• Bulletin of the Korean Chemical Society
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• 제12권5호
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• pp.560-564
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• 1991

The gas-phase pyrolysis reactions of iminoethers (Ⅱ), 2-alkoxypyridines (Ⅲ), 2-N-alkylated pyridones (Ⅳ) and N-alkylated acetamides (Ⅴ) have been studied MO theoretically with the AM1 method. The decomposition of these compounds proceeds by a concerted retro-ene process through a six-membered cyclic transition state. The reactivity decreases in the order (Ⅱ) > (Ⅲ) > (Ⅳ) > (Ⅴ), with a greater reactivity for the imine series, (Ⅱ) and (Ⅲ), compared to the amide series, (Ⅳ) and (Ⅴ), and a difference in basicity between the N and O atoms. Within a given series, however, the reactivity is dictated mainly by the aromaticity in the transition state. The reactivity order with respect to side alkyl chain of a species was found to increase as the steric crowding effect increases. The AM1 reactivity in this work agree well with the experimental results.

• 한국안전학회지
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• 제11권2호
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• pp.60-66
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• 1996

In order to look into the internal structure and electrical properties of insulating Silicone rubbers added reinforcing fillers ; Silica(0-140 phr ), and to examine the behavior of charged particles, and the properties of thermally stimulated current (TSC) are investigated, respectively. From the TSC which are formed by applying the electric field of 2~5 ㎸/mm to specimen at temperature range from -150 to $270^{\circ}C$, the results arp as following. In the case of non-filled specimen, four peaks of $\delta$, $\gamma$ , $\beta$ and u are obtained at the temperature of $-120^{\circ}C$, $-60^{\circ}C$, $20^{\circ}C$ and $130^{\circ}C$, respectively and the case of filled specimen, three peaks of $\delta$, ${\alpha}_2$ and ${\alpha}_1$ are observed at the temperature of of $-120^{\circ}C$, $80^{\circ}C$ and $130^{\circ}C$, respectively. The origins of these peaks are that, the $\delta$ peak seems to the result from the contribution of side chain methyl radical, and the $\beta$ peak from the depolarization of space charge polarization owing to added imputity during during manufacturing specimens, and the $\beta$ peak from the orientation of $Si-CH_3$dipole, and the ${\alpha}_2$ near the temperature of $130^{\circ}C$ from carboxyl acid that is formed by the thermal oxidation of high temperature.

• Bulletin of the Korean Chemical Society
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• 제12권2호
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• pp.143-148
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• 1991

In the unhydrated and hydrated states, conformational free energies of L-ascorbic acid anion (AAA) were computed with an empirical potential function and the hydration shell model (a program CONBIO). The conformational energy was minimized from possible starting conformations expressed with five torsion angles of the molecule. The conformational entropy of each low energy conformation in both states was computed using a harmonic approximation. As found in L-ascorbic acid (AA), intramolecular hydrogen bonds (HBs) are proved to be of significant importance in stabilizing the overall conformations of AAA in both states, and give the folded conformations, which are quite different from those in crystal. There are competitions between HBs and hydration around O3 atom of the lactone ring and hydroxyls of the acyclic side chain. Especially, the whole conformation of AAA is strongly dependent on the water-accessibility of O3 atom. Though there is a significant effect of the hydration on conformational surface, the lowest energy conformation of the unhydrated AAA is conserved. The different patterns of HBs and hydration result in the conformations of AAA in both states being different from those of AA. It can be drawn by several feasible conformations obtained in the hydrated state that there exists an ensemble of several conformations in aqueous solution.

• Bulletin of the Korean Chemical Society
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• 제28권12호
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• pp.2209-2213
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• 2007

Ginseng has long been used as a traditional medicine in Asian countries including Korea and China. In recent years, it has been reported that the biological activities of ginseng are due to its active components, ginsenosides. Ginsenosides are represented by triterpenes of the dammarane type. Ginsenoside Re consists of two glucose rings, one rhamnose ring, and the triterpene ring. In the present study ginsenoside Re has been isolated from the Korean ginseng (Panax ginseng) and the tertiary structure has been determined using NMR spectroscopy. Flexibilities around each linkages described by seven torsion angles were considered. The structures of ginsenoside Re obtained by NMR spectroscopy show the rigidity around the glucopyranosyl ring II and alkene side chain. The dihedral angles of φ5, φ6, φ7 are about 150o, 50o and 45o, respectively. In addition, flexibility exists around rhamnopyranosyl and glucopyronosyl moiety. The linkage around the rhamnopyranosyl and glucopyranosyl ring I, are divided into three groups. This flexibility seems to play important role in regulation of the hydrophobic surface exposed to the solvent. Because of the growing need for the structural determination of ginsenoside, this result can help to understand their well-accepted pharmacological effects of ginsenoside Re.

