• Bulletin of the Korean Chemical Society
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• 제11권1호
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• pp.65-69
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• 1990

The nucleophilic substitution reactions of naphthalene-1,5-disulfonyl chloride and 4-fluorosulfonylbenzenesulfonyl chloride with p-substituted anilines and methyl substituted pyridines in methanol-acetonitrile mixtures and hydrolyses of those disulfonyl halides have been studied by means of conductometric and polarographic methods. A large difference in the selective parameter, ${\rho}_N$ between mono-sulfonyl chloride and disulfonyl halide can be taken as an evidence that the second $SO_2Cl$ grolup of naphthalene-1,5-disulfonyl chloride also takes part in the reaction in contrast to sulfonyl fluoride in 4-fluorosulfonylbenzenesulfonyl chloride, which only acts as a substituent in the nucleophilic substitution reaction.

• Bulletin of the Korean Chemical Society
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• 제7권3호
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• pp.201-204
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• 1986

Reduction of N-arylpyridinium compounds by $NaBH_4$ gave mixtures of the corresponding 1,2-dihydropyridine(major) and 1,4-dihydropyridine(minor), whereas similar reduction by $Na_2S_2O_4$ produced 1,4-dihydropyridines regioselectively. The proportion of 1,4-isomer in the product by $NaBH_4$ reduction appeared to increase with the electron-donating ability of N-aryl groups. When the N-aryl group is p-methylphenyl, p-ethylphenyl or p-methoxyphenyl, the 1,2-dihydropyridines in ethanol-water (4:1) solutions isomerized to the corresponding 1,4-dihydropyridines. N-(p-methylphenyl)-1,2-dihydropyridine and N-(p-ethylphenyl)-1,2-dihydropyridine in solid state also isomerized to the corresponding 1,4-dihydropyridines. The different behaviors of reduction among N-arylpyridiniums and isomerization of the reduction products depending on the substituent in N-aryl group were explained in terms of difference in the electronic effects of the substituents.

• 한국전기전자재료학회논문지
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• 제14권2호
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• pp.145-151
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• 2001

In this study, blue light emiting, soluble PPV copolymers were synthesized by Witting reaction and characterized. ITO/copolymer/Ca and ITO/copolymer/A1 structured light emitting diodes(LED) were fabricated and their I-V characteristics were examined. Copolymers showed $\pi$-$\pi$ transition in UV-Vis./NIR spectra. The PL and abosorption spectrum showed the symmetric vibration modes with mirror images which means that copolymers are highly aligned. By introducing aliphatic hydrocarbon group on polymer main chain, the solubility of copolymers was improved and no significant effects of substituent were observed. The band offset of copolymers are well suited as light emitting material for LED application than monomer or oligomer does. THe band offset of copolymers is ∼3eV in PL spectrum and the threshold voltages of ITO/copolymer/Ca and ITO/copolymer/Al structured LED 3V, 12V respectively. In the case of ITO/copolymer/Ca LED, it is believed that the amount of electrons and holes is well balanced and the recombination of opposite charges occurs easily because the work functions of Ca and Al electrodes are 2.9 and 4.3eV respectively and the difference in barrier height between polymer and electrode was small.

• Bulletin of the Korean Chemical Society
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• 제15권2호
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• pp.161-167
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• 1994

Rate constants have been measured spectrophotometrically for the nucleophilic substitution reactions of aryl substituted benzenesulfonates (3) with alkali metal ethoxides ($EtO^-M^+$) and butane-2,3-dione monoximates ($Ox^-M^+$) in ethanol at $25^{\circ}C$. The reactivity of the alkali metal ethoxides decreases in the order $EtO^-K^+> EtO^- > EtO^-Li^+$, indicating that $K^+$ ion behaves as a catalyst and $Li^+$ ion acts as an inhibitor for all the substrates studied. For the corresponding reactions of 3 with Ox^-M^+$, $Li^+$ ion also exhibits inhibitory effect for all the substrates, while, $K^+$ ion shows catalytic or inhibitory effects depending on the nature of substituents on the acyl and phenyl moieties. A study of substituent effect on rate has revealed that both EtO^- $and Ox^-$ systems have the same reaction mechanism. The different behavior shown by $K^+$ ion for the reaction of 3 with $EtO^-$ and $Ox^-$ would be attributed to a difference in charge polarization of S=O bond in the transition state between the two systems and/or a change in conformation of Ox^-K^+$.

