Abstracts of J. Oleo Science Vol.50, No.6


REGULAR PAPERS


Preparation and Surface Activities of Zwitterionic Surfactants Derived from Cotelomers of 4-Vinylpyridine and Methyl Acrylate,
T. YOSHIMURA¹, R. TOKUNAGA¹, H. SHOSENJI¹ and K. ESUMI²,
¹: Department of Applied Chemistry and Biochemistry, Faculty of Engineering, Kumamoto University, 2-39-1 Kurokami, Kumamoto-shi, Kumamoto 860-8555, JAPAN and ²: Department of Applied Chemistry, Institute of Colloid and Interface Science, Science University of Tokyo, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, JAPAN.
Cotelomer type zwitterionic surfactants having multi-hexyl chains and multi-carboxylate and multi-pyridinium functions (R₆S-zR₆VPQ-wVP-yAA, w and y mean the number of 4-vinylpyridine and sodium acrylate, respectively ; z means number of hexyl chains by quaternization) were prepared by quaternization and hydrolyses of cotelomers, which were prepared by cotelomerization of 4-vinylpyridine and methyl acrylate in presence of hexanethiol, and examined for their surface activities. Critical micelle concentration (cmc) of zwitterionic cotelomers shifted to lower concentration with increasing number of hexyl chains. The cmcs of R₆S-zR₆VPQ-wVP-yAA with z of 2.1-3.8 were from one 110th to one 4th of those of the corresponding cationic cotelomers. Zwitterionic cotelomers gave surface tension of 40-44 mN m^-1 at the cmc. The increase of number of hexyl chains in R₆S-zR₆VPQ-wVP-2.3AA series reduced the surface activities. Vigorous shaking of the mixtures of water and chloroform solution of zwitterionic cotelomers formed oil-in-water type emulsion. Highly stable emulsion was formed by using R₆S-zR₆VPQ-wVP-2.3AA with z of 1.4-2.1 and the degrees of emulsification were kept at the level of 60-70% after 360 min of standing. Zwitterionic cotelomers gave interfacial tension of 2-4 mN m^-1 at the water-chloroform interfaces and oriented themselves easier than equimolar mixtures of cationic cotelomer and anionic cotelomer.
J. Oleo Sci. 50, 467-473 (2001).


Three-phase Emulsification of Hexadecane with Dimyristoylphosphatidylglycerol Sodium Salt in Water: An Interpretation by New Phase Transition in Bilayer Assembly,
K. TAJIMA¹, Y. IMAI¹, A. NAKAMURA² and M. KOSHINUMA³,
¹: Faculty of Engineering, Kanagawa University, 3-27-1 Rokkakubashi, Kanagawa-ku, Yokohama-shi 221-8686, JAPAN, ²: School of Design and Architecture, Nagoya City University, 2-1-10 Kitachikusa, Chikusa-ku, Nagoya-shi 464-0083, JAPAN and ³: Faculty of Informatics, Teikyo Heisei University, 2289-23 Uruido, Ichihara-shi, 290-0193, JAPAN.
Properties of the three-phase emulsion of hexadecane have been investigated at 40°C as a function of mole fraction of hexadecane (X) in the mixture of hexadecane and dimyristoylphosphatidylglycerol sodium salt (NaDMPG). NaDMPG used as an emulsifier was the aqueous dispersion of the IM or the Gel-2 state. Here the IM state was a nematic-like metastable state that appeared above the critical temperature T^* (31.7°C), while the Gel-2 state was a stable gel state that was established after approximately 15 day aging of the IM state. DSC data showed that hexadecane was solubilized into the NaDMPG bilayers up to approximately X=0.5, and that at X>0.5 stable hexadecane emulsions were formed regardless of the states of the NaDMPG dispersions. XRD data showed that hexadecane emulsions were stabilized with the NaDMPG multibilayers solubilizing hexadecane in their palisade layers. In the region of X<0.5, hexadecane solubilized into the IM phase promoted formation of a gel structure of the IM phase, while hexadecane solubilized into the Gel-2 phase promoted hydrolytic cleavage of the ester bonds between glycerol and myristic acid in NaDMPG molecules. The emulsion prepared with the NaDMPG dispersions in the Gel-2 state were more stable than these prepared with the dispersions in the IM state, reflecting the different physical states of the NaDMPG dispersions.
J. Oleo Sci. 50, 475-484 (2001).