• Elastomers and Composites
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• 제40권2호
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• pp.136-142
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• 2005

주사슬에 $SO_2$를 포함하고 곁사슬에는 메소겐기을 유연격자에 연결시킨 액정 poly (allylsulfone) network를 합성하여 이들의 기체 투과도 및 선택투과 특성을 조사하였다. 곁사슬에 메톡시를 갖는 단량체I은 한 개의 알릴단위를 갖고, 단량체II는 양쪽 말단에 두개의 알릴 단위를 가져 network 형성을 제어할 수 있도록 구성되었다 가교밀도의 증가는 고분자 network 내의 분자운동을 제한시키며 단량체 II 함량이 5% 이하인 경우는 segment의 운동이 충분히 펼쳐질 수 있어 등방상으로의 상전이가 일어날수 있다. Poly(II-5 $01/I-OCH_3$ 99)의 기체 투과도는 산소($O_2$)의 경우 2.58 barrel 인데 비하여, 수소($H_2$)의 경우는 18.4 barrer로서, 선택 투과도 ${\alpha}(H_2/O_2)$가 7에 가까우며, 또 선택 투과도 ${\alpha}(H_2/N_2)$는 23.9로서 가장 높은 값을 가짐을 관찰하였다. 가교도가 10%로 증가된 Poly(II-5 $10/I-OCH_3$ 90)의 경우 선택 투과도 ${\alpha}(H_2/N_2)$는 36.8로서 가교도 증가에 따르는 선택투과도의 증가를 보여주었다.

• Elastomers and Composites
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• 제31권5호
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• pp.335-340
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• 1996

In order to look into the internal structure and the properties in the silicone rubbers added reinforcing fillers; silica $additives(O{\sim}140phr)$, and to examine the behavior of charged particles, the properties of thermally stimulated current(TSC) and X-Ray diffraction are investigated, respectively. And then, from the TSC which are formed by applying the electric field of $2{\sim}5kV/mm$ to specimen at the temperature range from -150 to $260^{\circ}C$, the results are as follwing: In the case of non-filled specimen, four peaks of ${\delta},\;{\gamma},\;{\beta}\;and\;{\alpha}$ are obtained at the temperature of $-120^{\circ}C,\;-60^{\circ}C,\;20^{\circ}C\;and\;130^{\circ}C$, respectively and the case of filled specimen, three peaks of ${\delta},\;{\alpha}_2\;and\;{\alpha}_1$ are observed at the temperature of $-120^{\circ}C,\;80^{\circ}C\;and\;130^{\circ}C$, respectively. The origins of these peaks are that, the ${\delta}$ peak seems to the result from the contribution of side chain methyl radical, and the ${\gamma}$ peak from the depolarization of space charge polarization owing to be added impurity during manufacturing specimens, and the ${\beta}$ peak from the orientation of $Si-CH_3$ dipole, and the ${\alpha}_2$ near the temperature of $80^{\circ}C$ from hydroxyl in carboxylic radical, and finally, the ${\alpha}_1$ peak near the temperature of $130^{\circ}C$ from carboxyl acid that is formed by the thermal oxidation of high temperature.