• 한국응용과학기술학회지
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• 제7권1호
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• pp.93-105
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• 1990

Semicarbazone formation of nine monosubstituted benzaldehydes was studied kinetically in 20% methanol buffer solution at 15, 25, 35, and $45^{circ}C$. The rate of p-nitrobenzaldehyde semicarbazone formation is 2.7 times as fast as that of benzaldehyde, while p-hvdroxybenzaldehyde is 3.6 times as slow as that of benzaldehyde. Activation energies for p-chlorobenzaldehyde, benzaldehyde, p-methylbenzaldehyde, p-methoxybenzaldshyde, p-hydroxybenzaldehyde, and p-dimethylaminobenzaldehyde semicarbazone formation are calculated as 5.80, 6.19, 6.57, 7.06, 8.03, and 6.46 kcal/mol respectively. It is concluded from the effect of ionic strength that the reaction is affected by not ions but neutral molecules involving hydrogen bonding between oxygen atom of carbonyl group and hydrogen atom of acid-catalyst, and concerted attack of the necleophilic reagent, free base on carbonyl compound. Also, the effect of solvent composition is small in 20% and 50% methanol (and ethanol) aqueous solutions. The ${\rho}-{\sigma}$ plots for the rates of semicarbazone formation at pH 7.1 show a linear ${\rho}-{\sigma}$ relationship (${\rho}=0.14l$, in contrast to that at pH 2.75 and pH 5.4 corresponding to ${\rho}-{\sigma}$ correlations reparted by Jencks. The rate of semicarbazone formation at pH 5.4 show a relationship which is convex upward, resulting in a break in the curve but at pH 2.75, slight difference from a linear relationship. As a result of studying citric acid catalysis, second-order rate constants increase linearly with citric acid concentration and show a 2 times increase as the catalyst concentration is varied from 0.025 to 0.1 mol/1 at pH 2,9, but slight increase at pH 5.3. The rate-determining step is addition below pH 5 but is dehydration between pH 5 and 7. Conclusively, the rate-determining step of the reaction changes from dehydration to addition in respect to hydrogen ion activity near pH 5. The ortho: para rate ratio of the hydroxybenzaldehydes for semicarbazone formation is about 17 at $15^{\circ}C$. It is concluded that the results constitute strong evidence in favor of greater stabilization of p- than o-hydroxybenzaldehyde by substituent which donate electrons by resonance and is due to hydrogen bonding between the carbon-bound hydrogen of the-CHO group and the oxygen atom of the substituent.

• 멤브레인
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• 제27권5호
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• pp.399-405
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• 2017

계면동전위라 불리는 제타전위(zeta potential)란 표면 전하적 특성을 정량화 한 값으로 전기동역학적 현상으로 발생하는 전위차를 말한다. 제타전위는 막오염(fouling)과 표면전하 분석을 통한 개질 확인 및 치환기 확인에 대한 연구가 활발히 진행되어 왔다. 그리고 제타전위를 측정하는 방법으로는 전기영동(electrophoresis), 전기삼투(eletrosmosis), 유동전위(streaming potential)를 기초로 개발되었고, 그중에서도 평막은 유동전위 측정이 적합하다고 알려졌다. 따라서, 본 연구에서는 poly(styrene-ethylene-butylene-styrene) 고분자에 암모늄을 도입하여 아민화된 SEBS 평막 형택의 분리막을 제조하고, 계면동전위 측정기를 이용하여 제조된 분리막들의 유동전위를 측정하여 결과를 분석하였다.

• 한국가금학회지
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• 제39권4호
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• pp.297-303
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• 2012

본 시험은 옥수수 주정박의 첨가가 소화 부위별 아미노산 소화율에 미치는 영향을 조사하기 위하여 수행하였다. 공시계는 Ross종 육계 수컷 24수를 이용하였다. 시험사료는 옥수수-대두박 위주의 사료(CP 19%, ME 3,150 kcal/kg)를 기초 사료로 하였으며, 주정박을 6%와 12% 첨가한 사료를 시험사료로 하였다. 시험 설계는 사료 내에 주정박을 첨가시킨 양에 따른 3처리구(처리구당 8수)로 나누고, 소화물 채취 부위에 따른 4처리구로 나누어 $3{\times}4$의 복합 요인으로 소화율을 조사하였다. 소화율 측정을 위한 시료 수집 부위는 공장의 말단부(DJ, the distal end of the jejunum), 회장의 중부(MI, the middle part of the ileum), 회장의 말단부(DI, the distal end of the ileum) 및 직장의 말단부(DR, the distal end of the rectum)로 하였다. 주정박 첨가 수준과 채취 부위 사이에는 유의한 상관관계가 없었다. 본 시험의 진정 소화율은 부위에 따라서는 유의적인 차이는 발견되지 않았다(P<0.05). CDDGS 첨가 수준에 따른 소화율은 필수 아미노산 중 lysine의 소화율이 CDDGS 첨가구에서 감소하였다(P<0.05). 또한 비필수 아미노산에서는 glycine의 소화율이 CDDGS 첨가구에서 감소하였으며(P<0.05), 다른 아미노산들은 처리구간에 차이가 없었다. 따라서 CDDGS는 lysine과 glysine 소화율은 대조구에 비해 낮았으나, 대체적으로 대조구와 유사한 소화율을 보여 부존 자원으로서 가금 사료에 이용할 수 있으리라 사료된다.