Suppression of SOS-Inducing Activity of Chemical Mutagens by Yakuchinone A from Alpinia oxyphylla in the Salmonella typhimurium TA1535/pSK1002 umu Test,
M. MIYAZAWA¹, Y. NAKAMURA¹, K. SAKANO¹, S. NAKAMURA² and H. KOSAKA²,
¹: Department of Applied Chemistry, Faculty of Science and Engineering, Kinki University, Kowakae, Higashiosaka-shi, Osaka 577-8502, JAPAN and ²: Osaka Prefectural Institute of Public Health, Nakamichi-1, Higashinari-ku, Osaka 537-0025, JAPAN.
The methanol extract from Alpinia oxyphylla showed a suppressive effect on umu gene expression of SOS response in Salmonella typhimurium TA 1535/pSK1002 against the mutagen 2-(2-furyl)-3-(5-nitro-2-furyl)acrylamide (furylfuramide). The methanol extract from A. oxyphylla was successively re-extracted with CH₂Cl₂, EtOAc, BuOH, and water. A dichloromethane fraction showed a suppressive effect. The suppressive compound in the dichloromethane fraction was isolated by SiO₂ column chromatography and identified as yakuchinone A (1) by GC, GC/MS, ¹H and ¹³C NMR spectroscopy. Compound 1 suppressed the SOS-inducing activity of furylfuramide in the umu test. Compound 1 suppressed 51.7% of the SOS-inducing activity at a concentration of 0.32 mM/mL. The ID₅₀ value (50% inhibition dose) of compound 1 was 0.30 mM/mL. This compound was assayed with an other mutagen, 3-amino-14-dimethyl-5H-pyrido[4,3-b]indole (Trp-P-1), which requires a liver metabolizing enzyme, activated Trp-P-1.
J. Oleo Sci. 50, 485-489 (2001).


Oxidative Stability of Conjugated Polyunsaturated Fatty Acids and Their Esters in Bulk Phase,
R. SUZUKI, K. NAKAO, M. KOBAYASHI and K. MIYASHITA,
Division of Marine Bioscience, Graduate School of Fisheries Science, Hokkaido University, 3-1-1 Minato, Hakodate 041-8611, JAPAN.
The oxidative stability of conjugated linoleic acid (CLA) and its ethyl ester (ethyl CLA) was compared with that of linoleic acid (LA) and ethyl LA in the bulk phase at 50°C. Progress of oxidation was determined by the measurement of oxygen absorption. The oxidative stability of CLA was almost the same as that of LA, but ethyl CLA was oxidatively more stable than ethyl LA. In the present study oxidative stabilities of soybean-triacylglycerol (TG) and TG containing CLA (CLA-TG) were also compared. Although the content of CLA (59.4%) in CLA-TG was slightly higher than that of LA (55.3%) in soybean-TG, CLA-TG was much more stable to oxidation than soybean-TG. On the other hand, the oxidative stability of a-linolenic acid (LN) and docosahexaenoic acid (DHA) decreased by the isomerization of double bonds in both fatty acids. The same result was obtained in the case of their ethyl esters. The isomerized LN and DHA contained conjugated trienes other than conjugated dienes. The lower oxidative stability of isomerized LN and DHA would be due to conjugated trienes in these PUFAs, whereas conjugated dienes had little effect on their oxidative stabilities.
J. Oleo Sci. 50, 491-495 (2001).


