Pure enantiomers can be produced by chemical and enzymatic methods. Enzymatic methods to produce pure enantiomers are more advantageous. High enantiomeric excess is the advantage of enzymatic method, resulting from the inherent selectivity of the enzyme. Lipase (EC 188.8.131.52) enzymes are widely used for the synthesis of chirally pure enantiomers because of their stereoselectivities which can satisfy the growing demand for obtaining optically active compounds. Various methods are used for the synthesis of chirally pure enantiomers, however kinetic resolution and asymmetric synthesis are more common. The ability to produce enantiomerically pure compounds is probably most important in the pharmaceutical industry, where approximately 80% of the drugs currently under development are chiral. The main problems regarding the use of lipases are the cost of lipase and slower reaction rate. However, by immobilizing the enzyme on a suitable matrix or support, this problem can be solved. Furthermore, immobilization of enzyme increases the chances of re-usability.
The enzymatic indirect method for simultaneous determinations of 3-chloro-1, 2-propanediol fatty acid esters (3-MCPD-Es) and glycidyl fatty acid esters (Gly-Es) make use of lipase from Candida cylindracea (previously referred to as C. rugosa). Because of low substrate specificity of the lipase for esters of polyunsaturated fatty acids (PUFA), such as docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA), fish oils high in PUFAs are currently excluded from the range of application of the method. The objective of this study was to make the enzymatic indirect method applicable to fats and oils containing PUFAs. By using a Burkholderia cepacia lipase, and by removing sodium bromide from hydrolysis step and adding it after completion of the hydrolysis step, satisfactory recovery rates of 91–109% for 3-MCPD, and 91–110% for glycidol (Gly) were obtained from an EPA and DHA concentrated sardine oil, three DHA concentrated tuna oils, two fish oils, and five fish-oil based dietary supplements spiked with DHA-esters or oleic acid-esters of 3-MCPD and Gly at 20 mg/kg. Further, results from unspiked samples of seven fish oil based dietary supplements and five DHA concentrated tuna oils analyzed by the improved enzymatic indirect method were compared with the results analyzed by AOCS Cd 29a. For all 3-MCPD, 2-MCPD and Gly, the 95% confidence intervals determined by the weighted Deming regression for slopes and intercepts contained the value of 1 and 0, respectively. It was therefore concluded that the results from the two methods were not statistically different. These results suggest that fish oils high in PUFAs may be included in the range of application for the improved enzymatic indirect method for simultaneous determinations of 3-MCPD and Gly esters in fats and oils.
Oil used for deep-frying is often left to stand after cooking. A major concern is oxidation during standing that might be avoidable, especially in the case of oil used repeatedly for commercial deep-frying as this involves large volumes that are difficult to cool in a conventional fryer. This paper describes a method to minimize oil oxidation. French fries were deep-fried and the oil temperature decreased in a manner typical for a commercial deep-fryer. The concentration of polar compounds generated from thermally oxidized oil remarkably increased at temperature higher than 100°C but little oxidation occurred below 60°C. Heating the oil showed that the peroxide and polar compound content did not increase when the oil was actively cooled using a running water-cooled Graham-type condenser system to cool the oil from 180°C to room temperature within 30 min. When French fries were fried and the oil was then immediately cooled using the condenser, the polar compound content during cooling did not increase. Our results demonstrate that active cooling of heated oil is simple and quite effective for inhibiting oxidation.
