• 한국환경과학회지
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• 제22권10호
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• pp.1317-1325
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• 2013

Paulownia coreana is a medicinal, edible and industrial plant with the largest leaf, and is native to Korea. We evaluated the reducing power activities, 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical scavenging activities (RSAs), nitrite scavenging activities (NSAs) and 2,2-azino-bis-(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) cation RSAs by solvent extraction of P. coreana bark by using $50^{\circ}C$ hot water and $25^{\circ}C$ methanol. The antioxidative effect of P. coreana bark extract on corn seed oil was evaluated using the Rancimat test. The extraction yields on dry weight basis with 15 folds of hot water and methanol were 23.88% and 5.30%, respectively; further the flavonoid content in the hot water extract was over 2.5 times more than that in the methanol extract. The DPPH RSA of the methanol extract was substantially higher than that of the water extract, whereas the NSA of the water extract was higher than that of the methanol extract at pH 1.2. The ABTS RSAs of the two extracts were almost the same as that of ascorbic acid and 2,6-ditertiarybutyl hydroxytoluene. The two extracts of P. coreana bark in this study were found to slightly improve the oxidation stability of corn seed oil.

• Bulletin of the Korean Chemical Society
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• 제33권11호
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• pp.3657-3664
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• 2012

Reactions of 1-adamantylmethyl chloroformate ($1-AdCH_2OCOCl$, 1) and 1-adamantylmethyl fluoroformate ($1-AdCH_2OCOF$, 2) in hydroxylic solvents have been studied. Application of the extended Grunwald-Winstein (G-W) equation to solvolyses of 1 in a variety of pure and binary solvents indicates an addition-elimination pathway in the majority of the solvents except an ionization pathway in the solvents of relatively low nucleophilcity and high ionizing power. The solvolyses of 2 show an addition-elimination pathway in all of the mixed solvents. The leaving group effects ($k_F/k_{Cl}$), the kinetic solvent isotope effects (KSIEs, $k_{MeOH}/k_{MeOD}$), and the enthalpy and entropy of activation for the solvolyses of 1 and 2 were also calculated. The selectivity values (S) for each solvent composition are reported and discussed. These observations are compared with those previously reported for other alkyl haloformate esters.

• 자원리싸이클링
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• 제26권2호
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• pp.3-10
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• 2017

희토류 원소는 첨단 산업용 소재의 구성 성분으로 고순도가 요구된다. 국내산 monazite광과 Ni-MH전지는 경희토류를 함유한 자원이다. 이러한 자원을 염산으로 침출한 용액에서 경희토류성분을 용매추출로 분리하는 공정에 대해 고찰하였다. 양이온 추출제와 3차 아민의 혼합추출제로 경희토류를 추출시 상승효과가 있으며 pH 감소가 둔화된다. 혼합추출제 사용시 수상의 pH가 금속의 추출 및 상승효과에 미치는 영향을 분석하였다. 향후 양이온과 아민의 혼합추출제에 의한 경희토류 분리공정을 개발하기 위해서는 mixer-settler의 조업 자료 확보가 필요하다.

• 산업식품공학
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• 제15권4호
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• pp.289-296
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• 2011

Twenty four fractions by solvent extraction and/or acid precipitation from fruit body and culture broth of Inonotus obliquus were prepared, and their inhibitory effect against acetylcholinesterase (AChE) was investigated. Among these fractions, acid (1 M HCl) precipitates from cell-free culture broth and fruit body exhibited the highest inhibitory effect on AChE in vitro. Acid precipitates inhibited AChE activity in a concentration-dependant manner and $IC_{50}$ values of both acid precipitates were 0.53 mg/mL. The inhibition pattern was general non-competitive inhibition. The energetic parameters were also determined by dual substrate/temperature design. Both acid precipitates increased the values of Ea, ${\Delta}H,/;{\Delta}G$ and ${\Delta}H^{\ast}$ decreasing the value of ${\Delta}S$ for AChE. The results implied that the acid precipitates from I. obliquus increased the thermodynamic barrier, leading to the breakdown of ES complex and the formation of products as inhibitory mechanism.

• Bulletin of the Korean Chemical Society
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• 제17권3호
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• pp.234-238
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• 1996

Second-order rate constants have been measured spectrophotometrically for the reaction of p-nitrophenyl acetate (PNPA) with morpholine, piperazine and piperidine in MeCN-H2O mixtures of varying compositions. The rate of the present aminolysis decreases upon additions of MeCN into H2O up to near 30-40 mole % MeCN and remains nearly constant upon further additions of MeCN. The reaction of PNPA with anionic nucleophiles, such as HO-, p-chlorophenoxide and butane-2,3-dione monoximate, has also exhibited two distinguishable reactivity zones. However, the reactivity trend for the anionic nucleophiles is quite different from the one obtained for the amine system, e.g. an initial rate decrease in the H2O-rich region followed by an increasing rate trend upon further additions of MeCN in the MeCN-rich region. The rate behaviors shown by the amine system in the MeCN-rich and by the anionic system in the H2O-rich region are unexpected based on the Hughes-Ingold rules. The present unusual rate trends have been attributed to changes in the solvent structure and pKa of the nucleophiles upon the addition of MeCN into H2O. The effect of solvent appears to be more significant for the TS than the GS, and the TS structure is considered to become tighter in the higher MeCN concentration.

