Abstracts of  J. Oleo Science Vol. 51, No. 3


REGULAR PAPERS

Isolation of New Egonol Compounds from Seeds of Styrax japonica Sieb. et Zucc.,
Masahide TAKANASHI¹ and Yasuomi TAKIZAWA²,
¹: Keiogijuku Yochisha, 2-35-1, Ebisu, Shibuya-ku, Tokyo 150-0013, JAPAN and ²: Department of Chemistry, Tokyo Gakugei University, 4-1-1, Nukuikita-machi, Koganei-shi, Tokyo 184-8501, JAPAN.
  Five egonol compounds were isolated from the lipids of immature seeds of Styrax japonica Sieb. et Zucc. Two compounds were new and three, known. The structures of the new compounds, EI and DHEG2, were determined to be egonol 2-methylpropanoate, and 5-[3-(b-gentiobiosyloxy)propyl]-2-(3',4'-dimethoxyphenyl)benzofuran (7-demethoxyhomoegonol b-gentiobioside), respectively, based on chemical and spectroscopic analysis. The known compound, 7-demethoxyegonol acetate (DEAc) was first isolated from the natural plants. The other two were identical with egonol 2-methylbutanoate (EMB) and 7-demethoxyegonol 2-methylbutanoate (DEMB), previously reported by the authors.
J. Oleo Sci., 51, 151-155 (2002).

Molecular Behaviors of n-Fatty Acids in Liquid State,
Makio IWAHASHI¹, Yasutoshi KASAHARA¹, Hideyuki MINAMI¹, Hideyo MATSUZAWA¹, Masao SUZUKI² and Yukihiro OZAKI³,
¹: School of Science, Kitasato University, Sagamihara 228-8555, JAPAN, ²: Advanced Science and Technology Research Center, Kyushu University, Kasuga, Fukuoka 816-8580, JAPAN and ³: School of Science, Kwansei Gakuin University, Nishinomiya 662-8501, JAPAN.
  Through near infrared spectroscopy and ¹³C-NMR spin-lattice relaxation time measurements it was revealed that the molecules of the normal fatty acids in the liquid state are strongly dimerized even at 363K by hydrogen bonding between their carboxylic groups. Thus, dimer molecules for the acids are the units in their intra- and intermolecular movements. The dynamic molecular and aggregate structures of the fatty acids (C8-C18) in the liquid state were estimated through the analyses of their self-diffusion coefficient D, viscosity h, molar volume and X-ray diffraction. The apparent hydrodynamic radius evaluated from D and h for the fatty acid was almost constant, irrespective of the hydrocarbon chain length. This suggests that only a longitudinal translation (translational movement along molecular axes) would be allowed for the dimer molecules of fatty acids. In addition, the distribution function curves obtained from the X-ray diffraction data suggest that, in the pure liquid state, rod-like fatty acid dimers highly aggregate in parallel and probably make clusters that would be randomly aligned.
J. Oleo Sci., 51, 157-164 (2002).

Properties of Fatty Acid Soap with Sodium N-Methyltaurine as Counter-ion. II. N-Methyltaurine for Detergent Application,
Reiji MIYAHARA¹, Takahiro AKUTSU², Kouji ABE², Kunihiko YOSHIDA¹, Yasunari NAKAMA² and Tomiyuki NAMBA²,
¹: Shiseido Basic Research Center, ²: Shiseido Products Development Center, 2-2-1 Hayabuchi, Tsuzuki-ku, Yokohama-shi 224-8558, JAPAN.
  In a previous study, sodium N-methyltaurine was shown to apparently function as fatty acid counter-ion and free lauric acid may become more separaterd from solution of fatty acid soap whose counter-ion is sodium N-methyltaurine at high temperature or lower concentration. Surface tension of sodium N-methyltaurate laurate solution and interfacial tension with silicone oil were low compared with those of sodium laurate solution. C.m.c. of sodium N-methyltaurate laurate exceeded that of sodium laurate. The properties of sodium N-methyltaurate laurate thus differ from those of sodium laurate. Sodium N-methyltaurate laurate as detergent was compared with other laurate soaps. Compared with sodium laurate and potassium laurate, both foam and detergency performance of sodium N-methyltaurate laurate solution are high because its surface tension and interfacial tension with oil are low. Its detergency was similar to that of triethanolammonium laurate. Less calcium laurate was noted to form with calcium ions in hard water and adsorb to skin when washing with sodium N-methyltaurate laurate solution compared to other lauric acid soap solutions. This suggests that sodium N-methyltaurate laurate should less likely lead to skin stiffness in that less calcium laurate adsorbs to skin.
J. Oleo Sci., 51, 165-173 (2002).

