Abstracts of  J. Oleo Science Vol. 51, No. 2


REGULAR PAPERS

Influence of Rosemary Extract on the Oxidative Stability of Tuna Orbital Oil and on the Effect in vivo of the Oxidized Oil on Rat Liver,
Keiko YOSHIOKA¹, Ai YAMADA¹ and Shun WADA²,
¹: Department of Food and Nutrition, Nakamura Gakuen University, 5-7-1 Befu, Jonan-ku, Fukuoka 814-0198, JAPAN and ²: Department of Food Science and Technology, Tokyo University of Fisheries, 4-5-7 Konan, Minato-ku, Tokyo 108-8477, JAPAN.
  Rosemary extract was added to tuna orbital oil (fish oil) to restrain oxidation, and both the peroxide value (PV) and the fatty acid composition of the fish oil were determined under autoxidation conditions. The oxidative stability of fish oil added with rosemary at levels of 0.02% or 1.0% of rosemary extract (w/w) was more effective compared to the original fish oil under autoxidation for 8 days at 20°C, which thus demonstrated the antioxidative ability of rosemary. Further, rosemary extract was added to the diet of rats and the influence of the oxidized fish oil on the liver lipids and fatty acid was examined. The lipid content and PV of the liver lipid of rats administered oxidized fish oil and rosemary did not show much difference among experimental groups. The changes in the fatty acid composition in rat liver lipid were considered to reflect the metabolism of unsaturated fatty acids in vivo.
J. Oleo Sci., 51, 73-81 (2002).

Phosphonoglycolipids in Marine Crustacean: Structural Characterization of Two Novel Phosphonocerebrosides, from the Crab, Erimacrus isenbeckii,
Koji KIMURA¹, Saki ITONORI¹, Noriyasu HADA², Osamu ITASAKA¹, John T. DULANEY³, Tadahiro TAKEDA² and Mutsumi SUGITA¹,
¹: Department of Chemistry, Faculty of Liberal Arts and Education, Shiga University, 2-5-1, Hiratsu, Otsu-shi, Shiga 520-0862, JAPAN, ²: Department of Pharmacognosy and Phytochemistry, Kyoritsu College of Pharmacy, 1-5-30, Shibakoen, Minato-ku, Tokyo 105-8512, JAPAN and ³: Department of Medicine, Division of Nephrology, The University of Tennessee, 951 Court Avenue 649D, Memphis TN 38163, USA.
  Two novel phosphonoglycolipids, named PnGC₁ and PnGC₂ were isolated from the marine crab, Erimacrus isenbeckii by successive column chromatography on ion exchange Sephadex (DEAE- and QAE-Sephadex) and silicic acid (Iatrobeads). Their chemical structures were characterized as phosphonocerebrosides, 4'-O-(2-aminoethylphosphonyl)Glc_pb1-1ceramide for PnGC₁ and 4'-O-(N-methyl-2-aminoethylphosphonyl)Glc_pb1-1ceramide for PnGC₂ by IR, MALDI-TOF MS, ¹H-NMR, GC and GC-MS analyses of the water-soluble products after acid hydrolysis, and methylation of the product of hydrogen fluoride degradation. In both phosphonocerebrosides, the ceramide moieties were composed of tetradeca-4-sphingenine as the sole sphingoid, and stearic, arachidic, behenic and docosamonoenoic acids as the major fatty acids.
J. Oleo Sci., 51, 83-91 (2002).

Behavior of Tocopherol and Vitamin K₁ in the Hydrogenation of Edible Oil,
Takeshi YAMAGAMI¹, Minoru AOYAMA¹, Nobuhiro SAKURAI², Takashi TSUTSUMI², Shigeru TOKAIRIN², Hiroshi EHARA², Takenori MARUYAMA¹ and Isao NIIYA¹,
¹: Japan Institute of Oil & Fats, Other Foods Inspection, Foundation, 3-27-8, Nihonbashi-Hamacho, Chuo-ku, Tokyo 103-0007, JAPAN and ²: Tsukishima Foods Industry Co., Ltd., 3-17-9, Higashi-Kasai, Edogawa-ku, Tokyo 134-8520, JAPAN.
  Determination was made of a- and g-tocopherol, vitamin K₁ and 2',3'-dihydrovitamin K₁ in vegetable oil during the course of hydrogenation under various conditions. Iodine value(IV) was found to decrease from 80 to 60 with hydrogenation, with consequently considerable reduction in vitamin K₁. At IV 50 or less, vitamin K₁ was virtually essentially absent (0.1 mg/kg or less). 2',3'-dihydrovitamin K₁ increased with decrease in vitamin K₁. 2',3'-dihydrovitamin K₁ peaked at 2.9 mg/kg at IV 50, and then decreased. a- and g-Tocopherol content remained basically the same under all conditions. Subsequent to oil hydrogenation and then deodorization at 260°C for 120 minutes, a-tocopherol showed the highest residual ratio (80%) of all the vitamins, followed by 2',3'-dihydrovitamin K₁ (66%) and vitamin K₁ (60%).
J. Oleo Sci., 51, 93-96 (2002).