Soybean lecithin is a by-product obtained during degumming step of crude soybean oil refining. Crude soybean lecithin (CSL) contains major amount of phospholipids (PLs) along with minor amount of acylglycerols, bioactive components, etc. Due to presence of PLs, CSL can be used as an emulsifier. Crude soybean lecithin (CSL) was utilized to synthesize hydroxylated soybean lecithin (HSL) by hydroxylation using hydrogen peroxide and catalytic amount of lactic acid to enhance the hydrophilicity and emulsifying properties of CSL. To reduce the reaction time and to increase rate of reaction, HSL was synthesized under ultrasound irradiation. The effect of different operating parameters such as lactic acid, hydrogen peroxide, temperature, ultrasonic power and duty cycle in synthesis of HSL were studied and optimized. The surface tension (SFT), interfacial tension (IFT) and the critical micelle concentration (CMC) of the HSL (26.11 mN/m, 2.67 mN/m, 112 mg/L) were compared to CSL (37.53 mN/m, 6.22 mN/m, 291 mg/L) respectively. The HSL has better emulsion stability and low foaming characteristics as compared to CSL. Therefore, the product as an effective emulsifier can be used in food, pharmacy, lubricant, cosmetics, etc.
A method of analyzing the detergency of various soils by assuming normal distributions for the soil adhesion and soil removal forces was developed by considering the relationship between the soil type and the distribution profile of the soil removal force. The effect of the agitation speed on the soil removal was also analyzed by this method. Washing test samples were prepared by soiling fabrics with individual soils such as particulate soils, oily dyes, and water-soluble dyes. Washing tests were conducted using a Terg-O-Tometer and four repetitive washing cycles of 5 min each. The transition of the removal efficiencies was recorded in order to calculate the mean value (μrl) and the standard deviation (σrl) of the removal strength distribution. The level of detergency and the temporal alteration in the detergency can be represented by μrl and σrl, respectively. A smaller σrl indicates a smaller increase in the detergency with time, which also indicates the existence of a certain amount of soil with a strong adhesion force. As a general trend, the values of σrl were the greatest for the oily soils, followed by those of the water-soluble soils and particulate soils in succession. The relationship between the soil removal processes and the soil adhesion force was expressed on the basis of the transition of the distribution of residual soil. Evaluation of the effects of the agitation speed on µrl and ơrl showed that σrl was not affected by the agitation speed; the value of µrl for solid soil and oily soil increased with increasing agitation, and the µrl of water-soluble soil was not specifically affected by the agitation speed. It can be assumed that the parameter ơrl is related to the characteristics of the soil and the adhesion condition, and can be applied to estimating the soil removal mechanism.
We have characterized an emulsion system stabilized by an amphiphilic random copolymer, methoxy polyethylene glycol-23 methacrylate/glyceryl diisostearate methacrylate copolymer (MPM-GDM). The combined results of the static surface tension and transmission electron microscopy with freeze-fracture technique (FF-TEM) suggested that this copolymer forms aggregates in aqueous solutions. The membrane emulsification method produced an oil-in-water (O/W) emulsion in the mixture of squalane, water, and MPM-GDM, where the squalane concentration was set at 10 - 60 wt% and the MPM-GDM concentration was either 1 or 5 wt%. The prepared emulsion was stable against coalescence due to the formation of an adsorption layer of MPM-GDM. Based on the FF-TEM results, it is confirmed that a relatively large island-like structure is formed on the emulsion droplet surface. Furthermore, MPM-GDM can act as a thickening agent of the continuous liquid phase, which enhances the stability against creaming. The cooperative two effects improve the stability of the emulsion system without adding co-stabilizer such as low molecularweight surfactants.
1H-nuclear magnetic resonance (1H-NMR) measurements can identify the specific protons that contribute to interactions between molecules. Using this technique, micelles formed by four bile salts: sodium taurocholate (NaTC), taurodeoxycholate (NaTDC), taurochenodeoxycholate (NaTCDC), and tauroursodeoxycholate (NaTUDC) were measured and compared in viewpoint of molecular interactions. Rotating-frame nuclear Overhauser effect and exchange spectroscopy (ROESY) analysis of the four bile salts showed differences with respect to the type of micelle formation. For all four bile salts, the key protons contributing to hydrophobic interactions were found to be the methyl protons at positions 18 and 19. The cross-peak patterns for the four bile salt species indicated pairs of characteristic proton depending on a bile salt species. The spin-lattice relaxation time (T1) of the alkyl side-chain in NaTC was relatively long compared to that of the three other bile salts, even when the concentration was higher than the critical micelle concentration (cmc). This unique behavior indicates that the hydrophilic region of NaTC molecules is flexible within their micelles. Moreover, T1 values for the typically hydrophobic methyl protons at sites C18 and C19 of NaTC were almost constant above the cmc. These results may suggest that NaTC micelles remain as small primary structures in solution unlike the three other bile salt molecules investigated in the study.
