Abstracts of  J. Oleo Science Vol. 51, No. 4


REGULAR PAPERS

Surface Activities of Mixtures of Partially-Quaternized 2-Vinylpyridine Telomers and Cationic Gemini Surfactant,
Tomokazu YOSHIMURA^1,2, Kosuke KAWASHIMA¹, Yoshifumi KOIDE¹, Hideto SHOSENJI¹ and Kunio 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 and Institute of Colloid and Interface Science, Science University of Tokyo, 1-3, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, JAPAN.
  The surface activities of mixed surfactants of partially-quaternized 2-vinylpyridine telomers (xR_n-2VPQ, x is the total number of alkyl chains, n is the alkyl chain length) and monomeric alkyltrimethylammonium bromide (1R_nQ) or gemini 1, 2-bis(alkyldimethylammonio)ethane dibromide (2R_nenQ) were investigated at pH 2 by surface tension, foaming property, interfacial tension and emulsification power. The mixed critical micelle concentrations (cmcs) were intermediate between the pure component xR_n-2VPQ and 1R_nQ or 2R_nenQ. xR_n-2VPQ / 2R_nenQ system was higher efficiencies in lowering the surface tension than xR_n-2VPQ / 1R_nQ. The surface tension was influenced by the alkyl chain length of binary surfactants and the mole fraction (a) of xR_n-2VPQ. In particular, 2.0R₁₀-2VPQ / 2R₁₀enQ system with a = 0.50 showed the lowest surface tension. The mixtures of two cationic multi-alkylated surfactants improved the foaming properties as compared with the pure component cationic surfactants. The similar trends in the surface tension and the foaming properties were observed for the lowering abilities of the interfacial tension at the water / toluene interface and emulsion stabilities.
J. Oleo Sci., 51, 221-227 (2002).

Preparation and Surface-Active Properties of N-Alkyl Maleamic Acid Telomer Type Surfactants Having Several Hydrocarbon Chains,
Tomokazu YOSHIMURA^{1, 2}, Yoshifumi KOIDE¹, Hideto SHOSENJI¹ and Kunio 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 and Institute of Colloid and Interface Science, Science University of Tokyo, 1-3, Kagurazaka, Shinjuku-ku, Tokyo 162-8601, JAPAN.
  Telomerization of N-alkyl maleamic acid monomer (R_nMaAm, n is the alkyl chain length; n=6-14), which was synthesized by reaction of maleic anhydride with alkylamine, in the presence of alkanethiol as a chain transfer agent gave the telomers (xR_nMaAm, x is total number of alkyl chains; x=2.9-3.2) in 60-90 % yields. The surface-active properties such as surface tension, foaming property and emulsion stability were examined in water as well as in hard water containing 300 ppm of Ca²⁺. The critical micelle concentrations (cmcs) of 2.9-3.2R_nMaAm telomers were 1/142-1/42 of those of R_nMaAm monomers with the same alkyl chain length. The surface tensions of aqueous solutions of R_nMaAm monomers and 2.9-3.2R_nMaAm telomers were 30-35 and 24-32 mN m^-1, respectively. The addition of Ca²⁺ to the aqueous solutions of 2.9-3.2R_nMaAm lowered the cmc, while gave a low efficiency at reducing the surface tension. Of the telomers, 3.0R₁₂MaAm gave the highest foaming ability and the highest foam stability in water. Shaking of the mixtures of organic solvent and the aqueous solutions of xR_nMaAm telomers formed oil-in-water type emulsions. The emulsion stabilities were in the orders of toluene > n-octane > n-dodecane > n-hexadecane > kerosene as an oil phase. The highly emulsions for toluene or n-dodecane were formed by using 3.0R₈MaAm and 3.0R₁₀MaAm. The aqueous solutions of R_nMaAm monomers and 2.9-3.2R_nMaAm telomers gave interfacial tension of 8-10 and 4-6 mN m^-1, respectively, for the interface with toluene. Thus, N-alkyl maleamic acid telomer type anionic surfactants having several alkyl chains showed greater surface activities than the corresponding monomeric monomers as well as the conventional surfactants.
J. Oleo Sci., 51, 229-236 (2002).

