Abstracts of  J. Oleo Science Vol. 51, No.1


REGULAR PAPERS

Rapid Identification of Carotenoids in a Combination of Liquid Chromatography / UV-Visible Absorption Spectrometry by Photodiode-Array Detector and Atomospheric Pressure Chemical Ionization Mass Spectrometry (LC/PAD/APCI-MS),
Takashi MAOKA¹, Yasuhiro FUJIWARA¹, Keiji HASHIMOTO¹ and Naoshige AKIMOTO²,
¹: Kyoto Pharmaceutical University, Misasagi, Yamashina-ku, Kyoto 607-8414, JAPAN and ²: Graduate School of Pharmaceutical Sciences, Kyoto University, 46-29 Yoshida-shimoadachi-cho, Sakyo-ku, Kyoto 606-8501, JAPAN.
  The combination method of high performance liquid chromatography / UV-Visible (Vis) absorption spectrometry by photodiode-array detector and atmospheric pressure chemical ionization mass spectrometry (LC/PAD/APCI-MS) were applied for the rapid identification of carotenoids obtained from several natural sources. APCI-MS spectra provided not only information of the molecule weight but also the presence of functional groups such as hydroxy, acetyl and glycosyl groups in carotenoids. On the other hand, UV-Vis spectra gave the information of chromophores which consist of the conjugated double bonds and end groups in carotenoids. This combination method allows the carotenoids to be characterized by retention time in HPLC, APCI-MS and UV-Vis spectral data so that it offers rapid and accurate method for the identification of carotenoids extracted from various natual sources.
J. Oleo Sci., 51, 1-9 (2002).

Phase Diagram for Binary Mixture of Sterols: 5-cholesten-3b-ol, 5a-cholestan-3b-ol, 5b-cholestan-3a-ol and 5b-cholestan-3b-ol,
Hideyuki MINAMI, Yukari SAKAMOTO and Makio IWAHASHI,
Department of Chemistry, School of Science, Kitasato University, Sagamihara 228-8555, JAPAN.
  Phase diagrams for binary mixtures of sterols such as 5-cholesten-3b-ol (I), 5a-cholestan-3b-ol (II), 5b-cholestan-3a-ol (III) and 5b-cholestan-3b-ol (IV) were studied. II is similar to I in its straight, plank-like skeletal structure and in the direction of OH moiety linking directly to the steroid ring. III is similar to IV in its bending skeletal structure and differs in the direction of OH moiety from I, II and IV. From phase diagrams for all of their binary mixtures, it became clear that in I/II and also in II/IV systems the molecules of each component are phase-separated from each other in the solid state and provide a eutectic mixture. In I/III, II/III and III/IV systems, two kinds of molecules whose OH moieties are in opposite directions to each other made a 1:1 compound. On the other hand, in I/IV system I and IV molecules made an incongruent melting (peritectic) compound, which was less stable and, before its melting, decomposed into solid I and a 1:1-molar-ratio solution of I and IV at 373 K.
J. Oleo Sci., 51, 11-17 (2002).

Synthetic Search for Cosmetic Ingredients: Preparations, Tyrosinase Inhibitory and Antioxidant Activities of Caffeic Amides,
Takahiro TADA¹, Kazuomi OHNISHI², Takashi KOMIYA¹ and Kunio IMAI¹,
¹: Faculty of Bio-resources, Mie University, 1515 Kamihama-cho, Tsu, Mie 514-8507, JAPAN and ²: Research & Development Department, Mikimoto Pharmaceutical Co., Ltd., 1425 Kurose-cho, Ise, Mie 516-8581, JAPAN.
  Six caffeic amides 1-6 were synthesized by condensing caffeic acid (CA) with serine or lysine derivatives. Tyrosinase inhibitory and antioxidant activities were measured to find effective cosmetic ingredients. Most of the derivatives prepared showed tyrosinase inhibition stronger than or comparable to CA, the amino acids, chlorogenic acid (CGA) or arbutin, and showed antioxidant activity stronger than the most popular whitening agents, kojic acid or arbutin. N-Caffeoyl-O-acetylserine methyl ester 3 showed the strongest activity in two assay systems and proved to be a promising candidate for cosmetic ingredients.
J. Oleo Sci., 51, 19-27 (2002).