Polymeric Antioxidants. V. Ortho Methylene-bridged and Direct-linked Sesamol Oligomers,
Kouichi ASAKURA¹, Eitoshi HONDA¹, Shuichi MATSUMURA¹, Shuichi OSANAI¹ and Kazuo KAWADA²,
¹: Faculty of Science and Technology, Keio University, 3-14-1, Hiyoshi, Kohoku-ku, Yokohama-shi 223-8522, JAPAN and ²: School of Science, Kitasato University, 1-15-1, Kitasato, Sagamihara-shi 228-8555, JAPAN.
  Two types of sesamol oligomers, ortho methylene-bridged and direct-linked oligomers, were prepared and their antioxidant effects on the autoxidation of lard and tetralin were evaluated. The methylene-bridged oligomers were prepared by the reaction of sesamol, a major antioxidative compound in sesame seed, with ethylmagnesium bromide and subsequent oligomerization with paraformaldehyde. During the reaction, methylidenedioxy moieties of the sesamol oligomers were partially cleaved and the addition of hydroxyl groups was observed. The methylene-bridged oligomers had much stronger antioxidant effects on the autoxidation of lard than the sesamol monomer. And the oligomers, having a larger average number of hydroxyl groups per sesamol unit, were a more efficient antioxidant for lard. Direct-linked oligomers were synthesized by an oxidative coupling of sesamol by hydrogen peroxide using horseradish peroxidase as a catalyst. Molecular structures of the direct-linked oligomers were influenced by the pH of the buffer solution in which the oxidations were carried out. Oligomers having a larger number of hydroxyl groups were prepared under more acidic conditions. The direct-linked oligomers prepared in acidic conditions were better antioxidants of lard than the sesamol, whereas oligomers prepared under neutral and alkaline conditions did not improve the antioxidant effect. Both methylene-bridged and direct-linked oligomers inhibited the autoxidation of tetralin; but, in contrast to the lard results, almost all of the oligomers were less effective antioxidants for tetralin than the sesamol monomer.
J. Oleo Sci., 51, 97-102 (2002).

Adiabatic Compressibility of Aqueous Solutions of Amphiphiles with an Ammonium Group as the Hydrophilic Domain,
Kazuhiro FUKADA¹, Jinhua LI², Masatoshi FUJII², Tadashi KATO² and Tsutomu SEIMIYA²,
¹: Department of Biochemistry and Food Science, Faculty of Agriculture, Kagawa University, Ikenobe 2393, Miki-cho, Kagawa 761-0795, JAPAN and ²: Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, Hachiohji, Tokyo 192-0397, JAPAN.
  The apparent molar volume and the apparent molar adiabatic compression of aqueous solutions of n-alkylammonium bromide (C_nH_2n+1NH₃Br; n = 1-8, 10) and n-alkyltrimethylammonium bromide (C_nH_2n+1N(CH₃)₃Br; n = 1, 8, 10) were measured using a vibration-tube density meter and a sing-around ultrasound velocity meter at 5°C, and the partial molar volume and the partial molar adiabatic compression at infinite dilution (f_V⁰ and f_K⁰) were evaluated. It was confirmed that f_K⁰ linearly decreased with increasing alkyl chain length while f_V⁰ linearly increased. Differences of f_K⁰ between C_nH_2n+1NH₃Br and C_nH_2n+1N(CH₃)₃Br with the same alkyl chain were negligibly small, which was in good agreement with the fact that the successive N-methylation of ammonium cation had only a little effect on compression. These results could be interpreted in terms of the compensation between the increase of hydrophobic hydration and the decrease of electrostriction of water around the ammonium group, leading the net compression being almost constant. When the amphiphiles with an octyl or a decyl group form micelles above their critical micelle concentration, on the contrary, the adiabatic compression of C_nH_2n+1NH₃Br was distinctly larger than that of C_nH_2n+1N(CH₃)₃Br. The reason for the difference in compression of these micelles was discussed concerning the counter ion binding and the aggregation number.
J. Oleo Sci., 51, 103-111 (2002).