New Functions of 20-Hydroxyecdysone in Lipid Peroxidation,
A. I. KUZMENKO¹, E. NIKI² and N. NOGUCHI²,
¹: A.V. Palladin Institute of Biochemistry, Ukrainian National Academy of Sciences, 9 Leontovich St., Kiev, 01601, UKRAINE and ²: Research Center for Advanced Science and Technology, University of Tokyo, Meguro, Tokyo 153-8904, JAPAN.
The antioxidizing action of 20-hydroxyecdysone was investigated in several systems in vitro. Changes in the parameters of chemiluminescence in the presence of 20-hydroxyecdysone were found in rat liver mitochondrial fractions. The effect of 20-hydroxyecdysone on methyl linoleate micelles free radical oxidation was studied. The rate of oxygen uptake in methyl linoleate micelles was found to be smaller when 20-hydroxyecdysone was present than at its absence. The action of 20-hydroxyecdysone in the liposomal membranes oxidation was investigated by means of a-tocopherol consumption. A lower rate of a-tocopherol consumption in the oxidation of liposomal membranes was found when 20-hydroxyecdysone was present.
The effect of cholesterol on free radical formation in liposomal membranes was investigated. The rate of free-radical formation was smaller when cholesterol was present in the membrane than in membranes free of cholesterol. The a-tocopherol antioxidant effect in the membrane was also lower when cholesterol was present. We show here for the first time that 20-hydroxyecdysone has an antioxidant action in combination with a-tocopherol in membranes with cholesterol overload. Kinetic measurements were revealed the 20-hydroxyecdysone antioxidant effect on free radical reactions in membranes.
J. Oleo Sci. 50, 497-506 (2001).


Mechanism for Oxidative Decomposition of Anthraquinone Dye with Hydrogen Peroxide,
N. YAMAMOTO, T. KUBOZONO and Y. KINOSHITA,
Lion Corporation, Material Science Research Center, 7-13-12 Hirai, Edogawa-ku, Tokyo 132-0035, JAPAN.
Hydrogen peroxide has been used in detergent products as a bleaching agent for many years owing to its oxidizing capacity. In bleaching, decoloration occurs through oxidative decomposition of colored stain with hydrogen peroxide. The mechanism for this process has been extensively studied but detailed aspects remain unclarified. This study was conducted to provide further clarification of this mechanism using the anthraquinone dye, Alizarin Red S (ARS), as a model of colored stain. ESR was carried out for analysis of decomposition reactions of ARS. Four radical intermediates were noted to be formed through three elementary reactions. The first intermediate was to be a semiquinone radical of ARS, suggesting oxidative decomposition initiated by one-electron transfer from the dye to hydrogen peroxide. This intermediate induced the second decomposition by attacking hydrogen peroxide anions to afford two second intermediates, is followed by formation of phthalic acid as the final product. Kinetic study indicated the formation of the first intermediate, i.e., electron transfer from hydrogen peroxide to the dye, to be the rate-determining step of oxidative decomposition.
J. Oleo Sci. 50, 507-513 (2001).


NOTES


Conversion of 18-carbon Fatty Acids to Long Chain Polyunsaturated Fatty Acids in Some Thraustochytrids,
S.C. LALI¹, T. YOKOCHI² and T. NAKAHARA²,
¹: Centre for Biochemical Technology (INDIA), Mall Road, Delhi-110007, INDIA and ²: National Institute of Bioscience and Human-Technology, Higashi 1-1, Tsukuba, Ibaraki 305-8566, JAPAN.
Four strains that produce docosahexaenoic acid (DHA), two Schizochytriums (SR21/N1-27) and two Thraustochytriums (F3-1/W20), were cultured using oleic acid (OA), linoleic acid (LA), and a-linolenic acid (ALA) as carbon sources. These fatty acids in the medium were emulsified with Tween 80 using a ultrasonicator. Though SR21 grew faster than the other strains did, the fatty acid profile of SR21 did not changed throughout the culture period and the DHA content was not affected by the three fatty acids. The fatty acid profiles of the other three strains were affected by the fatty acids, i.e., ALA resulted in a higher DHA content and LA in a lower DHA content. Schizochytrium limacinum SR21 seems to have a different fatty acid synthetic pathway from the other strains and none of OA, LA and ALA seem to become precursors of DHA in the strain.
J. Oleo Sci. 50, 515-520 (2001).


