• Title/Summary/Keyword: solvent effect

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Screening of the Physiological Activity of Solvent Extracts of Paulownia coreana Bark and Antioxidative Effect of the Extracts on an Edible Oil

  • Lee, Nam Gull;Jeong, Kap Seop
    • Journal of Environmental Science International
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    • v.22 no.10
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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.

Rate and Product Studies of 1-Adamantylmethyl Haloformates Under Solvolytic Conditions

  • Park, Kyoung-Ho;Lee, Yelin;Lee, Yong-Woo;Kyong, Jin Burm;Kevill, Dennis N.
    • Bulletin of the Korean Chemical Society
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    • v.33 no.11
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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.

Separation of Light Rare Earth Elements by Solvent Extraction with a Mixture of Cationic and Tertiary Amine (양이온 추출제와 아민의 혼합추출제에 의한 경희토류금속의 분리)

  • Lee, Man-Seung;Son, Seong Ho
    • Resources Recycling
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    • v.26 no.2
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    • pp.3-10
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    • 2017
  • Rare earth elements with high purity are demanded for the manufacture of advanced materials. Light rare earth elements are contained in domestic monazite and Ni-MH batteries. In this paper, solvent extraction to separate the light rare earth elements from hydrochloric acid leaching solutions of these resources was discussed. A mixture of cationic and tertiary amine shows synergistic effect on the extraction of LREEs and the extent of pH decrease during extraction is reduced. The effect of solution pH on the extraction and synergism was reviewed. Acquisition of the operation data with mixer-settler on the separation of LREEs by this mixture is necessary to develop a process.

Kinetic and Thermodynamic Analysis of AChE Inhibition of Solvent Extract Fractions from Inonotus obliquus (차가버섯 용매추출분획의 Acetylcholinesterase 저해활성에 대한 동역학 및 열역학적 해석)

  • Kim, Hak-Kyu;Hur, Won;Hong, Eok Kee;Lee, Shin-Young
    • Food Engineering Progress
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    • v.15 no.4
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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.

The Effect of Solvent on Reactions of p-Nitrophenyl Acetate with Alicyclic Secondary Amines and with Anionic Nucleophiles in MeCN-H₂O Mixtures of Varying Compositions

  • 엄익환;신은희;권동숙
    • Bulletin of the Korean Chemical Society
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    • v.17 no.3
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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.

Initial State and Transition State Solvation for the Solvolysis of trans-$[Co(N-eten)_2Cl_2]$+ in Binary Aqueous Mixtures: Excess Free Energy, Free Energy Cycle and Reacton Mechanism

  • Park, Yu-Chul;Cho, Young-Je
    • Bulletin of the Korean Chemical Society
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    • v.11 no.4
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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.

Effect of Solvent Annealing on the Characteristics of PEDOT:PSS as a Ammonia Gas Sensor Film (용매열처리에 따른 PEDOT:PSS 암모니아 가스 감지막 특성 변화)

  • Noh, Wang Gyu;Yeom, Se-Hyuk;Lee, Wanghoon;Shin, Han Jae;Kye, Ji Won;Kwak, Giseop;Kim, Se Hyun;Ryu, Si Ok;Han, Dong Cheul
    • Journal of Sensor Science and Technology
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    • v.26 no.2
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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.

Standard Transfer Free Energy of Sodium and Cupric Ions in Water-Acetylacetone Solvent System (물-아세틸아세톤 용매계에서 나트륨이온과 구리이온의 표준이동 자유에너지)

  • Lee Heung Lark;Park Jong-Taek
    • Journal of the Korean Chemical Society
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    • v.36 no.5
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    • pp.632-637
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    • 1992
  • Standard transfer free energies of sodium and cupric perchlorates in water-acetylacetone solvent system have been determined by electromotive force measurements of galvanic cell and these energies of sodium and cupric ions in this solvent system have been evaluated by the tetrabutylammonium tetraphenylborate assumption as the extrathermodynamic procedure. Standard transfer free energy values of sodium and cupric ions from water to acetylacetone solvent were 5.09 and 4.16 kcal/mol at 25${\circ}C$, respectively. These values mean that acetylacetone is much weaker donor solvent to sodium and cupric ions than water. The standard transfer free energy value of cupric ion from water to mixture solvents which contain small amount of acetylacetone is changed by an unusual form. This is because of the chelate formation effect of acetylacetone to cupric ion.

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Applications of Third Order Models in Solvolytic Reaction of Aliphatic Substituted Acyl Derivatives in 2,2,2-Trifluoroethanol-Ethanol Systems

  • Ryu, Zoon-Ha;Lim, Gui-Taek;Bentley, T. William
    • Bulletin of the Korean Chemical Society
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    • v.24 no.9
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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.

Retention Behavior of the Phenols on the Binary and Ternary Mobile Phases in Reversed-Phase Liquid Chromatography (역상 액체크로마토그래피에 있어서 이성분과 삼성분 이동상에 대한 페놀류의 머무름 거동)

  • Dae Sub Oh;Sun Haing Lee;Soo Han Kim;Sang Tae Kim
    • Journal of the Korean Chemical Society
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    • v.30 no.4
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    • pp.352-358
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    • 1986
  • An extensive experimental survey on the retention behaviors of phenols in the binary solvent system such as methanol-water, acetonitrile-water and tetrahydrofuran-water as well as the ternary solvent system such as methanol-acetonitrile-water and methanol-tetrahydrofuran-water is presented. A linear equation, which describes the capacity factor as a function of the solvent composition in the mobile phase and is able to predict the retention behaviors of phenols, was obtained. The iso-eluotropic lines for the binary and ternary solvent system are based on the equal strength of the methanol-water solvent which shows an optimum separation of the phenols used. The specific effect of each solute in the binary solvent system appeared to be larger than those in the ternary system.

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