• 한국연초학회지
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• 제20권2호
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• pp.178-182
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• 1998

Previously, we showed that acetone enhanced aryl hydrocarbon hydroxylase (AHH) activity in only 3-methylcholanthrene (MC)- or $\beta$-naphtoflavone (BNF)-inducible microsomes of rat liver. In the present study, the possible mechanism underlying acetone action on AHH was investigated in the liver microsomes from MC-pretreated rats. Other n-alkylketones except acetone did not increase AHH activity, which rather decreased significantly with the length of alkyl side chain. Acetone had no effect on the activity of NADPH-cytochrome P450 reductase or inhibited the formation of 3-OH benzo(a)pyrene (B(a)P) in nonenzymatic model ascorbic acid system. However, in cumene hydroperoxide (CuOOH)-supported B(a)P hydroxylation, acetone enhanced its velocity remarkably by 30% at the optimal concentration (30 $\mu$M CuOOH and 1.0% acetone). From these results, we conclude that acetone may facilitate the formation of an activated oxygen species or the insertion of oxygen into B(a)P molecule in CYP1A rich microsomes.

• Macromolecular Research
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• 제11권2호
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• pp.115-121
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• 2003

In this research, the in vitro anti-thrombogenecity of artificial materials was evaluated using hydrophilic/hydrophobic copolymers containing oiligosaccharide as hydrophilic moiety and phospholipid as hydrophobic moiety respectively. N-(p-vinylbenzyl)-[O-$\alpha$-D-glucopyranosyl-(1longrightarrow4)]$_{n-1}$-D-glucoamide(VM7A) was (VM7 A) was adopted as hydrophilic oligosaccharide and 2-acryloxybutyl-2-(triethylammonium)ethyl phosphoric acid (HBA-choline) was adopted as hydrophobic phospholipid. Copolymers having various monomer feeding molar ratios were synthesized through radical polymerization. The synthesized copolymers were identified using FT-IR, $^1$H-NMR, XPS, and DSC. The surface energy of the copolymers were evaluated by dynamic contact angle (DCA) method and checked different roles of VM7A as hydrophilic moiety and HBA-choline as hydrophobic moiety on surface. The surface morphological differences between hydrated and unhydrated surfaces of copolymers were observed and evaluated using Am. The platelets were separated from canine whole blood by centrifugation and adopted to the anti-thromobogenecity test of the copolymers. From the results, we find out that as VM7A ratio increases, so did anti-thrombogenecity. Such results show the possibility of using these copolymers as blood compatible materials in living body.y.

• Macromolecular Research
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• 제11권4호
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• pp.236-240
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• 2003

Fabrication of a graded index profile was possible via photochemical reaction of cinnamoyl groups with 350 nm wavelength UV light to form crosslinked structures. Such structural change may induce the change in the refractive index. In order to generate graded index profile in the PMMA polymer optical fiber (POF) with cinnamoyl groups by photochemistry, a methyl methacrylate monomer containing a cinnamoyl functional group in the side chain were prepared. This monomer was then copolymerized with methyl methacrylate with various compositions not only to utilize advantages of poly(methyl methacrylate) but also to overcome the drawbacks of the cinnamate homopolymer. Changes of refractive indices were investigated with various contents of cinnamoyl group and varying irradiation time. Large change in the refractive index (${\Delta}{\approx}0.01$) and its proper profile shape ($g{\approx}2.2$) can be obtained by changing irradiation time.

• Bulletin of the Korean Chemical Society
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• 제28권8호
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• pp.1299-1304
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• 2007

New sulfur functionalized cyclopentadiene ligands, 1-[2-(thioanisole)]-2,5-dimethylcyclopentadiene (3), 1-[2- (thioanisole)]-2,3,5-trimethylcyclopentadiene (4), and 1-[2-(thioanisole)]-2,3,4,5-tetramethylcyclopentadiene (5), were prepared. In these ligands, the S-donor atom is connected to a cyclopentadiene ring by a rigid phenylene spacer. CpCo(III)-diiodo half-sandwich complexes (6-8) were obtained from reaction the ligands (3- 5) with Co2(CO)8, followed by treatment of I2. Substitution reaction of CpCo(III)-diiodo complexes with MeLi yielded the corresponding CpCo(III)-dimethyl complexes (9-11). Further transformation to the corresponding cationic cobalt complexes (12-14) were achieved by reaction of the CpCo(III)-dimethyl complexes with HB(ArF)4·2Et2O and trapping with CD3CN. The new sulfur functionalized cyclopentadiene ligands having a rigid phenylene spacer and the corresponding cobalt complexes were characterized by 1H, 13C and 19F NMR spectroscopy. The diiodo Complex 6 was also characterized by a single crystal X-ray diffraction method.