A review on 130 original papers for the 22 th Japan Oil Chemists' Society Award is presented. Distributions and structures of 5-olefinic non-methylene-interrupted polyenoic acids from Gymonospermae seeds and marine invertebrates, cis-5-icosenoic acid in sea urchins, geometrical configurations of parinaric and other conjugated acids, components and compositions of marine lipids, packed column and open-tubular GC of lipid components, HPLC separations of mono-and diacyl- and alkylglycerol enantiomers on chiral stationary phases, preparation of peracid type resins and epoxidation with them, olefine metathesis with tungstene hexachloride and cocatalyst, and autoxidation and lipoxygenase oxidation of various unsaturated fatty acid esters are described.

View full abstract

Lipases were coupled with polyethylene glycol with molecular weight of 5000. The modified lipases were soluble in organic solvents such as benzene, toluene and chlorinated hydrocarbons and exhibited high enzymic activity. The modified lipases catalyzed the reversed reaction of hydrolysis in organic solvents, ester synthesis and ester exchange reactions. These reactios also proceeded in hydrophobic substrates without organic solvents. Polyethylene glycol-modified lipase was conjugated with magnetite to form magnetic lipase. The magnetic lipase dispersed stably and catalyzed ester synthesis in organic solvents. Magnetic lipase particles could be readily recovered by magnetic force without loss of enzymic activity.

View full abstract

While increasing lipase production by Mucor javanicus IAM 6108, reduction in cultivation time and stabilization of lipase in the broth were investigated. The addition of 1 % soybean oil to the initial medium containing 3 % corn steep liquor, 1 % soluble starch, 0.2 % KH₂PO₄, 0.05 % MgSO₄·₇ H₂O, 0.05 % KCl, and 1 % soybeanyuto reduced the cultivation time of lipase production from 50 h to 30h.
Lipase activity in the broth decreased rapidly after reaching a maximum. To avoid this, the 1 % soybean oil was added to the broth at 25 h of cultivation before the maximum had been reached, As a result, maximum lipase activity was maintained for more than 10 h. This appeared due to the presence of fatty acids or triglycerides with double bonds on the broth.

View full abstract

The reactions of water-soluble or surface active hydroxamic acids each containing an oligo (oxyethylene) group, with ρ-nitrophenyl carboxylates (substrates) were investigated in aqueous solution at 30°C and pH 8.80 under pseudo-first-order rate conditions. The apparent second-order rate constant for the deacylation of the substrate by the hydroxamic acid was determined. Hydroxamic acids containing a dodecyl or tetradecyl group as the hydrophobic part showed excellent micellar catalytic effect on the deacylation of hydrophobic substrates such as ρ-nitrophenyl octanoate, nonanoate, decanoate and dodecanoate. The influence of ion strength and pH on the rate constants for both hydrophilic and hydrophobic substrates was investigated. The introduction of an oligo- (oxyethylene) group afforded long-chain alkylhydroxamic acids with good water-solubility. It thus follows that the title compounds may be used micellar catalysts in aqueous solution without the requirement for other organic additives.

View full abstract

High purity water is now required in many industries. Ion exchange resins are the best means for obtaining such water. The present study was carried out to obtain the profiles of leachables from typical strong acid cation exchange resins (SAGER, three gel and two porous types) widely used for the production of highly pure water. These resins in the H form and fully cleaned were put in purified water which had been purged with nitrogen gas for a hundred days at 50°C. The amounts of organic compounds that could be leached from the SACERs were 4.2 × 10^-2 to 1.7 Cmg/h per dried resin of liter wet resin as total organic carbon. The leachables from SACERs had similar gel filtration chromatograms and the amounts of components was different from those of the others. The high molecular weight (M, W.) leachables ranged from several hundred thousand by assuming them as polystyrene sulfonate, Phenolsulfonic acid and p-sulfobenzoic acid were found to be present in low M. W, leachable components by reverse phase chromatography.