Dynamic surface tensions of two types of heterogemini surfactants with nonidentical hydrophilic headgroups consisting of a quaternary ammonium salt (cationic) and a gluconamide (nonionic) or sulfobetaine (zwitterionic) group were measured using the maximum bubble pressure method. For these compounds, effects of alkyl chain length, structure of the hydrophilic groups, and surfactant concentration were investigated using diffusion coefficients and parameter x. The parameter x is related to the difference between the energies of adsorption and desorption of the surfactant. The values of x of heterogemini surfactants increased as the alkyl chain length increased, and they were slightly larger than that for the corresponding monomeric surfactant. This is because of an increase in hydrophobicity caused by two alkyl chains, as well as interactions between two different hydrophilic groups. Adsorption rate of the heterogemini surfactants decreased with increasing alkyl chain length, indicating slow dynamics, and inhibited adsorption to the air/water interface as the chain length increased. However, at higher concentrations, the heterogemini surfactants showed rapid and effective adsorption and increased adsorption rates at higher concentrations. Diffusion coefficients of the heterogemini surfactants decreased with increasing concentrations for all chain lengths, indicating diffusion of the solute molecules to the subsurface and adsorption of the solute from the subsurface to the surface.
Docosapentaenoic acid (22:5n-3, n-3 DPA) is a n-3 polyunsaturated fatty acid (PUFA) found in fish oil, and has been reported to have health benefits. This study investigated conversion of n-3 DPA, and examined the anti-inflammatory effects of n-3 DPA on activated macrophages. Murine macrophage-like RAW264.7 cells were incubated in culture media containing n-3 DPA for 72 h. The level of n-3 DPA in the fatty acid composition of the total lipid fraction increased in a dose-dependent manner. Furthermore, the levels of docosahexaenoic acid (DHA) and eicosapentaenoic acid (EPA) were higher in treated cells than in control cells. In RAW264.7 cells stimulated by lipopolysaccharide (LPS), n-3 DPA significantly down-regulated mRNA expression of pro-inflammatory factors such as IL-6, IL-1β, iNOS and COX-2. Production of IL-6 was also reduced by n-3 DPA in a dose-dependent manner. We found that n-3 DPA treatment resulted in greater IL-6 mRNA down-regulation than that achieved with EPA treatment, and was similar to that of DHA treatment. Furthermore, expression levels of IL-6 and IL-1β mRNAs were measured in the presence of the delta-6 desaturase inhibitor SC26196 in the culture medium to inhibit the conversion of n-3 DPA to DHA. There was no significant difference in the down-regulation in the mRNA expression of pro-inflammatory cytokines in RAW264.7 cells by n-3 DPA with or without presence of SC26196. These results demonstrate that n-3 DPA exhibits anti-inflammatory effects in activated RAW264.7 cells, which are independent of DHA conversion.
Renal necrosis can be induced in weanling rats due to choline deficient diet. Menhaden oil has a protective effect against the development of renal necrosis in choline deficient weanling rats. The aim of this work was to determine the effects of menhaden oil in a model of acute kidney injury due to ischemia reperfusion. Wistar rats were divided into two groups and fed vegetable oils or menhaden oil as lipids. Unilateral renal ischemia was performed for 30 minutes and animals were sacrificed 48 hours later. Histopathological examination showed no significant differences between groups. Menhaden oil did not prevent histopathological lesions.