Determination of Docosahexaenoic Acid and n-3 Fatty Acids in Fish Oils by High Resolution Proton Nuclear Magnetic Resonance Spectroscopy: Collaborative Study by the Working Group (DHA/NMR subcommittee) Japan Oil Chemists' Society,
Tomoji IGARASHI^1,2, Kazuo WATANABE³, Yuko MIYAKE⁴, Nobuyoshi SHIMIDZU⁵, Yasukatsu OSHIMA⁶, Katsuhiko KUSHIDA⁷, Michio NONAKA¹ and Shun WADA⁸,
¹: Japan Marine Oil Association, 32-7 Motoyoyogi-cho, Shibuya-ku 151-0062, Tokyo, JAPAN, ²: Japan Food Research Laboratories Tama Laboratory, 6-11-10 Nagayama, Tama-shi, Tokyo 206-0025, JAPAN, ³: Sagami Chemical Research Center, Nishi-Ohnuma 4-4-1, Sagamihara, Kanagawa 229-0012, JAPAN, ⁴: Ajinomoto Co., Inc., 7-41, Daikoku-cho,Tsurumi-ku, Yokohama, Kanagawa 230-0053, JAPAN, ⁵: Nippon Suisan Kaisha Ltd., 559-6 Kitano-machi, Hachioji, Tokyo 192-0906, JAPAN, ⁶: Tohoku University, Graduate School of Agricultural Science, 1-1 Tsutsumi-dori Amemiya-machi, Aoba-ku, Sendai, Miyagi 981-8555, JAPAN, ⁷: Varian Technologies Japan Ltd.-NMR Application Division, 4-16-36 Shibaura, Minato-ku, Tokyo 108-0023 JAPAN and ⁸: Department of Food Science and Technology, Tokyo University of Fisheries, 4-5-7 Konan, Minato-ku, Tokyo 108-8477, JAPAN.
  Seven Japanese laboratories provided with high resolution nuclear magnetic resonance (NMR) equipment undertook a collaborative study for determining docosahexaenoic acid (DHA) and n-3 fatty acids in fish oils with NMR. This study was organized by the DHA/NMR subcommittee of the Japan Oil Chemists' Society and conducted as a part of an IUPAC collaborative study (Project 3/98 of the commission VI-6 on Oils, Fats, and Derivatives). At each laboratory, examination was made of six blind duplicate fish oils, as follows; refined tuna oil, two extracted tuna oils, extracted bonito oil, extracted salmon oil and extracted sardine oil 9 to 30 mol% DHA and 20 to 35 mol% n-3 fatty acids. To ensure maximum accuracy of determination, signal area measurement and addition of the internal standard solution were taken as critical control points. Repeatability coefficient of variation (CV_r) ranged from 0.8 to 2.6% and reproducibility coefficient of variation (CV_R) ranged from 1.4 to 3.3% for DHA weight concentration (mg/g); CV_r from 0.4 to 2.2% and CV_R from 0.7 to 3.1% for DHA (mol%); CV_r from 0.2 to 1.1% and CV_R from 1.1 to 2.2% for total n-3 fatty acids (mol%). The present method was thus shown to qualify for use as a tentative official method of the Japan Oil Chemists' Society.
J. Oleo Sci., 51, 175-182 (2002).

Effects of Fat Mixtures Similar to Japanese Diet on the Life Span of Stroke-Prone Spontaneously Hypertensive Rats (SHRSP),
Nakamichi WATANABE, Yasushi ENDO and Kenshiro FUJIMOTO,
Laboratory of Food and Bio-molecular Science, Graduate School of Agricultural Science, Faculty of Agriculture, TOHOKU UNIVERSITY, 1-1 Tsutsumidori-amamiyamati, Aoba-ku, Sendai 981-8555, JAPAN.
  Diet containing low-erucic rapeseed oil (canola oil) as the sole dietary fat has been shown to shorten the average life span of Stroke-Prone Spontaneously Hypertensive Rats (SHRSP) by as much as a half under 1% NaCl loading in drinking water compared to diet containing vegetable oils such as soybean, sunflower and perilla oils. Study was made to determine whether diet containing dietary fat mixtures commonly in Japanese food, with canola as the major oil, would have effect on the life span of SHRSP. 4 weeks-old SHRSP were fed diet containing 90% defatted commercial feed containing 10% experimental fat as follows; 1) Fat mixture similar to Japanese food (JPN-Ave); 2) Fat mixture all the vegetable oils in 1) of which had been replaced with canola oil (JPN-Can); 3) Canola; 4) Soybean and 5) Canola oil supplemented with 10% palmitoleic acid (Can-POA). Average life span was affected as follows; JPN-Ave > Soybean >= JPN-Can > Canola > Can-POA. The JPN-Ave diet containing canola oil as the major constituent, apparently does not shorten average life span. Phytosterol content of dietary fats , liver and abdominal aorta in dead SHRSP was higher in cases of shortened life span.
J. Oleo Sci., 51, 183-190 (2002).

