Fatty amides have been successfully synthesized from palm olein and urea by a one-step lipase catalyzed reaction. The use of immobilized lipase as the catalyst for the preparation reaction provides an easy isolation of the enzyme from the products and other components in the reaction mixture. The fatty amides were characterized using Fourier transform infrared (FTIR) spectroscopy, proton nuclear magnetic resonance (1H NMR) technique and elemental analysis. The highest conversion percentage (96%) was obtained when the process was carried out for 36 hours using urea to palm oil ratio of 5.2: 1.0 at 40°C. The method employed offers several advantages such as renewable and abundant of the raw material, simple reaction procedure, environmentally friendly process and high yield of the product.
Since deodorization distillate, a by-product of rice bran oil production, contains squalene (ca. 8%) and phytosterols (ca. 4%) as unsaponifiable components, the concentration of those materials for their use in the cosmetics and food industries is desirable. In the present work, a novel fractionation method of concentrating squalene and phytosterols from deodorization distillate or the unsaponifiable components of the deodorization distillate without oxidative deterioration was examined. Supercritical fluid extraction (SFE) with supercritical carbon dioxide was investigated under the following conditions: temperature, 30°C; pressure, 100 kg/cm2; flow rate of carbon dioxide, 7 mL/min. Under these conditions, squalene was effectively concentrated to 25% with nearly quantitative recovery, and then a more highly concentrated squalene (ca. 50% purity) was obtained by using a supercritical fluid chromatography (SFC) with silica gel packed into the extraction vessel. In addition, squalene with ca. 68% purity could be obtained by repeating the SFC twice. After the saponification of the deodorization distillate, followed by solvent fractionation with hexane, highly purified phytosterols (97% purity) could be obtained, and highly purified squalene (81% and 100% purity) could be also obtained by using SFC combined with the solvent fractionation technique for the unsaponifiable materials. Therefore, it is considered that the present fractionation method combined with SFC and solvent fractionation is an effective means of concentrating squalene and phytosterols.
The characteristics of a non-endcapped polymeric ODS column for the resolution of triacylglycerol positional isomers (TAG-PI) were examined using a recycle HPLC-atmospheric pressure chemical ionization/mass spectrometry system. A pair of TAG-PI containing saturated fatty acids at least 12 carbons was separated. Except for TAG-PI containing elaidic acid, pairs of TAG-PI containing three unsaturated fatty acids were not separated, even by recycle runs. These results indicate that the resolution of TAG-PI on a non-endcapped polymeric ODS stationary phase is realized by the recognition of the linear structure of the fatty acid and the binding position of the saturated fatty acid in TAG-PI. Chain length was also an important factor for resolution. This method may be a useful and simple for measuring the abundance ratio of TAG-PI containing saturated fatty acids in natural oils.
A novel method to quantify glycidol fatty acid esters (GEs), supposed to present as food processing contaminants in edible oils, has been developed in combination with double solid-phase extractions (SPEs) and LC-MS measurements. The analytes were five species of synthetic GEs: glycidol palmitic, stearic, oleic, linoleic and linolenic acid esters. The use of selected ion monitoring in a positive ion mode of atmospheric chemical ionization-MS with a reversed-phase gradient LC provided a limit of quantification of 0.0045-0.012 μg/mL for the standard GEs, which enables the detection of GEs in μg ranges per gram of edible oil. Using the double SPE procedure first in reversed-phase and then in normal-phase second, allowed large amounts of co-existing acylglycerols in the oils to be removed, which improved the robustness and stability of the method in sequential runs of LC-MS measurements. When the method was used to quantify GEs in three commercial sources of edible oils, the recovery% ranged from 71.3 to 94.6% (average 79.4%) with a relative standard deviation of 2.9-12.1% for the two oils containing triacylglycerols as major components, and ranged from 90.8 to 105.1% (average 97.2%) with a relative standard deviation of 2.1-12.0% for the other, diacylglycerol-rich oil. Although the accuracy and precision of the method may not be yet sufficient, it is useful for determining trace levels of GEs and will be helpful for the quality control of edible oils.
Hydrophobic organic-inorganic hybrid composite suspensions were prepared by mixing hydrophobic octylsilyl titanium dioxide particles having average diameter of 35 nm with drying oil or moisture cure room temperature vulcanization silicone gum in volatile silicone. They were spread on a glass plate by using a linear motor coater and an applicator. Spatially periodic stripe patterns parallel to the direction of dragging the applicator were usually generated. The phenomenon is called directional viscous fingering, i.e. spontaneous pattern formation by the growth of fluctuation in morphology of mobile interface during the dragging coat. The pattern spontaneously formed on the surface became double scale when stored samples were coated. In this case, the large scale spatially periodic pattern was formed by the directional viscous fingering and the small ragged random pattern may be due to the giant molecules formed by cross-linking of silicone gum. Double scale roughness patterns were also generated by double dragging coat. The large and small scale pattern was formed by the first and second dragging coat, respectively. The formation of double scale roughness enhanced the water-repellent property of the hydrophobic surface. In some cases, water contact angle increased by 20° to realize super water-repellent surface with a value exceeding 150°.
We found the generation of dissymmetric gemini surfactants from symmetric ones in aqueous micelle solutions of gemini surfactants with a spacer containing disulfide linkage. The equilibrium was attained during 5 h incubation at 25°C with 1:2 ratio of symmetric to dissymmetric ones when the total concentrations were sufficiently high compared with monomer concentrations. The generation of dissymmetric form is attributed to the disulfide exchange between the spacer chains, which occurs in the mixed micelles of gemini surfactants with different hydrocarbon chains. The pseudo-phase separation model for micellization was successfully used to predict not only the cmc of binary and ternary mixtures composed of symmetric and dissymmetric gemini surfactants but also the monomer concentrations after the equilibrium. Reversibility of the disulfide exchange was ascertained by the generation of symmetric gemini surfactants from dissymmetric ones.
The interaction of guanidine-type cationic surfactants with bovine serum albumin (BSA) and liposome were investigated. Dodecylguanidine hydrochloride (C12A0G) and several dodecanoylamide alkylguanidine hydrochlorides (C12AmG, m = 2, 3, 4, 6) were used as the guanidine-type surfactants. In the interaction of these surfactants with BSA as a model protein, the binding isotherms of the surfactants to BSA were analysed. The structural change of the protein was also examined on the basis of circular dichroism and UV absobance data. In the interaction of these surfactants with liposome as a lipid bilayer model, we studied the effects of the surfactants on the solubilisation of liposomes and the release of carboxyfluorescein from liposomes. In addition, the effect of the surfactant molecular structure on the skin irritation was evaluated in connection with the interactions of the surfactants with BSA and liposome. It was found that small amounts of binding of C12A0G caused both a partial destruction of a-helix and an aggregation of BSA. C12A0G also induced the aggregation of liposomes, whereas C12AmG showed no such action. The presence of Am group in C12AmG appeared to reduce the skin irritation in parallel with the weakening of the interaction of the guanidine group with the protein and the lipid bilayer.
The removal of the carbon black (CB) particles from the polymer substrates was investigated in water/ethanol mixtures. As substrates, the films and the fibrous assemblies of polyethylene, nylon 6 and cellulose acetate were used. The ultrasonic wave was applied as a mechanical action for cleaning. The detergency of the CB particles for the films and the fibrous assemblies was assessed with the quartz crystal microbalance (QCM) technique and the reflectometry, respectively. The detergency for the films was discussed with the wetting force calculated from the experimentally determined contact angle on the substrate and surface tension of the water/ethanol mixture.