Effects of Alkanols on the Solubilizaion of Methanol and Ethanol in Red Palm Oil for Biofuel,
K. DZULKEFLY¹, W. H. LIM², S. HAMDAN³ and S. NORLIZAH¹,
¹: Department of Chemistry, University Putra Malaysia, 43400 UPM, Serdang, Selangor, MALAYSIA, ²: Advanced Oleochemical Technology Centre (AOTC), Lot 9&11, Jalan P/14 Seksyen 10, 43650 Bandar Baru Bangi, Selangor, MALAYSIA and ³: Faculty of Science and Technology, University College Terengganu, 21031 Kuala Terengganu, MALAYSIA.
  Solubilizations of methanol and ethanol in crude palm oil (CPO) and red palm oil (RPO) were studied by using different hydrocarbon chain-length alkanols (C₄ - C₁₂) as solubilizers. Ternary phase diagrams of oil/methanol/alkanol and oil/ethanol/alkanol were constructed to determine the solubilization (isotropic) region. Results showed that the solubilization of methanol and ethanol is more favourable in unsaturated RPO than in saturated CPO in the presence of long-chain alkanols. The relatively large isotropic regions were formed with long-chain alkanols in both the methanol and ethanol systems. The order of decreasing isotropic regions in both methanol and ethanol systems was dodecanol > decanol > octanol > octan-2-ol > hexanol > pentanol > butanol > t-butanol. The branched chain alkanols and mixed oleyl alcohol/alkanol do not promote solubilization. Cold-stability test has shown all isotropic solutions were stable at 24 °C for both methanol and ethanol systems. Kinematic viscosity of the selected isotropic solutions increased with the increase in both the chain length and percentage of alkanols. Long-chain alkanols (dodecanol, decanol and octanol) showed a steady increased in kinematic viscosity with increasing alkanol content. Solubilization of RPO/methanol/medium-chain alkanols (butanol, pentanol and hexanol) systems significantly reduced the kinematic viscosity of RPO from 43.7 mm²s^-1 to the range allowable for No. 2 diesel fuel (1.9 - 4.1 mm²s^-1 at 40.0 °C).
J. Oleo Sci., 51, 237-242 (2002).

S-Propyl-Cysteine Sulfoxide and DL-Methionine Sulfoxide Inhibit the Secretion of Apolipoprotein B100 and Lipids in HepG2 Cells,
Seo-young HAN¹, Yu-ming WANG¹, Nobuhiro FUKUDA², Koji NAGAO¹ and Teruyoshi YANAGITA¹,
¹: Department of Applied Biological Sciences, Saga University, 1 Honjo, Saga 840-8502, JAPAN and ²: Department of Biochemistry and Applied Biosciences, Miyazaki University, 1-1 Gakuen Kibanadai, Miyazaki 889-2192, JAPAN.
  It is known that high levels of apolipoprotein B100 (apoB100) and lipids in the serum are risk factors for atherosclerosis. In the present study, we evaluated the effects of four sulfur-containing amino compounds, S-propyl-cysteine sulfoxide, DL-methionine sulfoxide, S-carboxymethyl cysteine, and S-carboxyethyl cysteine, found in Allium species on lipid metabolism and apoB100 secretion in human liver model cells, HepG2. Both S-propyl-cysteine sulfoxide and DL-methionine sulfoxide inhibited apoB100 secretion into the medium in vitro and reduced the secretion of newly synthesized triacylglycerol (TAG) and cholesterol without affecting cellular lipid synthesis from [¹⁴C]acetate. S-carboxymethyl cysteine and S-carboxyethyl cysteine also reduced the secretion of newly synthesized TAG and cholesterol into the medium. A correlation between the hypolipidemic activity and the length of alkyl chain bound to cysteine was observed. These compounds had no effect on MTT activity and intracellular protein concentration compared with the untreated cells. These results suggest that sulfur-containing amino compounds in onion and garlic reduce the secretion of apoB100, TAG and cholesterol in human liver model cells, by inhibiting apoB100-containing lipoprotein assembly and secretion. Thus, these components of Allium species may be beneficial to reduce risk factors for atherosclerosis.
J. Oleo Sci., 51, 243-250 (2002).

Synthesis and Antibacterial Activity of a-Methylene-g-Alkylbutyrolactones,
Kennosuke TONARI and Aya KANOH,
Course of Industrial Chemistry, Kinki Polytechnic College, 1778 Inaba-cho, Kishiwada, Osaka 596-0103, JAPAN.
  a-Methylene-g-alkylbutyrolactones were synthesized by usual method and assessed for antibacterial activity against Bacillus subtilis and Escherichia coli. Using substituent constants(p) of the compounds, regression analysis was made on the effect of alkyl side chains of the methylenelactones. The correlation coefficient(r) between observed and calculated minimum inhibitory concentration(MIC) expressed in molar concentration as log(1/C) was 0.739 and 0.725 for B. subtilis and for E. coli, respectively. On using steric parameter of E's, r was up to 0.894 and 0.884 for B. subtilis and E. coli, respectively. Consideration of p derived from the smallest MIC, a-methylene-g-nonalactone 6 or a-methylene-g-decanolactone 7 suggested the strongest antibacterial activity.
J. Oleo Sci., 51, 251-254 (2002).