Heat Deterioration of Phospholipids. II. Isolation and Identification of New Thermally Deteriorated Products from Soybean Lecithin,
Ryoji SONO¹, Seishiro SAKAMOTO², Nobutoshi HAMAGUCHI¹, Shin-ichi TEBAYASHI², Chul-Sa, KIM², Hen-Sik, KOH¹ and Michio HORIIKE²,
¹: Research and Development Division, Tsuji Oil Mills Co., Ltd., 565-1, Niwanosho, Ureshino-cho, Ichishi-gun, Mie 515-2314, JAPAN and ²: Faculty of Agriculture, Kochi University, B200, Monobe, Nankoku, Kochi, 783-8502, JAPAN.
  Soybean lecithin is known to be less stable at 60°C or elevated temperatures and susceptible to discoloration upon heating for a long period of time, but its major phospholipids remain unchanged at temperatures up to 100°C, with minor components undergoing discoloration as reported previously. As an accelerated thermal-deterioration test, soybean lecithin was refluxed in octane(bp 125.7°C), and then, its thermally deteriorated or decomposed products exhibiting the UV absorption maxima at wavelengths of 350 nm, 280 nm and 240 nm were yielded, respectively. The thermally deteriorated product exhibiting the UV absorption maximum at a wavelength of 350 nm was separated, purified and studied, leading to the finding that the four, heretofore unknown compounds were chemically and structurally identified as a thermally deterioration substance derived from phosphatidylethanolamine. The thermally deteriorated product of soybean lecithin yielded after refluxing in octane for 9 hrs was deffated with acetone and extracted with methanol, and the extract was treated with hexane, washed with 60% aq. ethanol and extracted with 90% aq. methanol. The extract was chromatographed on a silica gel column (elution with a 2:3 mixture of methanol:chloroform), and the isolated four compounds were subjected to acidic methanolysis, followed by chromatographic analysis to determine the fatty acid compositions and spectral analysis by use of IR. ¹H-NMR, ¹³C-NMR and MS to conduct the structural identifications. The identified four compounds were all found to contain phosphatidylethnolamine intact, except that the terminal amino group is involved in the formation of [4,2,0]-diazabicyclic structure.
J. Oleo Sci., 51, 191-202 (2002).

NOTES

Isolation and Synthesis of Cosmetic Substances from African Dietary Leaves, Celosia argentea L. for Skin Depigmentation,
Akiyoshi SAWABE¹, Masato NOMURA², Yoshihito FUJIHARA², Takahiro TADA³, Fumihiro HATTORI³, Satoko SHIOHARA³, Kenji SHIMOMURA³, Yoshiharu MATSUBARA¹, Sadao KOMEMUSHI¹, Tadashi OKAMOTO¹ and Saburou KAWAMURA¹,
¹: Department of Agricultural Chemistry, Faculty of Agriculture, Kinki University, Nakamachi 3327-204, Nara 631-8505, JAPAN, ²: Department of Chemistry and Environmental Technology, Faculty of Engineering, Kinki University, Umenobe 1, Takaya, Higashihiroshima 739-2116, JAPAN and ³: Natural Material Group, Research & Development Division, Mikimoto Pharmaceutical Co., Ltd., Kurose 1425, Ise, Mie 516-0018, JAPAN.
  Six compounds were isolated from the leaves of Celosia argentea L.. Tyrosinase inhibitory and superoxide scavenging activity of the compounds was examined so as to obtain a skin depigmentation agent for cosmetic application. Eugenyl O-b-D-glucopyranoside (citrusin C, 1) showed strong tyrosinase inhibitory activity. Two-step inhibitory effects of successive tyrosine and DOPA oxidation for tyrosinase were stronger compared to arbutin used commercially at present (47.20% inhibition of tyrosine oxidation and 87.93%, DOPA oxidation, compared to 63.00% for tyrosine and 7.70% for DOPA oxidation in the case of arbutin). Moreover, we succeed in providing compound 1 abundantly in the synthetic study which used acetobromo-a-D-glucose and Sn(OTf)₂.
J. Oleo Sci., 51, 203-206 (2002).

