Contents of vitamin D3 and 25-OH-vitamin D3 in marine animal products(20 species) were determined by HPLC. The isomers of vitamin D, D2 and D3, were not clearly separated on a reversed phase, μ Bonda Pak, with 20% methanol-acetonitrile, and on a normal phase, Zorbax SIL. with 0.4% isopropanol-hexane, but 25-OH-vitamin D2 and-D3 were separated on either μ Bonda Pak with 10% methanol-acetonitrile, or on Zorbax SIL with 2.2% isopropanol-hexane, respectively. Although levels of vitamin D3 and 25-OH-vitamin D3 varied remarkably according to species, their average value(fish : l,l87sim36,007 I.U/sample 100g, mussel : 58~1,706 I.U/sample 100g, pickle: 1,208~79,358 I.U/sample 100g) was greatly higher than that of meat(80~100 I.U/sample 100g) and dairy products(400~800 I.U/sample 100g). Fatty tissues of fish and pickled fish intestines contained high level of vitamin D3 and 25-OH-vitamin D3, while the clam and mussel known to have various kinds of sterol including δ7-sterol showed very low levels of vitamin D3 and its derivative.

본 연구에서는 Cholestery1 bipheny1 ester계열 화합물을 합성하여 편광현미경이 부착된 hot-stage와 시차열분석기로 물성을 조사하였다. 이 계열 화합물들은 모두 콜레스테릭 액정상을 나타내며, 알콕시 사슬 3번부터 스메틱상이 형성됨을 보여 준다. 또한, 일반적인 콜레스테릭 액정화합물에 비해 높은 상전이 온도를 보유하고 있으며, 넓은 온도 범위에 걸쳐 액정상을 나타낸다.

The hydrolysis kinetics of 2-furyl chalcone derivatives [I]~[V] was investigated by ultraviolet spectrophotometery in 30% dioxane-H2O at 25℃ and the structure of these compounds were ascertained by means of ultraviolet, infrared and NMR spectra. The rate equations which were applied over a wide pH range(pH 1.0~12.0) were obtained. The substituent effects on 2-furyl chalcone derivatives [I]~[V] were studied, and the hydrolysis were facilitated by the electron attrecting groups. On the basis of the rate equation, substituent effect, general base effect and final product. the plausible hydrolysis mechaism was proposed: Below pH 4.0, it was only proportional to concentration of hydronium ion, at pH 4.0~9.0, neutral H2O molecule competitively attacked on the double bond. By contrast, above pH 9.0, it was proportional to concentration of hydroxide ion.

The kinetics of the hydrolysis of indolylacrylophenone derivatives(IA) was investigated by ultraviolet spectrophotometry in 30% dioxane-H2O at 25℃ Rate equations were obtained over a wide pH range. On the basis of rate equation, general base catalysis and Hammett's plot, the mechanism of hydrolysis to the (IA) were proposed: Below pH 3.0, the hydrolysis of (IA) was proportional to hydronium ion concentration, between pH 4.0~9.0 neutral water molecule and hydroxide ion were added to carbon-carbon double bond and over pH 10.0 hydrolysis of (IA) was proportional to hydroxide ion concentration.

The kinetics of the addition of 1-benzylindole-3-(p-substituted) acetophenone derivatives was investigated by ultraviolet spectrophotometery in 30% dioxane -H2O at 25℃. A rate equation which can be applied over wide pH range was obtained. The Substituent effects on 1-benzylindole-3-(p-substituted) acetophenone derivatives were studied, and addition were facilitated by electron attracting groups. On the base of the rate equation, substituent effect, and general base effect the plausible addition mechanism was proposed : Below pH 3.0, only neutral thiourea molecule was added to the carbon-carbon double bond, and in the range of pH 0.0~14.0, netural thiourea molecule and thiourea anion competitively attacted the double bond. By contrast, above pH 10.0, the reaction was dependent upon only the addition of thiourea anion.

The kinetics of hydrolysis of cinnamenylisophorone derivatives (rho-H, rho-Br, P-Cl, rho-OCH3) was investigated using ultraviolet spectrophotometry in 20%(v/v) dicxane-H2O at 25℃. A rate equation which can be applied over wide pH range (pH 1.0~13.0) was obtained. In order to investigate the substituent effects on cinnarnenylisophorone derivatives, Hammett constant was plotted. As the result, the rate of hydrolysis of cinnamenylisophorone derivatives was facilitated by electron donating group. Final products of the hydrolysis were benzaldehyde and isophorone, From the measurement of reaction rate constant according to pH changes, substituent effect, and final products, it was found that the hydrolysis of cinnarnenylisophorone derivatives was initiated by the neutral H2O molecule which does not dissociated at below pH 9.0, and in the range of pH 9.0~11.0 this reaction occurs by H2O or hydroxide ion competitively, but proceeded by the hydroxide ion above pH 11.0. On the basis of this kinetic study, the reaction mechanism of the hydrolysis of cinnamenylisophorone derivatives was proposed.