View full abstract

Interactions of a nonionic surfactant such as hexaoxyethylene glycol dodecyl ether (6 ED) with several anionic surfactants were investigated by measuring the absorption spectra of aqueous triiodide ion (I^-₃) solutions and surface tension. Two anionic surfactants, sodium dodecyl sulfate (SDS) and sodium 4-sulf obutyl laurate (11 C-4), were compared for their structural effects on I^-₃ -6 ED complex formation by mixing nonionic and anionic surfactants. The maximum absorption wavelength of I^-₃-6 ED shifted, and absorbance decreased in all cases with increase in the concentration of the added anionic surfactant. Two break points, A and B, were observed in a plot of maximum absorption wavelength against the anionic surfactant concentration. The slope of the plots between points A and B indicated interactions to occur between 6 ED and anionic surfactants, The SDS concentration at the points A and B was less than that of 11 C-4. Interactions of the 6 ED/SDS system were found to occur more easily than those of the 6 ED/11 C-4 system.
A flat portion was observed on the surface tension curve in the 6 ED/11 C-4 mixed system, and in this portion, a mixed micelle was noted to be formed. The surface tension was found to decrease when the concentration of 6 ED was made high. In contrast, the absorbance of I^-₃ increased regularly, due to interaction of the 6 ED micelle with I^-₃, owing to the presence of 6 ED in excess. By the present I^-₃ solubilization method, some single 6 ED micelles and 6 ED rich mixed micelles were confirmed to be formed in the higher concentration region of 6 ED.

View full abstract

The chemical and biochemical degradation of telomers from acrylamide (Ls-CONH₂), vinyl pyrrolidone (Ls-VPr), cotelomers of vinyl pyrrolidone and methyl acrylate (Ls-VPr-MA), saponificated telomers of Ls-CONH₂ (Ls-COONa), and water soluble polymers and surfactants as controls were studied under aerobic conditions. The above telomers and cotelomers provided excellent detergency when used as detergent builders.
The results showed chemical oxygen demand and biochemical oxygen demand to be closely related. Biodegradability was influenced by the radical group of telomers, the order of biodegradability being follows : carboxyl>pyrrolidone>carbamoyl group. The biodegradability of Ls-VPr-MA telomers decrease with increase in the degree of saponification of the telomers, even though the number of carboxyl groups of the telomers increased as the process of saponification proceeded. This was considered to result from mutual action between carboxyl and pyrrolidone groups.
The biodegradability of telomers was generally good, exceeding that of poly (acrylamide) and poly (sodium acrylate). The biodegradability of certain telomers was comparable to that of sodium oleate.

View full abstract

The synergistic antioxidant effects of d-tocopherol (Toc) and L-ascorbyl stearate (AS) on several solid fats having different physical properties were investigated by storage tests at 30°C or 40°C. The effects were compared to those in the liquid state by AOM tests. The fats were fully hardened beef tallow mixed lard olein or stripped safflower oil, and fully hardened palm kernel oil mixed stripped safflower oil at different ratios.
1) In the storage test at 40°C, AS synergistically enhanced the antioxidant effect of a mixed tocopherols concentrate (m-Toc) on fully hardened beef tallow mixed lard olein in the solid state, as well as that in the liquid state by the AOM test. However, the synergistic effect in the solid state was more pronounced than that in the liquid state. These effects were also observed on the hardened tallow mixed stripped safflower oil.
2) Fully hardened palm kernel oil mixed stripped safflower oil had less SFC and was softer but much more stable against oxidation than fully hardened beef tallow mixed with liquid oil in the same ratio. Thus, the synergistic effect of AS with m-Toc could not be clearly detected in the solid state by the storage test at 30°C. However, the results of the AOM test indicated AS to possibly enhance antioxidant effect of m-Toc on mixed fats in the solid state as well as that in the liquid state.
3) The remnant ratios of Toc and AS following storage at 30°C or 40°C for 100 days indicated Tocs to decompose with the production of hydroperoxides in substrates, and AS to rapidly decompose in all cases.

View full abstract

The reaction of N-succinimidyl benzoates (1) with an aliphatic primary amine (2) to give the corresponding N- (arylcarbonyl) amines (3) was studied kinetically in organic solvents at 30°C. The rates roughly increased with increasing polarity (D : dielectric constant) of the solvent. The rates for meta- and para-substituted (1) correlated with the Hammet σ value, giving a positive ρ of 1.0. However, the rate for ortho-substituted (1) was less than that expected from the ionization constant of the corresponding benzoic acid and this resulted from steric hindrance of the substituent. Based on these findings, a probable mechanism involving nucleophilic attack is proposed and discussed.