Synthesis and Antibacterial Activity of a-Methylenecamphor and Isophorone Derivatives,
Kennosuke TONARI¹ and Naoyuki MATSUMOTO²,
¹: Course of Industrial Chemistry, Kinki Polytechnic College, 1778 Inaba-cho, Kishiwada, Osaka 596-0103, JAPAN and ²: Settsu Oil Co., Ltd., 6-5-77, Noda, Fukushima-ku, Osaka 553-0002, JAPAN.
  a-Methylenecamphor and a-methyleneisophorone derivatives were synthesized and their antibacterial activity on Escherichia coli was examined. a-Methylenated camphor and isophorone derivatives showed stronger antibacterial activity than the compounds before a-methylenation, as anticipated. Data of the electronic parameters of the absolute electronegativity(c), the quantity of electron transfer(DN) and the stabilization energy(DE) with cysteine strongly supported this finding.
J. Oleo Sci., 51, 255-258 (2002).

Synthesis and Antibacterial Activity of a-Methylene-g(b)-carboxy-g-Butyrolactones,
Kennosuke TONARI¹ and Kenji YONEMOTO²,
¹: Course of Industrial Chemistry, Kinki Polytechnic College, 1778 Inaba-cho, Kishiwada, Osaka 596-0103, JAPAN and ²: Siraishi Kogyo Co., Ltd., 78-4 Motohama-cho Amagasaki, Hyogo 660-0085 JAPAN.
  a-Methylene-g(b)-carboxy-g-butyrolactones(5 and 10) are considered to have strong antibacterial activity owing to large absolute electronegativity(c), electron transfer(DN) and stabilization energy(DE) compared to potent cyclopentanone antibiotics. a-Methylene-g-carboxy-g-butyrolactone(5) was synthesized starting from L-glutamic acid and a-methylene-b-carboxy-g-butyrolactone (a-methylene paraconic acid 10) was obtained via ethyl a-formylsuccinate(6) or hydroxymethylation of ethyl a-carbethoxysuccinate(11). a-Methylenationed 5 and 10 showed no strong antibacterial activity as we expected formerly.
J. Oleo Sci., 51, 259-264 (2002).

Detergency of Extracted Saponin,
Emiko KOMATSU¹, Miyuki MORITA², Yukari IWAFUNE² and Michiko KIMURA³,
¹: Tenshi College (Part-time Lecturer), Higashi-3, Kita-13, Higashi-ku, Sapporo 065-0013, JAPAN, ²: Hokkaido University of Education Sapporo, Sapporo 002-8502, JAPAN and ³: Touhokubunkagakuen University, Sendai 981-8511, JAPAN.
  Examination was made of the conditions for the extraction, critical micelle concentration (cmc) and detergency of saponin from plants. Extraction volume was maximum at 100°C over a period of 1-3 hours. To control saponin concentration, cmc of this compound had to be determined by the conductivity method. The detergency of standard soybean saponin was maximum at 1.2 times cmc, pH10.0 for 30 minutes at 40°C. Extraction exceeded that of the model detergent by 70%. The extraction of saponin from adenophora, mandarin orange, adzuki bean, soybean was 40% in each case.
J. Oleo Sci., 51, 265-270 (2002).

NOTES

Structure and Antibacterial Activity of Cinnamic Acid Related Compounds,
Kennosuke T0NARI¹, Katsue MITUI¹ and Kenji YONEMOTO²,
¹: Course of Industrial Chemistry, Kinki Polytechnic College, 1778 Inaba-cho, Kishiwada, Osaka 596-0103, JAPAN and ²: Siraishi Kogyo Co., Ltd., 78-4 Motohama-cho, Amagasaki, Hyogo 660-0085, JAPAN.
  Antibacterial activity of 17 cinnamic acid related compounds against Bacillus subtilis and Escherichia coli was investigated to elucidate the structure responsible for the activity. Absolute hardness(h) was well correlated with minimum inhibitory concentration (MIC) expressed in logarithm. The correlation coefficient(r) between log (MIC) and h was 0.944 for B.subtilis and 0.932 for E.coli. Considering h and structure, the compound having the substituted phenyl group in propiolic aldehyde or its ester form should possess the strongest antibacterial activity.
J. Oleo Sci., 51, 271-273 (2002).

Deep-frying Oil Properties of Diacylglycerol-rich Cooking Oil,
Yoshimi OHNO,
Department of Food Science and Nutrition, School of Human Environmental Sciences, Mukogawa Women's University, 6-46 Ikebiraki, Nishinomiya, Hyogo 663-8558, JAPAN.
  Deep-frying oil properties of diacylglycerol-rich cooking oil (DG oil) were examined so as to assess the extent of thermally oxidative deterioration. The results obtained were compared with those for triacylglycerol-rich oil (TG oil). Autoxidation of DG oil at 50°C was much slower compared to TG oil. The viscosity of DG oil exceeded that of TG oil and both these parameters increased with the heating of either oil. Acid value (AV) of fresh DG oil (0.49) was higher than that of TG oil (0.11). AV, carbonyl and p-anisidin values of DG and TG oil increased with the number of uses. It follows from the present findings that the thermal oxidation of DG oil during deep-frying is basically the same as that of TG oil.
J. Oleo Sci., 51, 275-279 (2002).