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.

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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.

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ムコールジャバニカスIAM6108のリパーゼをスケールアップ生産するにあたり, 培養時間の短縮と培養液の安定化を試みた。コーンスチープリカー3%, 可溶性デンプン1%, リン酸二水素カリウム0.2%, 硫酸マグネシウム0.05%, 塩化カリウム0.05%及び大豆油糖1%の基本培地に大豆油1%を添加すると, 培養時間は50hから30hに短縮された。一方, 培養中のリパーゼ活性は最高値に達した後急速に低下した。これを防ぐため, 最高値に達する時間に先だって, 25hで更に大豆油1%を添加すると, 最高値のリパーゼ活性は10h保持された。培養液のリパーゼ活性の安定化は, 二重結合をもつ脂肪酸またはトリグリセリドによるものと考えられた。

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オリゴ (オキシエチレン) 基を有する水溶性または界面活性ヒドロキサム酸とρ-ニトロフェニルカルボン酸エステル (基質) との反応を, 擬一次反応速度条件下, 30℃, pH8.80の水溶液中で検討し, ヒドロキサム酸による基質の脱アシル化の見掛けの二次反応速度定数を求めた。疎水部にドデシル基またはテトラデシル基を有するヒドロキサム酸は, オクタン酸, ノナン酸, デカン酸, ドデカン酸ρ-ニトロフェニルのような疎水性基質の脱アシル化において優れたミセル触媒効果を示した。さらに, 親水性及び疎水性基質に対する速度定数に及ぼすイオン強度とpHの影響について検討した。オリゴ (オキシエチレン) 基の導入により, アルキルヒドロキサム酸が水溶性となり, 表題化合物は他に有機化合物を加えなくても, 水溶液中でミセル触媒として応用が可能であることがわかった。

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現在, 高純度の水が多くの産業において求められている。この純水はイオン交換樹脂を用いることにより得られている。本研究は純水を作るために広く用いられている代表的な強酸性陽イオン交換樹脂 (ゲル型3種と多孔性2種) から溶出してくる溶出物の挙動に関するものである。
充分洗浄した再生型 (H型) のこれらの陽イオン交換樹脂を, あらかじめ窒素ガスを吹き込んだ精製純水中で100d, 50℃で浸漬した。溶出してきた溶出物量は1L湿潤樹脂の乾燥樹脂当たり4.2×10^-2から1.7Cmg/hであった。溶出物はゲル瀕過クロマトグラフィー分析の結果, 良く似たクロマトグラフィーを与える物質であるが各成分量は各樹脂で異なっていた。高分子量成分としては, ポリスチレンスルホン酸塩換算の分子量で数百から約十万の範囲であった。また逆相クロマトグラフィーによって溶出物の低分子量成分中にp-フェノールスルホン酸及びp-スルホ安息香酸が存在することがわかった。

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ヘキサオキシエチレングリコールドデシルエーテル (6ED) とアニオン界面活性剤の相互作用をI^-₃水溶液の吸収スペクトル変化と表面張力測定値から調べた。ここで, 二種類のアニオン界面活性剤の硫酸ドデシル・ナトリウム (SDS) と4-スルホンブチルラウレートナトリウム (11C-4) を使って, アニオン界面活性剤とI^-₃-6ED錯体との混合状態からそれらの構造効果を検討した。
6EDとI^-₃の濃度を一定に保ちアニオン界面活性剤の量を変化させると, 最大吸光度の波長が370nmからシフトし始め, 最後の350nmに到達して, 二つの屈曲点 (点A, B) を生じた。6EDとアニオン界面活性剤の相互作用が点A, B間におこるが, SDSの点A, Bにおける濃度は11C-4より小さい, これは6ED/SDSの相互作用が6ED/11C-4よりおきやすいことが推定される。
また, 6ED/11C-4混合水溶液において一定表面張力領域が現れ, これは混合ミセルの形成に関係づけられる。さらに6EDの高濃度側で表面張力値は減少し, これに対して過剰の6EDより形成されたI^-₃-6ED錯体のために, I^-₃の吸光度は急速に増加した。これらの対比結果から, 6EDの高濃度側に単独の6EDミセルとリッチな6ED混合ミセルが作られることが考えられる。

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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.

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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.

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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.

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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.

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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.

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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.

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エゴ (Styrax japonica Sieb. Et Zucc) 未熟種子油の不けん化物成分中のベンゾフラン化合物を検索した。紫外線ランプ下で強い蛍光を示した三種類のベンゾフラン化合物 : 5- (3-hydroxypropyl) -2- (3', 4'-methylenedi-oxy phenyl) benzofuran [デメトシキエゴノール], エゴノール, 5- (3-hydroxypropy1) -2- (3'、4'-dimethoxy-phenyl) benzofuran [デメトキシホモエゴノール] を単離, 同定し, それらの含有組成をGLCより決定した。また, デメトキシホモエゴノールが天然物から単離されたのは, これが初めてであることもわかった。

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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.

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IUPAC油脂及び同誘導体委員会はHPLC法による植物油脂中のトコフェロール・トコトリエノール定量に関する合同実験を1983-1987年に実施した。11ヶ国の17機関がこれに参加し, 日本からはエーザイ株式会社, 化学技術研究所, 日本食品油脂検査協会が参加した。実験結果に基づいて, 標記トコフェロール定量のIUPAC公定法 (コード番号2・432) が制定された。IUPAの機関誌Pure & Applied Chemistry, 60,877 (1988) に掲載されたトコフェロール・トコトリエノール定量法及び合同実験結果の全文をここに転載する。

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