Leaf Lipids of Oil Palm (Elaeis guineensis Jacq.): Comparison between the Bifid Lobe of the Seedling and the Leaflet of the Matured Oil Palm Fronds,
Masakazu YAMAOKA¹, Shiho HAYAKAWA^1,$, Marzuki AZAHARI², Idris ABU-SEMAN², Mhd. Haniff HARUN² and Ariffin DARUS²,
¹: National Institute of Advanced Industrial Science and Technology, Central-6, 1-1-1, Higashi, Tsukuba, Ibaraki 305-8566, JAPAN, ^$ Present address: National Institute of Genetics, Mishima 411-8540, Shizuoka, JAPAN and ²: Malaysian Palm Oil Board, No.6, Persiaran Institusi, Bandar Baru Bangi, 43000 Kajang, Selangor, MALAYSIA,
  The morphology of oil palm (Elaeis guineensis Jacq.) leaves varies drastically during the growth stage from the seedling to the mature tree. In this paper the leaf lipids of the bifid lobe of the oil palm seedling and of the leaflet from frond 1 and frond 17 of the mature oil palm are reported on and compared with each other. Chlorophyll content decreased significantly in the order leaflet from frond 17, frond 1 and seedling leaf. The chlorophyll a / b ratio also decreased in the same order. Total lipid content and polar lipid content were increased in the order seedling leaf, leaflet from frond 1 and leaflet from frond 17. Foliar polar lipids of oil palm were monogalactosyldiacylglycerol (MGDG), digalactosyldiacylglycerol (DGDG), sulfoquinovosyldiacylglycerol (SQDG), and phosphatidylglycerol (PG). In comparison with DGDG, SQDG and PG, the fatty acid composition of MGDG showed higher content of a-linolenic acid in both the seedling leaf and the mature oil palm leaf. The amount of a-linolenic acid in DGDG, SQDG and PG of the seedling leaf was lower than that of the mature oil palm leaf. The amount of palmitic acid in DGDG and SQDG of the seedling leaf was higher than that of the mature oil palm leaf. No significant difference was found in fatty acid composition between leaflets from frond 1 and frond 17.
J. Oleo Sci., 51, 207-211 (2002).

Free Fatty Acid Level and Galactolipase Activity in a Red Tide Flagellate Chattonella marina (Raphidophyceae),
Masaru TERASAKI and Yutaka ITABASHI,
Laboratory of Bioresources Chemistry, Graduate School of Fisheries Sciences, Hokkaido University, 3-1-1, Minato-cho, Hakodate-shi, Hokkaido 041-8611, JAPAN.
  Free fatty acid (FFA) level and galactolipase activity in a marine microalga causing red tides, Chattonella marina, were examined. The FFA content increased greatly during the growth from 2.8% of total lipids in the mid-logarithmic phase to 15.4% in the late stationary phase. A crude enzyme preparation derived from the alga had activities hydrolyzing the acyl groups of various glycoglycerolipids and phospholipids, especially monogalactosyldiacylglycerol (MGDG) molecules. The results suggest that FFAs in C. marina are released mainly from MGDG, which is a major lipid class in the alga, by galactolipase.
J. Oleo Sci., 51, 213-218 (2002).

ERRATUM

  The authors of "Enthalpy-Entropy Compensation Rule and the Compensation Temperature Observed in Micelle Formation of Different Surfactants in Water. What is the so-called Compensation Temperature?" [J. Oleo Sci., Vol. 50, No. 1 (2001)], G. SUGIHARA, T. NAKANO, S.B. SULTHANA and A.K. RAKSHIT have notified JOS of errors in equations on page 37 of their manuscript.
  The corrected and error versions appear below.

  The corrected version:
and the intercept is:
     -[1-T_f(DDS/DDH)]DH₁+DG₁ =T_f[(DDS/DDH)DH₁-DS₁]
  Here, the ratio of the differences of entropy and enthalpy changes, (DDH/DDS), corresponds to the compensation temperature, T_c (called "Cross-compensation temperature"). Therefore, the Gibbs energy changes for different species should have the following relation:
     DG=(1-T_f/T_c)DH+T_f(DH₁/T_c-DS₁).   [10]
  This indicates that only when DG has a linearity with DH, a constant cross-compensation temperature can be determined. Even when the fixed temperature is by mere chance equal to the compensation temperature (T_f=T_c), DG is given as DH-T_cDS at any DH.

  The error version:
and the intercept is:
     -[1-T_f(DDS/DDH)]DH₁+DG₁=T_f[(DDS/DDH)-DS₁]
  Here, the ratio of the differences of entropy and enthalpy changes, (DDH/DDS), corresponds to the compensation temperature, T_c (called "Cross-compensation temperature"). Therefore, the Gibbs energy changes for different species should have the following relation:
     DG=(1-T_f/T_c)DH+T_f(1/T_c-DS₁).   [10]
  This indicates that only when DG has a linearity with DH, a constant cross-compensation temperature can be determined. Even when the fixed temperature is by mere chance equal to the compensation temperature (T_f=T_c), DG is given as 1-T_cDS at any DH.