Requirement of Polar Organic Solvents for Photosensitized Oxidation of Dibenzothiophenes and Biphasic Photooxidative Desulfurization of Light Gas Oil,
K. YAZU¹, Y. YAMAMOTO², K. MIKI¹ and K. UKEGAWA¹,
¹: Institute for Energy Utilization, National Institute of Advanced Industrial Science and Technology, 16-3 Onogawa, Tsukuba, Ibaraki 305-8569, JAPAN and ²: Department of Chemistry and Biotechnology Graduate School of Engineering, The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-8656, JAPAN.
Photooxidation of dibenzothiophene in the presence of molecular oxygen and a photosensitizer like anthraquinone (AQ) proceeded in MeCN, AcOH, acetone and MeOH but not in benzene or n-octane, indicating the requirement of polar solvents. The addition of MeCN to nonpolar solvent initiated the AQ-sensitized photooxidation even when the solvent was biphasic as in an n-octane/MeCN mixture. The major oxidation product of dibenzothiophene was the corresponding sulfoxide. 4,6-Dimethyldibenzothiophene is a very unreactive sulfur compound during hydrodesulfurization but its photooxidation proceeds about 4 times faster than that of dibenzothiophene during the co-photooxidation. Sulfur content in light gas oil was reduced to below 10 ppm in the AQ-sensitized photooxidation in biphasic system consisting of light gas oil and MeCN.
J. Oleo Sci. 50, 521-525 (2001).


Naphthalenetetracarboxydiimides and Related Compounds: Preparation and Characterization,
Y. SUGA, T. ARIMURA, S. IDE, H. SUGIWARA, T. NISHIOKA and M. TACHIYA,
National Institute of Materials and Chemical Research, COE laboratory, Higashi 1-1, Tsukuba, Ibaraki, 305-8565, JAPAN.
New 1,4,5,8-naphthalenetetracarboxydiimide (NDIM) derivatives were prepared in order to evaluate their solubilities and binding properties to form dimers via hydrogen bonds. Di-tert-butylphenyl groups of NDIMs effectively disturbed their intermolecular interaction even in high concentration and in low-polar solvent. The ¹H NMR titration studies in CDCl₃ indicated that all diimide derivatives did not exhibit the p-p stacking of naphthalene rings even in high concentration, and N-(2,5-di-tert-butylphenyl)-N'-hydrogen- 1,4,5,8-naphthalenetetracarboxydiimide (2,5-BDIM), N-(3,5-di-tert-butylphenyl)-N'-hydrogen- 1,4,5,8-naphthalenetetracarboxydiimide (3,5-BDIM), and N-(3,3-diphenylpropyl)-N'hydrogen-1,4,5,8-naphthalenetetracarboxydiimide (3,3-PDIM) showed self-assembly properties through intermolecular hydrogen bondings.
J. Oleo Sci. 50, 527-532 (2001).


Novel Synthetic Route to 2,5-Disubstituted Furan Derivatives through Surface Active Agent-Catalysed Dehydration of D(-)-Fructose,
K. HAMADA¹, H. YOSHIHARA² and G. SUZUKAMO³,
¹: Organic Synthesis Laboratory, Sumitomo Chemical Co. Ltd., 2-10-1, Tsukahara, Takatsuki-shi 569-1093, JAPAN, Current address : Central Research Laboratory, Pias Corporation, 3-1, 1-chome, Murotani, Nishi-ku, Kobe 651-2241, JAPAN, ²: Organic Synthesis Laboratory, Sumitomo Chemical Co. Ltd., 2-10-1, Tsukahara, Takatsuki-shi 569-1093, JAPAN, Current address : Oita Branch, Sumika Technoservice Corporation, 2200, Oaza-Tsurusaki, Oita-shi 870-0106, JAPAN and ³: Organic Synthesis Laboratory, Sumitomo Chemical Co. Ltd., 2-10-1, Tsukahara, Takatsuki-shi 569-1093, JAPAN.
5-Chloromethyl-2-furfural, generated in situ by surface active agent-catalysed dehydration of D(-)-fructose, was conducted to obtain 5-methyl-2-furfural,2,5-dimethyl furan,2,5-hexanedione and 2,5-dimethyl-1-thioureidopyrrole.
J. Oleo Sci. 50, 533-536 (2001).