Four novel amphoteric surfactants of N-(2-alkylamidoethyl)-N, N-dimethyl ammonioacetates were synthesized. The each reaction between four saturated fatty acids containing 10, 12, 14 and 16 carbon atoms and N, N-dimethylethylene diamine permitted to give the intermediate products, N-(2-alkylamidoethyl)-N, N-dimethylamines. Quaterinzation of these intermediates was permitted to form N-(2-alkylamidoethyl)-N, N-dimethyl, ammonioacetates, whose sturctures were identified by CC, TLC, elemental analysis, IR pectrophotometry and 1HNMR spectrometry. The products yielded from 48% to 58%. The isoelectric points were shown in the range of 4.30~6.64. It showed a tendency to learn to the acidic site and its range was broadened as increase of the hydrophobic group length. Surface tensions of the aqueous solution in the 10-6~10-1mol/l of amidobetaines were measured. and the critical micell concentration(cmc) were shown in the range of 8.37×10-6~8.96×10-2mol/l, and γcmc were reduced to 32.3~38.2 dyne/cm. A linear relationship between log cmc and the number of carbon in the hydrophobic alkyl chain was presented by the formula of log cmc=2.38-0.5n, and the contribution-rate of n on the standard free energy change in micellization ɘ(δG0m)/ɘn, was calulated as -0.5RT.

The thermodynamics of micellization of a new series of ionic surface-active agents, dimethyl alkyl-2-deoxy-2-epi-inosityi-ammonium chlorides, has been examined, A minimum in the critical micelle concentration versus temperature has been observed at 25℃ It has been found that the standard entropy of micellization is always positive showing that miceliization is governed by the gain in entropy associated with the removal of the monomer from an aqueous environment to the micelle over a 15℃ to 45℃ temperature while governed by enthalpy directed process below 25C˚.

The rate constants for the addition reaction of thiourea to nitrone derivatives were determind at various pH and reaction rate equation which could be applied over a wide pH were obtained. The substituent effects and general base catalysis for the addition of thiourea to nitrone derivatives were observed. On the basis of these findings, a plausible reaction mechanism for the nucleophilic addition of thiourea to nitrone was proposed.

The kinetic of hydrolysis for cinnamylidene aniline derivatives has been investigated by ultraviolet spectrophotometry in 20% (v/v) dioxane - H2O at 25℃. A rate equation which can be applied over wide pH range was obtained. The substituent effects on cinnamylidene aniline derivatives were studied and the hydrolysis was facilitated by electron attracting group. Final products of the hydrolysis were cinnamaldehyde and aniline. From the rate equation, substituent effect and final products, the hydrolysis of cinnamylidene aniline derivatives was initiated by the neutral molecule of H2O which does not dissociate at below pH 9.0~12.0, but proceeded by the hydrogen ion at above pH 5.0~9.0.

The Kinetics of the addition of benzalacetophenone derivatives was investigated by ultraviolet spectrophotometery in 5% dioxane H2O at 50℃. A rate equation was obtained in wide range of pH. The substituent effects on benzalacetophenone derivatives were studied, and addition were facilitated by electron attracting groups. The final product was benzalacetophenone-β-thioglycolic acid synthesized by the addition of thioglycolic acid to benzalacetophenone. On the base of the rate equation, substituent effect, general base effect and final product, the plausible addition mechanism was proposed: Below pH 9.0, only neutral thioglycolic acid molecule was added to the carbon-carbon double bond, and in the range of pH 9.0~11.0, neutral thioglycolic acid molecule and thioglycolic acid anion competitively attacted the double bond. By contrast, above pH 11.0, the reaction was dependent upon only the addition of thioglycolic acid anion.

The Kinetics of the Hydrolysis of benzalacetophenone derivatives has been investigated by ultraviolet spectrophotometry in 5% dioxane - H2O at 50℃. A rate equation which can be applied over wide pH range was obtained. The substituent effect on the hydrolysis of benzalacetophenone derivatives were facilitated by electron attracting groups. Based on the rate equation, substituent effect, general base effect, activation parameters and final product, the hydrolysis of benzalacetophenone derivatives seems to be initiated by the netural molecule of H2O which does not dissociate at below pH 9.0 but proceeded by the hydroxide ion at above pH 11.0. In the range of pH 9.0~11.0 these two reactions occur competitively.

The rate constants of the hydrolysis of cinnamanilide derivatives were determined UV spectrometry in H2SO4 (5~20N), NaOH(5~11N) at 50~110℃ and rate equation could be applied over a strong acid and strong base were obtained. Final product of the hydrolysis was a cinnamic acid. The σ values obtained from the slope of linear plots of log kabs vs. Hammet tΣ constants were slightly negatives, Substituents on cinnamanilide showed a relatively small effect, with hydrolysis facilitated be electron donating group. Activation energy(Ea)was also calculated for the hydrolysis of the cinnamanilide. From this reaction rate equation, substituent effect and experimental of rate constants, that the hydrolysis of cinnamanillde was Initiated by the netural molecule of H2O which do not dissociate at strong acid, and proceeded by hydroxide ion at strong base.

