This review summarized my works concerning with the JOCS Award 1990 under the title mentioned above. It was mainly consisted of following items; 1) properties of substituted long-chain alkylphosphonic acids, 2) preparation of alkylphosphonic acids by radical reactions, 3) dealkylation of the dialkyl ester with a mixed reagent of Me₃SiCl/NaI or LiBr, 4) biological activities of aminodiphosphonic acids, 5) phosphorylation of alcohol by oxidation of P-H compounds with oxygen by coupling with the oxidation-reduction cycle of copper chloride, and 6) photo-chemistry of organophosphorus compounds : photochemical C-P bond cleavage of arylmethyl-phosphonic acids and formation of monomeric metaphosphate anion, novel photo-generation of phosphono (aryl) carbene from triarylmethylphosphonic acids, photo-coupling of two aryl groups of diaryl alkylphosphonates, and others. References cited in this review are 121.

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一連のs-デシルグルコピラノシドを合成し, それらの静的表面張力, 臨界ミセル濃度 (cmc), 分子占有面積, 動的表面張力低下能及び泡特性などの表面活性能, パン酵母を用いた発酵プロセスにおける抑泡力, 生分解性及び抗菌性について評価を行った。その結果, s-デシルグルコピラノシドはn-デシルグルコピラノシドに匹敵する優れた表面活性能と環境微生物による優れた生分解性を示した。n-デシルグルコピラノシドに比べてs-デシルグルコピラノシドの最も優れた特徴は動的表面張力低下能及び泡特性に見られた。動的表面張力低下能は親水性のグルコピラノシル基がアルキル鎖中央に結合している時に早く, 同様の傾向が起泡力及び泡安定性にも認められた。s-デシルグルコピラノシドは発酵プロセスにおいて抑泡剤として働くことが確認された。

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The peroxidation of human skin surface lipids was investigated by the CL-HPLC (chemiluminescence-high performance liquid chromatography) system, using a reversed phased HPLC column and hydroperoxide-specific luminescent reagent consisting of cytochrome c and luminol. Squalene hydroperoxide was detected as the most prominent chemiluminescent peak in oxidized skin surface lipids, and the retention time was identical with that of hydroperoxide of the autoxidized squalene. The chemiluminescent peak disappeared by sodium borohydride treatment. Skin surface lipids oxidized by natural exposure to sunlight were analyzed quntitatively and squalene hydroperoxide formation was confirmed.

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Four groups of weanling male rats were fed either palm, hardened or unhardened soybean oils or cacao butter, for 28d. Comparative studies were made on cholesterol and its metabolites in several tissues and feces from the rats, and on the chemical and physical properties of the dietary fats.
1) Hardening of soybean oil caused increase in octadecenoic acid, including trans-isomers, by conversion from linoleic and linolenic acids, regardless of the bound position in triglyceride. Amounts of saturated fatty acids, situated at the 2-position of triglyceride, were much less in cacaco butter than in palm oil. Cacao butter was mainly comprised of 2-oleo-1, 3-disaturated glycerides, thus causing it to show unique melting behavior.
2) Cholesterol concentrations in serum and liver were low in the hardened soybean oil group, but no significant differences between the cacao butter and palm or soybean oil groups could be detected. This was also observed for serum triglyceride and phospholipid. Analytical results on fatty acids in liver and fecal lipids suggested preferential excretion into the feces of octadecenoic acid, probably its trans-isomers, in the hardened soybean oil group, stearic acid in the cacao butter group, and palmitic acid in the palm oil group.
3) The amounts of cholesterol and its metabolites in feces from the hardened soybean oil group were essentially the same as those in the palm oil group. In the cacao butter group, however, cholesterol content was much higher than that in the palm oil group. Some metabolites subjected to the action of intestinal bacteria, such as coprostanol, lithocholic and deoxycholic acids, were present at significantly lower amounts than those in the other groups. Thus, the ratio of 21 metabolites to cholesterol in the feces was basically the same in all groups, except for the cacao butter group showing a smaller value.
4) From these results, the effects of hardened soybean oil on cholesterol metabolism may be equivalent to those of palm and soybean oils, but cacao butter may somewhat differently affect the metabolism and action of intestinal bacteria.

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By the method of Terada et al. [Kolloid Z.Z. Polym., 251, 139 (1973)], the binding of bilirubin to the highest affinity site on bovine serum albumin was studied at pH 7.5 and 25°C. The number of binding sites, n, was 1.0 and binding constant, K, 1.85×10⁷ M^-1 as determined spectrophotometrically. Values of n and K were 1.08 and 4.21×106 M^-1, respectively, based on fluorescence, and agreed with literature values. Results by the method of Terada et al. were obtained using a small amount of the sample solution.

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Reactions of fluoroalkanoyl peroxides [R_FCO₂O₂CR_F, R_F=C₃F₇, C₆F₁₃, CF (CF₃) OC₃F₇, CF (CF₃) OCF₂CF (CF₃) OC₃F₇] with vinylsilanes [R₃SiCH=CH₂, R=CH₃, OCH₃, OC₂H₅] and allylsilanes [R₃SiCH₂CH=CH₂, R=CH₃, OCH₃, OC₂H₅, OSi (CH₃) ₃] were studies, Fluoroalkyl radicals (R_F·), produced by the thermal decomposition of fluoroalkanoyl peroxides, added to vinylsilanes to give fluorine-containing silicon oligomers [R_F- (CH₂-CHSiR₃) n₁-R_F, n₁=2, 3]. Allylsilanes reacted with fluoroalkanoyl peroxides to give 1 : 1 adducts [R₃SiCH₂CH (OCOR_F) CH₂R_F] without oligomer formation.
The synthesis of these new fluorine-containing silicon compounds is possible under very mild conditions (3040°C) to give excellent to moderate yields. Products bearing alkoxy groups were found particularly useful for surface active substances and have good water-and oil-repellency.

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Study similar to the previous one was made on commercially available margarines in England. The samples used were 15 brands of margarine (including 10 of the high linoleic type), 14 ones of low fat spread (including 5 of the high linoleic type), and 5 ones of dairy spread (compound type, only), totaling 34.
1) The contents of lipid and water in margarine averaged 80.8 and 16.0%, respectively, while taht of lipid in low fat spread ranged from 72.1 to 19.1%. To low fat products large amounts of stabilizers of emulsion, were added, as well as sorbic acid.
2) Almost all the samples were fortified with vitamins A and D₃, and vitamin B₁₂ was also found in a few samples. To high linoleic products, α-tocopherol was added, and palm oil was blended about half the samples, since tocotrienols had been detected.
3) Cholesterol was detected only a trace amount in products labelled as vegetable oils on the package, butΔ⁷-stigmastenol and avenasterol were present in greater amounts in products labelled as sunflower oil than in others.
4) The levels of c, c-18 : 2 fatty acid in both high linoleic types of the margarine and low fat spread averaged 49.1 and 43.8%, respectively. Each level of t-18 : 1 averaged 6.0% in the former, 7.9% in the latter and 10.1% in the dairy spread, the values being relatively low.
5) On SFC curves, high linoleic margarine was shown to be softer at low temperature, but showed more SFC with rise in temperature than the other types. This finding was consistent with the melting point.

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