View full abstract

The influence of hardened fish oil (HFO) on the biosynthesis of 1, -ascorbic acid and certain hepatic enzymatic activities was investigated in the following 2 feeding experiments using male rats (Exp. I, Exp. II). In Exp. I, the animals were fed diets containing 20% HFO, 20% soybean oil (SO) or 5% SO (control) for 56 days, and in Exp. IT, diets containing 20 HFO, HFO replaced with 110% safflower oil or SO (control) for 28 days. Urinary excretion and concentration of L-ascorbic acid in the liver, kidney and serum and the concentration of cytochrome P-450 and activities of uridine diphosphate glucose dehydrogenase in liver microsomes were measured.
1) In Exp. I, temporary increase in liver weight in the HFO group and its resumption with prolonged feeding were confirmed.
2) The urinary excretion of L-ascorbic acid in the HFO group markedly increased after 4 and 14 days, but was resumed with prolonged feeding. The liver and kidney levels of 1, -ascorbic acid also increased, but not those in the serum, suggesting stimulation of 1, -ascorbate biosynthesis by HFO. This increase was suppressed to some extent by the addition of safflower oil at 3% or more.

View full abstract

The lipid peroxide levels in sera of ca. 500 patients suffering from various diseases were determined by the potentiometric POV method.
The average values of serum lipid peroxide levels in patients suffering from cerebrovascular disease, heart disease, hypertension, hepatic disease, cataract and glaucoma, bronchitis, ulcer and bronchial asthma were found to exceed those of the normal human group. In patients with cerebrovascular disease, hypertension and hepatic disease, the levels of serum lipid peroxides were particularly higher statistically than those of the normal human group with a 5% significance level.
The large standard deviations in average peroxide levels of these groups were considered to arise from differences in age, sex, the particular diseases of the patient and his /her condition. The ratios of samples showing high levels of peroxide exceeding the normal range (40.9±22.8 neq/mL) were calculated for all the patients. The ratios of high level were observed in more than 30% of patients with cerebrovascular and hypertension, and in more than 20% with cancer and hepatic disease.
Moreover, it was obvious that lipid peroxide levels in the sera of patients suffering from these 4 diseases rose more than in normal humans, although no correlation between lipid peroxide and lipid levels could be found.

View full abstract

The rate curves for fatty soil removal under various mechanical conditions were drawn on the basis of spectrophotometric measurement data taken at different temperatures. The rate constant of soil removal (κ₁) and that of the redeposition of removed soil (κ_-2) were calculated from rate curves using the rate equation of fatty soil removal developed in the previous paper. The activation energy for removal (E_a) for each mechanical conditions was determined from Arrhenius plots of the rate constants. It was consequently found that with an increase in the mechanical force (rotation of stirrer), the activation energy, E_a, decreased and the detergency is enhanced. Further, the relationship between detergency, F_m, and mechanical force, M, above the temperature for liquid crystal formation in a ternary system, was determined as follows :
Fm=Cexp (-E_m⁰/aM) (1)
where C and a are constants and E_m⁰ is the activation energy related to the contribution of mechanical force. This equation is actually an Arrhenius equation expressing change in detergency as a function of mechanical energy. At a temperature above that for liquid crystal formation, the mechanical force in removal may possibly bring about an increase in the heat energy of the system in a manner similar to that by which rise in temperature causes such an increase.

View full abstract

Three fluorescent compounds under UV lamp were obtained from the unsaponifiables of immature fruit oil of Styrax japonica Sieb et Zucc, and their compositions were determined by GLC. The fluorescent compounds was found to be 5- (3-hydroxypropyl) -2- (3, 4-methylendioxyphenyl) benzof uran : (demethoxyegonol), egonol, and 5- (3-hydroxypropyl) -2- (3, 4-dimethoxyphenyl) benzof uran : (demethoxyhomoegonol).

View full abstract

The effect of CMCases obtained from the alkalophilic Streptomyces strain KSM-9 on the removal of clay soil from cotton fabrics was studied. In each experiment conducted for this purpose, a quantitative determination was made of residual soil following the washing of soiled test clothes. CMCase I was found to be the most effective for soil removal. The detergency of CMCase produced by Streptomyces lividans HNI (pCASI) possessing the CMCase I gene was also examined. This CMCase was noted to have the same power of detergency as CMCase I produced by the parental strain.

View full abstract

[in Japanese]

View full abstract