The adsorptions of 2-(dimethylalkylammonio)propanoates with straight chain alkyl group having from 12 to 16 carbon atoms on the liquid-air interface were decreased while lowering the surface tensions at critical micelle concentrations. In micellization, the standard free energy changes per methylene in alkyl group were found to make same contribution to the micelle formation of corresponding C-alkylcarboxybetaines, and the standard enthalpy and entropy changes were studied within the range of temperature from 30 to 50℃.

Isoelectric point and surface tension of twelve of the alkylcarboxy betaines such as 2-(trimethylammonio) dodecanoate, 2-(trimethyammonio) tetradecanoate, 2-(trimethylammonio) hexadecanoate, (dimethyldodecylammonio)ethanoate, (dimethyltetradecylammonio)ethanoate, (dimethylhexadecylammonio) ehtanoate, 2-(dimethylododecylammonio) propanoate, 2-(dimethyltetradecylammonio)proopanoate, 2-(dimethylhexadecylammonio)propanoate, 2-(dimethyltetradecylammonio)-3-phenyl propanoate, 2-(dimethyltetradecylammonio)-3-phenyl propanoate are tested. From the measurement of the isoelectric point, it was found that the isoelectric point were leaned toward the alkaline zone for c-alkylarbrxybetaines, and toward the acidic zone for N-alkylcarboxybetaines. At the range of the carboxybetaine concentration 2 × 10-2~2 × 10-5mole/l, the surface tension of the aqueous solution were decreased to 30-38 dyne/cm, showing the tendency that the ability of lowering the surafce tension was depending on the increase of carbon atom number in the lipophilic alkyl chain. The critical micelle concetration measured by the surface tension and concentration curves have been found at the range of 10-2~10-5mole/l.

Inosamine(deoxyaminoinositol) stereomers such as scyllo-inosamine, myo-inosamine-2, epi-inosamine-2 and myo-inesamine-4 have been synthesize from myo-inositol (1,2,3,5/4,6-hexahydroxycyclohexane) And sixteen of quaternary ammonium salt type deoxyaminoinositols such as dimethylalktl-deoxy-scyllo-inosityl-, dimethylalkyl-2deoxy-2myo-inosityl-, dimethylalkyl-2-deoxy-2-epi-inosityl and dimethylal inosityl-, dimethylalkyl-2-deoxy-2-myo-inosityl-, dimethylalkyl-2-deoxy-2-epi-inosityl and dimethylalkyl-4-deoxy-4-myo-imosityl ammonium chlorides with straight chain alkyl group having from eight to fourteen carton atoms have been synthesized from four kinds of the imosamine stereomers. The isolation and detection of dimethylalkyl-deoxy-inosityl ammonium chlorides have been investigated by column chromatography, paper chromatography, infrared absorption spectra and elementary analysis, respectively.

Surface chemical properties including surface tension, Ross-Miles foaming power, foam stabilities, emulsifying properties, emulsion stabilities, effectiveness of dispersion, dispersion stabilites of the quaternary ammonium salt type deoxyaminoimositol derivatives such as sixteen kinds of dimethylafkyl-deoxyscyllo-inosityl- dimethylalkyl-2-deoxy-2-myo-inosityl-, dimethylakyl-2-deoxy-2-epi-inosityl- and dimethylalkyl-4-deoxy-4-myo-inosityl ammonium chlorides are tested. And critical micelle concentration of these compounds are estimated from the curves of surface tension and concentration. The experimental results show that the members of this class of compounds have necessary surface active properties to make them effective surfactants.

Four amphoteric surfactants, 1-(N-alkyl-N,N-dimethyl ammonio)-4-naphthalene sulfonates, were prepared by the alkylation of 1-(N,N-dimethylamino)-4,naphthalene sulfonic acid with chloroalkanes such as 1-decylchloride, 1-tetradecyl chloride and 1-hexadecyl chloride. These quaternary ammonium compounds such as 1-(N-decyl-N, N-dimethylammonio)-4-naphthalene sulfonate, 1-(N-dodecyl-N,N-dimethylammonio)-4-naphthalene sulfonate, 1-(N-tetradecyl-N,N-dimethylammonio)-4-naphthalene sulfonate and 1-(N-hexadecyl-N,N-dimethylammonio)-4-naphthalene sulfonate could be separated by means of thin layes chromatography and column chromatography. The surface chemical properties such as surface tension, foaming power, foam stability, wetting efficiency and solubilizing effect for these four compounds were measured. Also critical micelle concentration and hydrophilic-lipophilic balance(HLB) were evaluated. These compounds showed good surface as O/W type emulsifying agent and detergent.