybrid solid catalyst was easily separated and reused for four runs without significant loss of catalytic activity.

Production of Diacylglycerol-enriched Oil by Glycerolysis of Soybean Oil using a Bubble Column Reactor in a Solvent-free System.

In this study, diacylglycerol-enriched soybean oil (DESO) was synthesized through Lipozyme 435-catalyzed glycerolysis of soybean oil (SO) in a solvent-free system using a modified bubble column reactor. The effects of enzyme load, mole ratio of glycerol to soybean oil, reaction temperature, gas flow and reaction time on DAG production were investigated. The selected conditions were established as being enzyme load of 4 wt% (mass of substrates), glycerol/soybean oil mole ratio of 20:1, reaction temperature of 80°C, gas flow of 10.6 cm/min, and a reaction time of 2.5 h, obtaining the DAG content of 49.4±0.5 wt%. The reusability of Lipozyme 435 was evaluated by monitoring the contents of DAG, monoacylglycerol (MAG) and triacylglycerol (TAG) in 10 consecutive runs. After purified by one-step molecular distillation, the DAG content of 63.5±0.3 wt% was achieved in DESO. The mole ratio of 1, 3-DAG to 1, 2-DAG was 2:1 and the fatty acid composition had no significant difference from that of soybean oil. However, the thermal properties of DESO and SO had considerable differences. Polymorphic form of DESO were mainly the ß form and minor amounts of the ß' form. Granular aggregation and round-shaped crystals were detected in DESO.

Epoxidized soybean oil/ZnO biocomposites for soft tissue applications: preparation and characterization.

Biocompatible and biodegradable nanocomposites comprising epoxidized soybean oil (ESO) as matrix, zinc oxide (ZnO) nanoparticles as reinforcements, and 4-dimethylaminopyridine (DMAP) as a catalyst have been successfully prepared via epoxidization of the double bonds of the vegetable oil, ultrasonication, and curing without the need for interfacial modifiers. Their morphology, water uptake, thermal, mechanical, barrier, tribological, and antibacterial properties have been investigated. FT-IR analysis revealed the existence of strong ESO-ZnO hydrogen-bonding interactions. The nanoparticles acted as mass transport barriers, hindering the diffusion of volatiles generated during the decomposition process and leading to higher thermal stability, and also reduced the water absorption and gas permeability of the bioresin. Significant improvements in the static and dynamic mechanical properties, such as storage and Young's moduli, tensile strength, toughness, hardness, glass transition, and heat distortion temperature, were attained on reinforcement. A small drop in the nanocomposite stiffness and strength was found after exposure to several cycles of steam sterilization or to simulated body fluid (SBF) at physiological temperature. Extraordinary reductions in the coefficient of friction and wear rate were detected under both dry and SBF conditions, confirming the potential of these nanoparticles for improving the tribological performance of ESO. The nanocomposites displayed antimicrobial action against human pathogen bacteria with and without UV illumination, which increased progressively with the ZnO content. These sustainable, ecofriendly, and low-cost biomaterials are very promising for use in biomedical applications, like structural tissue engineering scaffolds.

Enzymatic epoxidation of soybean oil using ionic liquid as reaction media.

An ionic liquid (IL) system for the enzymatic epoxidation of soybean oil was studied. The effects of active oxygen carriers (different fatty acids) and ILs ([Bmim]PF6 and [Bmim]BF4) on the enzymatic epoxidation were investigated. Response surface methodology (RSM) was used to study and optimize the effects of variables (reaction time, reaction temperature, molar ratio of H2O2/C=C-bonds, and molar ratio of fatty acid/C=C-bonds) on the epoxy oxygen group content (EOC) of epoxidized soybean oil (ESO). Results showed that the enzymatic epoxidation of soybean oil can be enhanced using tetradecanoic acid (C13H27COOH) as active oxygen carrier and [Bmim]PF6 as reaction medium. The optimum EOC of ESO was 5.9 ± 0.3% under the following conditions: reaction temperature 46°C, reaction time 11 h, enzyme load 3% (w/w, relative to the weight of soybean oil), molar ratio of H2O2/C=C-bonds 1.8:1, and molar ratio of C13H27COOH/C=C-bonds 0.5:1.

Carbonation of epoxy methyl soyate at atmospheric pressure.

Vegetable oils are important substrates for the development of biobased products that may replace products derived from petroleum. Carbonated methyl soyates were prepared at atmospheric pressures from epoxy methyl soyate by the introduction of carbon dioxide at the oxirane position. Carbonation was performed by sparging carbon dioxide gas through the neat epoxy esters at atmospheric pressure in the presence of tetrabutylammonium bromide catalyst. Analysis of reaction mixtures showed that 42% of the epoxide groups were carbonated after 18 h at 80 degrees C with 1 wt% catalyst compared to 63% using liquid carbon dioxide at 54 atm pressure.

Development of mineral oil free offset printing ink using vegetable oil esters.