Behaviors of Pyrethroid and Organophosphorus Pesticides in Edible Oils during Hydrogenation,
Toru FUKAZAWA¹, 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.
  Nine pyrethroid pesticides and 3 organophosphorus pesticides, which could not be removed during the oil refining process, were added to refined soybean oils at concentrations of 4 ppm each, and the oils were hydrogenated under 8 different conditions, then the persistence of these pesticides was examined. As a result, it was found that pyrethrin and permethrin persisted beyond other pesticides during hydrogenation and that these 2 pesticides decreased readily at a higher temperature, at a higher hydrogen flow rate or at a higher stirring speed. It was also clarified that any pyrethrin and permethrin persisting in an oil before hydrogenation can be eliminated by performing hydrogenation until the iodine value of the soybean oil attains 70 or less. Subsequently, pyrethrin and permethrin were added to a hydrogenated soybean oil at concentrations of 3 ppm each, and the oil was deodorized under the condition commonly used in oil plants, then the behaviors of these pesticides were examined. As a result, it was observed that the pyrethrin concentration was lowered below 0.01 ppm after deodorizing for 120 minutes, while permethrin remained at 0.32 ppm in the oil.
J. Oleo Sci., 51, 29-34 (2002).

Changes in Cell Membrane and Cellular Lipids in Apoptotic Cells Induced by Dolichyl Phosphate Differ from Findings in Cells Induced by Etoposide,
Akiko HORIUCHI¹, Etsuko YASUGI², Chizu IWASAKI³, Keiji FUJIMOTO³ and Mieko OSHIMA⁴,
¹: Division of Natural Science, International Christian University, 3-10-2, Osawa, Mitaka-shi, Tokyo 181-8585, JAPAN, ²: Department of Hematology, Research Institute, International Medical Center of Japan, 1-21-1, Toyama, Shinjuku-ku, Tokyo 162-8655, JAPAN, ³: Department of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama-shi, Kanagawa 223-8522, JAPAN and ⁴: Tohoku University of Community Service and Science, 3-5-1, Iimoriyama, Sakata-shi, Yamagata 998-0000, JAPAN.
  Cell membrane fluidity and changes of cellular lipids of U937 cells during apoptosis are compared between the cells treated with dolichyl phosphate (dol-P) and etoposide. Dol-P induced lateral cell membrane perturbation immediately after addition and continued for at least 40 min. However, etoposide induced apoptosis without increase in cell membrane fluidity. Phosphatidylethanolamine was translocated together with phosphatidylserine after 4 hr of treatment in both dol-P and etoposide treated cells. The concentration of lipid levels changed in dol-P-induced cells and the cholesterol/phospholipid ratio almost doubled. Conversely, none of the phospholipid and cholesterol levels changed in etoposide treated cells. Although both dol-P and etoposide induce apoptosis, dol-P, but not etoposide, appeared to function as a modulator of membrane fluidity and to change membrane constituents and membrane physiology during the course of apoptosis.
J. Oleo Sci., 51, 35-42 (2002).

Vesicles Formation of Double-Chain Cationic Surfactants with Different Chain-Lengths in Deep Sea Water,
Chihiro KAISE^1,2, Hideki SAKAI^1,3, Aritomo YAMAGUCHI^1,3, Shoko YOKOYAMA⁴, Teruhisa KANEKO², Youichiro ARAI² and Masahiko ABE^1,3,
¹: Faculty of Science and Technology, Science University of Tokyo, 2641,Yamazaki, Noda-shi, Chiba 278-8510, JAPAN, ²: SHU UEMURA Co., 5-7-17, Minamiaoyama, Minato-ku, Tokyo 107-8603, JAPAN, ³: Institute of Colloid and Interface Science, Science University of Tokyo, 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.
  Vesicle forming ability of double-chain cationic surfactants {dialkyldimethylammonium bromides {(C_nH_2n+1)₂(CH₃)₂N⁺Br^-; DDAB (n=12), DTDAB (n=14), DHDAB (n=16), DODAB (n=18)} in deep sea water was examined, and the effect of their chain length on the membrane properties and dispersability of vesicles formed was investigated.
  Any of the surfactants failed to form vesicles in 100% of deep sea water while they formed vesicles in a mixture of deep sea water (5%) / purified water (95%) and in deep sea water treated with reverse osmosis membrane (RO water). The particle size of vesicles was found to increase with the chain length of the cationic surfactants (except for DHDAB). For DTDAB with 14 carbon atoms in the alkyl chain, vesicles in RO water were more stable than in purified water, being stable for six months after preparation. The experimental findings demonstrated that the stability of the vesicles depended on the preparation temperature and the gel-liquid crystal phase transition temperature of the surfactants (in each system).
J. Oleo Sci., 51, 43-50(2002).