One approach to improve the oxidative stability of biodiesel is the partial hydrogenation of carbon-carbon double bonds. In the current work, an efficient catalytic system using Pd(OAc)2 dissolved in polyethylene glycol (PEG) which in situ generates palladium nanoparticles was developed in order to promote a selective partial hydrogenation reaction of sunflower oil FAMEs into mono-hydrogenated products avoiding the formation of saturated compounds or trans-isomers. High content of methyl oleate (85.0±1.4%) was obtained by hydrogenation of sunflower oil biodiesel with only 7.0±0.2% stearic acid. Through evaluating the palladium nanoparticles by TEM analysis, it is observed that 4 nm palladium nanoparticles generated in situ in PEG4000 are highly selective for the partial hydrogenation of sunflower oil biodiesel. And the Pd-PEG4000 catalyst can be resued for five times without obvious loss of activity or methyl oleate selectivity.
The discovery of potent cytotoxic isolates from botanicals provides an opportunity to explore this viable tool for cancer chemoprevention. The antileukemic potential of clerodane diterpene from Polyalthia longifolia leaves has already been established. However, in this present study, utilizing chromatographic techniques we report for the first time, the isolation of a rare tetranorditerpene (compound 1) from P. longifolia. The structure of compound 1 was elucidated and confirmed by spectrophotometric data. UPLC-MS analysis was conducted on the methanolic extract, ethyl acetate fraction, and isolated tetranorditerpene showed that the tetranorditerpene is one of the major constituents of the plant with a retention time of 30.78 min. In addition, a methyl ester derivative (compound 2) of the isolated tetranorditerpene was synthesized. Using the CCK-8 assay, we compared the cytotoxic potential of isolated tetranorditerpene (1) and methyl ester derivative (2) with the previously isolated clerodane diterpenes. Our results showed that the methyl ester derivative (2) displayed the highest inhibitory activity against human leukemia HL-60 cells. The isolated tetranorditerpene (1) did not exhibit significant inhibitory effect against HL-60 cells. Morphological examination indicated chromatin condensation and nuclear fragmentation suggesting induction of apoptosis in compound 2 treated HL-60 cells. The methyl esterification of the isolated tetranorditerpene (1) conferred on it a significant level of antileukemic activity suggesting the possibility of a synergistic relationship between pure compound isolation and synthetic reaction in the discovery of new chemopreventive agents.
Intake of trans fatty acid (TFA) is believed to change the ratio of low-density lipoprotein (LDL) to high density lipoprotein (HDL) cholesterol in blood, which leads to cardiovascular disease. In this study, thirteen types of TFA including monoene type TFA (trans-octadecenoic fatty acid isomers, t-18:1 isomers), diene type TFA (t9,t12-18:2), and triene type TFA (t-18:3) were added to cultured HepG2 cells to compare the amount of apolipoprotein A1 and B (those relating to levels of HDL and LDL cholesterol in blood, respectively) being secreted. We found that trans-5-18:1 increased the secretion of apolipoprotein B relative to oleic acid (cis-9-18:1, control). Secretion of apolipoprotein B was also increased by t-18:3; however, the amount was not significant compared with that observed in the control. The secretion amount of apolipoprotein B tended to increase with the number of double bonds in TFA among trans-9-18:1, t9,t12-18:2, and t-18:3. The secretion amount of apolipoprotein A1 after TFA treatment was also measured. No significant difference was detected among t-18:1 groups; however, t-18:3 increased the amount significantly compared to that in the control. These results suggest that the effect of TFA isomers on the ratio of LDL to HDL cholesterol in the blood follows a mechanism different from that in cultured cells.
Important Announcement for the Contributors of the Journal of Oleo Science;
At 0:00 AM on April 1, 2016 (Japan time), the Journal of Oleo Science will start charging Publication Charge for each case; 1: 20,000 yen (within 8 pages. /more than 8 pages, additional charge is necessary; 2,000 yen per page) for Members of Japan Oil Chemists’ Society (JOCS) (including Asian Members and Support Members), 2: 40,000 yen (within 8 pages. /more than 8 pages, additional charge is necessary; 4,000 yen per page) for Non-Members of JOCS.
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