Until the middle of this century, fats and oils are the major raw material source for paints, coating and lubricating applications. These markets are completely taken over by petroleum based stocks due to their abundance and versatility. However, recent public awareness to use environmentally acceptable products that minimize pollution, are compatible to human health and readily biodegradable created opportunities for vegetable oils for application in paints and printing inks. The formulation of vegetable oil methyl ester based 'green' offset printing ink that reduces the volatile organic compounds (VOC) has been discussed in the present study. Methyl esters of rapeseed, soybean, rice bran and palm oil have been prepared and their physical properties have been measured and compared with standard petroleum feed stock. Varnishes were prepared with these esters and their properties are also compared with that of the petroleum based products. Rheological properties of the inks are also evaluated and compared with standard printing ink using petroleum based solvent. In general performance of the ester-based printing inks are comparable with that of the mineral oil based product. On the basis of tack stability and gloss, ester based inks are much superior than the mineral oil based products. In conclusion, a new non-volatile diluent for printing ink has been developed. The diluent is made from common vegetable oils like rapeseed, soybean, rice bran and palm oil, a renewable source that is environmental friendly. Vegetable oil esters offer a cost effective solution for mineral oil based printing ink to meet VOCs regulations.

Synthesis and characterization of polymeric soybean oil-g-methyl methacrylate (and n-butyl methacrylate) graft copolymers: biocompatibility and bacterial adhesion.

Peroxidation, epoxidation, and/or perepoxidation reactions of soybean oil under air at room temperature resulted in cross-linked polymeric soybean oil peroxides on the surface along with the waxy soluble part, sPSB, with a molecular weight of 4690, containing up to 2.3 wt % peroxide. This soluble polymeric oil peroxide, sPSB, initiated the free radical polymerization of either methyl methacrylate (MMA) or n-butyl methacrylate (nBMA) to give PSB-g-PMMA and PSB-g-PnBMA graft copolymers. The polymers obtained were characterized by (1)H NMR, thermogravimetric analysis, differential scanning calorimetry, and gel permeation chromatography techniques. Polymeric oil as a plasticizer lowered the glass transition of the PSB-g-PMMA graft copolymers. PSB-g-PMMA and PSB-g-PnBMA graft copolymer film samples were also used in cell culture studies. Fibroblast and macrophage cells were strongly adhered and spread on the copolymer film surfaces, which is important in tissue engineering. Bacterial adhesion on PSB-g-PMMA graft copolymer was also studied. Both Staphylococcus epidermidis and Escherichia coli adhered on the graft copolymer better than on homo-PMMA. Furthermore, the latter adhered much better than the former.

Lipase-catalyzed interesterification of soybean oil with an omega-3 polyunsaturated fatty acid concentrate prepared from sardine oil.

To reduce the content of linoleoyl moiety in soybean oil, soybean oil that contains 53.0% linoleoyl moiety as molar acyl moiety composition was interesterified with an omega-3 polyunsaturated fatty acid (PUFA) concentrate (24.0 mol% eicosapentaenoic acid [EPA], 40.4 mol% docosahexaenoic acid [DHA]) prepared from sardine oil, using an immobilized sn-1,3-specific lipase from Rhizomucor miehei (Lipozyme IM). The reaction was carried out in a batch reactor at 37 degrees C under the following conditions: 500 micromol of soybean oil, molar ratio of omega-3 PUFA concentrate to soybean oil = 1.0-6.0,5.0 mL of heptane, and 30 batch interesterification units of enzyme. After the reaction time of 72 h, modified soybean oil, which contains 34.9% linoleoyl, 10.1% eicosapentaenoyl, and 14.2% docosahexaenoyl moieties, was produced at the molar reactant ratio of 6.0. In this oil, the total omega-3 acyl moiety composition reached 34.1%; the molar ratio of omega-3 to omega-6 acyl moieties was enhanced by five times compared with soybean oil. Compared with palmitic acid, DHA was kinetically six times less reactive, although the EPA was by 16% more reactive.

Evaluation of novel soya-lecithin formulations for dermal use containing ketoprofen as a model drug.

In this study soya-lecithin aggregates, prepared by a technique using compressed gas, are used to formulate new dermal preparations. Ketoprofen (KP), a nonsteroidal anti-inflammatory drug (NSAID) is included as a model drug. The technique offers the possibility of incorporating auxiliary agents, such as penetration enhancers, anti-irritants and moisturisers together with the drug in one process. Apparent partition coefficients for n-octanol-phosphate buffer were determined for each of the lecithin aggregates. In general, soya-lecithin improves the partition of KP into n-octanol. The resulting products were included in widely used hydrophilic and hydrophobic vehicles. After 24 h, the cumulative amount of drug released through an artificial membrane was higher from the hydrophilic gels (2.6-4.3 mg) and the hydrophobic creams (0.23-0.392 mg) than from the control preparations (control hydrogel: 1.3 mg; control hydrophobic cream: 0.141 mg). However, the cumulative amount released from the hydrophobic vehicles was generally lower than from the hydrophilic matrices. Cumulative amounts such as those released from the hydrophilic preparations can also be achieved using supersaturated formulations based solely on the drug-loaded lecithin aggregates and a suitable oily component (4.07 mg). Results from the diffusion studies using artificial membranes were confirmed by permeation studies using excised rat skin. The improvement in skin permeation is related to both the solubilising effect of the lecithin matrix and the penetration enhancing effect of lecithin itself. The novel soya-lecithin aggregates are promising candidates for new drug delivery systems in dermatology and cosmetology. Lecithin aggregates loaded with drugs are multifunctional carriers that also act as penetration enhancers.