Infrared External Reflection Spectra of Mixed Monolayers of Sodium Dodecyl Sulfate and Myristic Acid at an Air/Water Interface,
Takeshi KAWAI, Fumie KAWAGUCHI, Hiroaki KAMIO and Kijiro KON-NO, Department of Industrial Chemistry, Institute of Colloid and Interface Science, Science University of Tokyo,1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, JAPAN.
  The titled spectra were measured at various concentrations of SDS. IER spectra demonstrated that conformational order of alkyl chains of SDS and MA and surface composition at the air/water interface was clarified. Conformational order was found to improve on increasing SDS concentration up to [SDS]= 3 mM. MA showed essentially no change. The ratio of MA to SDS composition at the interface is exceeded that in bulk solution and decreased at greater SDS.
J. Oleo Sci., 51, 51-55 (2002).

NOTE

Cosmetic Substance Synthesis from Estragole Derivatives for Skin Depigmentation,
Masato NOMURA¹, Yutaka MOTOKI¹, Yoshihito FUJIHARA¹, Takahiro TADA² and Kenji SHIMOMURA²,
¹: Department of Chemistry and Environmental Technology, Faculty of Engineering, Kinki University, Umenobe, Takaya, Higashihiroshima 739-2116, JAPAN and ²: Natural Material Group, Reseach & Development Division, Mikimoto Pharmaceutical Co., Ltd., Kurose, Ise, Mie 516-0018, JAPAN.
  Natural material extracts are presently used as cosmetic ingredients. Their physiological effects were examined using estragole isolated from the essential oil of Foeniculum vulgare Miller as starting materials. Thirty derivatives were synthesized by condensation using ten thiols. The derivatives were examined for potential use as whitening agents possessing tyrosinase activity and superoxide dismutase. Derivative compounds were found good inhibitors of tyrosinase.
J. Oleo Sci., 51, 57-62 (2002).

RAPID PAPER

Lipid Peroxidation and the Antioxidant Effects of 3,5,7,4'-Tetrahydroxy-2'-Methoxyflavone; Direct Observation by Atomic Force Microscopy,
Shoko YOKOYAMA¹, Tadahiro TAKEDA¹, Hiromi TAKAHASHI¹, Yumiko OHTA², Sung Hee PARK², Takashi NISHIKAWA¹ and Masahiko ABE^2,3,
¹: Kyoritsu College of Pharmacy, 1-5-30, Shibakoen, Minato-ku, Tokyo 105-8512, JAPAN, ²: Faculty of Science and Technology, Science University of Tokyo, 2641, Yamazaki, Noda-shi, Chiba 278-8510, JAPAN and ³: Institute of Colloid and Interface Science, Science University of Tokyo, 1-3, Kagurazaka, Shinjuku-ku, Tokyo 162-0825, JAPAN.
  Lipid peroxidation and the antioxidant effects of 3,5,7,4'-tetrahydroxy-2'-methoxyflavone (THMF), isolated from the bark of Anaxagorea luzonensis A. GRAY, were observed by atomic force microscopy (AFM). The Langmuir-Blodgett film of 1-palmitoyl-2-linoleoyl-3-phosphatidylcholine (PLPC) was used for AFM. The antioxidant potency of THMF was compared with that of a-tocopherol as the positive control. The AFM images clearly indicated that THMF effectively inhibited lipid peroxidation and that the antioxidant effect of THMF was more potent than that of a-tocopherol. This is the first report of direct visual observation of the effects of an antioxidant on lipid peroxidation.
J. Oleo Sci., 51, 63-67 (2002).