Microemulsions in Poly (oxyethylene) Poly (dimethylsiloxane) Copolymer (Surfactant) Systems,
Hironobu KUNIEDA¹, Md. Hemayet UDDIN¹, Yuji YAMASHITA¹, Haruhiko FURUKAWA² and Asao HARASHIMA²,
¹: Graduate School of Environment and Information Sciences, Yokohama National University, Tokiwadai 79-7, Hodogaya-ku, Yokohama 240-8501, JAPAN and ²: Dow Corning Toray Silicone Co. Ltd., Chigusa-Kaigan 2-2, Ichihara 299-0108, JAPAN.
  A-B-type silicone copolymer (or surfactant), Me₃SiO(Me₂SiO)₁₂-Me₂SiCH₂CH₂CH₂-O-(CH₂CH₂O)_33.1H (Si₁₄C₃EO_33.1), forms lamellar liquid crystal (L_a) in a pure state. In a binary water-Si₁₄C₃EO_33.1 system, the L_a phase coexists with excess water in a dilute region, whereas the L_a phase changes to an isotropic solution (W_m) by replacing water with ethylene glycol. Although water enhances the segregation between hydrophilic and lipophilic chains of copolymer, it does not change the layer curvature of long lipophilic-chain copolymer to be positive. Since ethylene glycol is more soluble in the hydrophilic chain than water, it changes the curvature from zero to positive, where positive curvature means the copolymer-layer curvature is convex toward water or polar solvent. When ethylene glycol is replaced with PEG 300 (polyethylene glycol, M_n ca = 300), the L_a-H₁(normal hexagonal phase)-W_m transition takes place. With the further increase in the molecular weight of PEG, the L_a phase coexists with an excess PEG as well as the water-copolymer system and the solubilization of PEG in the L_a phase decreases. This change in the phase behavior may be attributed to the solubilization part of PEG in the hydrophilic chain of the silicone copolymer. On the other hand, non-polar solvent, octamethylcyclotetrasiloxane, D₄, is soluble in the lipophilic chain, and the L_a phase changes to a reverse micellar solution (O_m) via reverse hexagonal (H₂) phase. With the increase in the molecular weight of oil, the L_a phase retreats to the concentrated region and the solubilization of oil (poly(dimethylsiloxane)) in the L_a phase becomes very low. As a result, PEG and silicone oil change the surfactant (or copolymer) layer curvature in the opposite way, but, the swelling of high-molecular-weight solvents or homopolymers in the L_a phase is very restricted. In ternary water/ Si₁₄C₃EO_33.1/D₄, ethylene glycol/ Si₁₄C₃EO_33.1/D₄, and PEG/ Si₁₄C₃EO_33.1/poly (dimethylsiloxane) systems, isotropic microemulsions are formed at an equal polar/non-polar solvent ratio. The relationship between microemulsions with water and oil or with hydrophilic and lipophilic homopolymers is also discussed.
J. Oleo Sci., 51, 113-122 (2002).

Aqueous Properties of Mixed Anionic Gemini Surfactant and Conventional Anionic Surfactant,
Kazuyuki TSUBONE¹ and Kazuo TAJIMA²,
¹: Kanebo, LTD., Cosmetics Laboratory, 3-28, Kotobuki-cho-5- chome, Odawara-shi, Kanagawa, 250-0002 JAPAN and ²: Dept. Chem. Kanagawa Univ., 3-27 Rokkakubashi, Yokohama-shi, Kanagawa, 221-8686, JAPAN.
  In order to determine the characteristics of a mixed system of an anionic gemini surfactant with N,N-dialkylamide and carboxylate groups and a conventional anionic surfactant, aqueous solutions of (CH₂)₂[NCO(C₁₁H₂₃)C₂H₄CO₂Na]₂ (212)/sodium dodecanoate (soap) mixture were studied. The following parameters were measured: critical micelle concentration (cmc), micelle composition, surface tension, foaming power, degree of micelle ionization, and pH values. For the sake of comparison, mixtures of SDSa/soap (SDSa = sodium N-dodecanoylsarcosinate, the corresponding monomer of 212) were also investigated. The cmc values of the SDSa/soap mixture monotonously increase with increasing molar fraction of soap at 30°C. In contrast, the cmc values of the 212/soap mixture are intermediate between those for the pure surfactants over a broad region at 30°C. The composition of 212/soap mixture in micelles is kept at a 2:1 molar ratio in the plateau region. With increase in temperature of 212/soap mixture, cmc values reach a maximum at a soap molar fraction of 0.6. This is obvious at 50°C. The surface tension of 212/soap mixture is minimal at a soap molar fraction of 0.6 at 30°C, at which the surface tension is the lowest among those of the pure surfactants. The foaming power of the 212/soap mixture is maximal at the soap molar fraction of 0.6, at which the foaming power is the largest among those of the pure surfactants. Greater degree of micelle ionization for 212/soap mixture than for SDSa/soap mixture was observed over a broad region. The reason for this is the larger proton uptake by the carboxylate group of 212 than that of SDSa, which releases Na⁺ into the bulk phase in the mixed micellization process. The evidence for this is the larger increase in pH in the mixed cmc solutions for 212/soap mixture than for SDSa/soap mixture. The unexpected synergistic interaction between 212 and soap molecules is due to stronger reduction of the mutual repulsion between the anionic head groups in the 212 molecule in the presence of a soap molecule.
J. Oleo Sci., 51, 123-131 (2002).