• Bulletin of the Korean Chemical Society
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• 제11권4호
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• pp.309-313
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• 1990

The rates of solvolysis of trans-$[Co(N-eten)_2Cl_2)$+ (N-eten; N-ethylethylenediamine) have been investigated using spectrophotometric method in binary aqueous mixtures containing methyl alcohol, isopropyl alcohol, t-butyl alcohol, ethylene glycol and glycerol. The values of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ obtained from temperature effect on the rate constants were $80{\sim}84 kJmol^{-1}$ and $- 28{\sim} - 45 JK^{-1}mol^{-1}.$ Extrema found in the variation of the enthalpy and entropy of activation with solvent composition correlated very well with extrema in the variation of the physical properties of mixture which relate to sharp change in the solvent structure. The reaction mechanism was discussed in terms of correlation diagrams involving the exess molar Gibbs function of mixing for the binary mixtures. The behavior of this cobalt(Ⅲ) complex was compared with that of t-butyl chloride. The application of free energy cycle to the process initial state to transition state in water and in the mixture showed that the solvation of transition state had dominant effect on the rates in the mixtures. It was found that $S_N1$ character was increased with increasing the content of co-solvent in the mixture.

• 센서학회지
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• 제26권2호
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• pp.96-100
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• 2017

Poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been extensively studied as the active material in ammonia gas sensor because of its fast response time, high conductivity and environmental stability. It is well known that a post annealing process for organic devices based on PEDOT:PSS significantly increases the device performance. In this study, we propose the solvent annealing of PEDOT:PSS and investigated its effects. As a results, post solvent annealing on PEDOT:PSS lead to the surface chemical and physical properties change. These changes result in improved conductivity of the PEDOT:PSS. In additional, ammonia sensitivity of solvent annealed PEDOT:PSS become higher than pristine polymer film. The enhancement is mainly caused by the depletion of gas barrier PSS and structural re-forming PEDOT networks. We believe that the post solvent annealing is a promising method to achieve highly sensitivity PEDOT:PSS films for applications in efficient, low-cost and flexible ammonia gas sensor.

• 대한화학회지
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• 제36권5호
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• pp.632-637
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• 1992

물-아세틸아세톤 용매계에서 과염소산나트륨과 과염소산구리의 표준이동 자유에너지는 갈바니전지의 기전력을 측정하여 구하였으며, 이 용매계에서 나트륨이온과 구리이온의 표준이동 자유에너지는 extrathermodynamic procedure로서 테트라페닐붕산 테트라부틸암모늄 가정을 써서 계산하였다. 물로부터 아세틸아세톤 용매로 나트륨이온과 구리이온이 이동할 때의 표준자유에너지값은 25${\circ}C$에서 각각 5.09 및 4.16 kcal/mol이었다. 이 값은 아세틸아세톤이 물보다 나트륨이온과 구리이온에 대하여 약한 donor solvent임을 뜻한다. 물로부터 소량의 아세틸아세톤을 포함하는 혼합용매로 구리이온이 이동할 때의 표준자유에너지값은 이상하게 (-)값을 나타내는데, 이것은 아세틸아세톤이 구리이온과 반응하여 킬레이트를 생성하는 효과 때문이다.

• Bulletin of the Korean Chemical Society
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• 제24권9호
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• pp.1293-1302
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• 2003

Rate constants at various temperatures and activation parameters are reported for solvolyses of acyl chlorides (RCOCl), with R = Me, Et, i-Pr, t-Bu, cyclopentylmethyl, benzyl, thiophenylmethyl, 2-phenylethyl, diphenylmethyl, and phenylthiomethyl in 100% ethanol, 100% 2,2,2-trifluoroethanol (TFE), 80% v/v ethanol/ water and 97% w/w TFE/water. Additional rate constants for solvolyses with R = Me, t-Bu, and $PhCH_2$ are reported for TFE/water and TFE/ethanol mixtures, and for solvolyses with R = t-Bu, and PhCH2 are reported for 1,1,1,3,3,3-hexafluoropropan-2-ol/water mixtures, as well as selected kinetic solvent isotope effects (MeOH/MeOD and TFE). Taft plots show that electron withdrawing groups (EWG) decrease reactivity significantly in TFE, but increase reactivity slightly in ethanol. Correlation of solvent effects using the extended Grunwald-Winstein (GW) equation shows an increasing sensitivity to solvent nucleophilicity for EWG. The effect of solvent stoichiometry in assumed third order reactions is evaluated for TFE/ethanol mixtures, which do not fit well in GW plots for R = Me, and t-Bu, and it is proposed that one molecule of TFE may have a specific role as electrophile; in contrast, reactions of substrates containing an EWG can be explained by third order reactions in which one molecule of solvent (ethanol or TFE) acts as a nucleophile, and a molecule of ethanol acts as a general base catalyst. Isokinetic relationships are also investigated.

• 대한화학회지
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• 제30권4호
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• pp.352-358
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• 1986

페놀류의 머무름 거동에 대한 실험적 관찰을 이성분용매인 MeOH-Water, ACN-Water, THF-Water와 삼성분용매인 MeOH-Water, ACN-Water, THF-Water계에서 수행했다. 이 머무름 거동의 데이타들로써 용매의 성분비에 따른 크기인자를 예측할 수 있는 선형방정식을 얻었다. 또 페놀류의 최적 분리에 적합한 MeOH-Water이성분 용매를 기준하여 이론적으로 용매세기가 같은 이성분과 삼성분용매를 사용했고 이 등용매세기하에서 시료에 대한 머무름 거동의 특이성 효과는 이성분용매계가 삼성분용매계보다 더 크게 나타났다.