Electrochemical Behavior of a Ferrocene-Modified Cationic Surfactant Mixed with an Anionic Surfactant in Aqueous Solutions,
Koji TSUCHIYA¹, Hideki SAKAI^1,2, Kyungok KWON³, Takuto TAKEI¹ and Masahiko ABE^1,2,
¹: Department of Pure and Applied Chemistry, Tokyo University of Science, 2641, Yamazaki, Noda, Chiba 278-8510, JAPAN, ²: Institute of Colloid and Interface Science, Tokyo University of Science, 1-3, Kagurazaka, Shinjuku, Tokyo 162-8601, JAPAN and ³: Korea Fire Equipment Inspection Corporation, 29-16, Shinheung-dong, 3ga, Chung-ku, Inchon City, Seoul, KOREA.
  The aggregation behavior of molecular assemblies formed between oppositely charged surfactants in water was investigated through measurements of the electrochemical behavior of the cationic component, 11-ferrocenylundecyltrimethylammonium bromide (FTMA), in mixtures with the anionic component, sodium dodecylbenzenesulfonate (SDBS). FTMA/SDBS mixture was found to form various types of molecular assemblies such as micelles and vesicles in aqueous solutions depending on the mixing ratio. Cyclic voltammogram on FTMA in the molecular assemblies showed that the peak of oxidation current due to FTMA/SDBS complexes consisting of vesicles is observed on the anodic side of that due to FTMA molecules consisting of mixed micelles. Moreover, electrochemical measurements on the total surfactant concentration dependence of the phase behavior in solutions of 1:0.4 molar ratio of FTMA and SDBS revealed that vesicles begin to form at a concentration (critical aggregation concentration; cac) much lower than the critical micelle concentration (cmc) of FTMA alone and a phase containing both vesicles and micelles appears at a concentration higher than the cmc.
J. Oleo Sci., 51, 133-140 (2002).

NOTE

Effects of Brewer's Yeast Cell Wall on Serum Lipid Levels in Rats Fed a High Cholesterol and Fat Diet,
Yoshitaka HITOMI, Michiko YOSHIDA, Tomohiko NAKAMURA and Yoshiharu SHIRASU,
Applied Bioresearch Center, Research and Development Department, Kirin Brewery Co., Ltd., Miyahara Machi 3, Takasaki, Gunma 370-1295, JAPAN.
  We examined whether brewer's yeast cell wall (BYC) is able to reduce serum lipid levels in rats fed a high cholesterol and fat (HCF) diet. Male Sprague-Dawley rats were fed a standard diet, an HCF diet or an HCF diet containing 2.5% or 5.0% BYC for 14days. The addition of 5.0% BYC to the HCF diet significantly reduced the increment of serum total cholesterol levels. On the basis of the results obtained, BYC may be utilized as a cholesterol-lowering foodstuff.
J. Oleo Sci., 51, 141-144 (2002).

RAPID PAPER

Solubilization of Oil-soluble Medicines by Liposome with Deep Sea Water,
Chihiro KAISE^1,2, Hideki SAKAI^1,3, Aritomo YAMAGUCHI^1,3, Shoko YOKOYAMA⁴, Teruhisa KANEKO² and Masahiko ABE^1,3,
¹: Faculty of Science and Technology, Tokyo University of Science, 2641,Yamazaki, Noda-shi, Chiba 278-8510, JAPAN, ²: SHU UEMURA Co., 5-7-17, Minamiaoyama, Minato-ku, Tokyo 107-8603, JAPAN and ³: Institute of Colloid and Interface Science, Tokyo University of Science, 1-3, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, JAPAN and ⁴: Kyoritsu College of Pharmacy, 1-5-30, Shibakoen, Minato-ku, Tokyo 105-8512, JAPAN.
  Phospholipid liposomes were prepared using deep sea water and the liposomes obtained were used to solubilize oil-soluble medicines. In addition, the dispersion stability of the liposomes was examined. Deep sea water treated with reverse osmosis membrane (RO water) gave liposomes, whereas 100% deep sea water failed to yield liposmes. Soybean lecithin liposomes solubilizing oil-soluble medicine dispersed in RO water was more stable than those dispersed in distilled water. The time needed for the liposome-medicine system to attain solubilization equilibrium was shorter in RO water than in distilled water. Moreover, a better stability was suggested for easily oxidizable vitamin A when it was solubilized in liposomes dispersed in RO water.
J. Oleo Sci., 51, 145-149 (2002).