• Bulletin of the Korean Chemical Society
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• 제34권8호
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• pp.2251-2255
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• 2013

Second-order rate constants ($k_{HOO^-}$) for the nucleophilic substitution reactions of Y-substituted-phenyl diphenylphosphinates (4a-4i) with $HOO^-$ in $H_2O$ have been measured spectrophotometrically. The ${\alpha}$-nucleophile $HOO^-$ is 10-70 times more reactive than the reference nucleophile $OH^-$ although the former is ca. $4pK_a$ units less basic than the latter, indicating the ${\alpha}$-effect is operative. The Bronsted-type plot for the reactions of 4a-4i with $HOO^-$ is linear with ${\beta}_{lg}=-0.51$, a typical ${\beta}_{lg}$ value for reactions which were reported to proceed through a concerted mechanism. The Yukawa-Tsuno plot is also linear with ${\rho}=1.40$ and r = 0.47, indicating that a negative charge develops partially on the O atom of the leaving group, which can be delocalized to the substituent Y through resonance interactions. Thus, the reactions have been proposed to proceed through a concerted mechanism. The magnitude of the ${\alpha}$-effect (i.e., the $k_{HOO^-}/k_{HO^-}$ ratio) decreases linearly as the leaving-group basicity increases. It has been concluded that solvation effect is not solely responsible for the ${\alpha}$-effect found in this study but the transition-state stabilization through an intramolecular H-bonding interaction is also responsible for the ${\alpha}$-effect.

• Tribology and Lubricants
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• 제17권2호
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• pp.146-152
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• 2001

Environmentally adapted synthetic base oils of polyalkylene glycols (PAGs) and polyol esters (POEs) show a high polarity because of their functional groups containing oxygen atom. The lubricating performance of these polar base oils was investigated by using a four-ball tribometer under boundary lubrication condition. Four polyalkylene glycols and five polyol ester base oils were used as sample base oils of high polarity. A mineral oil (MO) and alkylnaphthalene (AN) were used as low polarity base oils. Tricrecylphosphate (TCP) was added to all the base oils, in the range of 10 mmol/L-2000 mmol/L, as an antiwear additive. All the TCP-for-mutated base oils showed optimum concentration characteristics for minimizing wear. The order of optimum concentration of all the base oils was in a good accordance with the order of relative stability of TCP in base oils. The interaction model on solvation between additive and different polar base oils can expect the stability order of TCP. Thus, the model on solvation can explain well the order of optimum concentration of all the base oils, by using the effect of polarity (dielectric constant, $\varepsilon$) and molecular size (molecular weight, MW) of them on stability of TCP in polar base oils. Finally, a good correlation of the optimum concentration for all the base oils was obtained when it was arranged as a function of C∝(M $W_{Base Oil}$/M $W_{TCP}$)$^{-2}$.71/.($\varepsilon$$_{Base Oil}$)$^{3.38}$ by these two parameters.s..

• 한국생물공학회:학술대회논문집
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• 한국생물공학회 2001년도 추계학술발표대회
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• pp.886-889
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• 2001

C-terminus specific immobilization often results in a increased structural stability resistant to various denaturation factors. In order to elucidate the immobilization effect on the c-terminus in molecular level, we made over 200 protein data set from Protein Data Bank(PDB), analyzed c-terminus structure of each protein, and investigated the structural relationship with the stabilizing factors such as hydrogen bond, ion pairs, cation pi, disulfide bond, solvation free energy, surface area, flexibility and so on.

• 한국수소및신에너지학회논문집
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• 제24권2호
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• pp.172-178
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• 2013

This study examined the electrochemical deposition and dissolution of lithium on nickel electrodes in 1 mol $dm^{-3}$ (M) $LiPF_6$ dissolved in propylene carbonate (PC) containing different 1,2-dimethoxyethane (DME) concentrations as a co-solvent. The DME concentration was found to have a significant effect on the reactions occurring at the electrode. The poor cycleability of the electrodes in the pure PC solution was improved considerably by adding small amounts of DME. This results suggested that the dendritic lithium growth could be suppressed by using co-solvents. After hundredth cycling in the 1 M $LiPF_6$/PC:DME (67:33) solution, almost no dead lithium has been found from the disassembled cell, resulting from suppression of dendritic lithium growth. Scanning electron microscopy revealed that dendritic lithium formation was greatly affected by the ratio of DME. Raman spectroscopy results suggested that the structure of solvated lithium ions is a crucial important factor in suppressing dendritic lithium formation.

• 대한화학회지
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• 제28권4호
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• pp.210-216
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• 1984

MeOH-MeCN 혼합용매의 Taft용매 파라미터인 ${\pi}^{\ast}$(용매의 polarity-polarizability), ${\alpha}$(용매의 수소결합 주게 산도) 그리고 ${\beta}$(용매의 수소결합 받게 염기도)를 여러 지시약을 사용하여 분광용매화 비교법으로 구하였다. 또한 Swain의 용매 파라미터인 A(음이온을 용매화 시키는 척도)와 B(양이온을 용매화 시키는 척도)를 반응속도 자료를 이용하여 최소 자승법으로 구하였다. 용매 상수 ${\beta}$는 용매의 염기도에 의존하며 혼합용매의 MeOH 함량이 증가할 수록 $(MeOH)_n$의 기여에 의해 증가하는 것을 알 수 있었다. ${\pi}^*$는 용매의 쌍극자 모멘트에 의존하며 혼합용매의 MeCN 함량이 증가할 수록 ${\pi}^{\ast}$값도 커지며 ${\alpha}$는 MeOH의 수소결합주게 효과에 의해 혼합용매의 MeOH함량이 증가할 수록 크게 증가하는 것을 나타냈다. 앞서 보고된 반응들에 용매 파라미터를 적용하여 반응상수를 구하였으며 Taft의 반응상수 a, s와 Swain의 반응상수 a, b사이에는 용매 척도의 차이 때문에 서로 연관성이 없었다. 그러나 그들의 비인 a/s와 a/b는 서로 좋은 직선관계를 보여 주었으며 이들 반응상수 비를 이용하여 반응 메카니즘이나 치환기 변화 및 이탈기 변화에 미치는 용매효과를 논의 하였다.

• Bulletin of the Korean Chemical Society
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• 제13권6호
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• pp.642-647
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• 1992

Second-order rate constants have been measured spectrophotometrically for the reactions of substituted phenyl acetates with butane-2,3-dione monoximate and p-chlorophenoxide anions in MeCN-H$_2$O mixtures of varying compositions. The reaction rate, unexpectedly, decreased remarkably upon initial additions of MeCN to H$_2$O up to 30-40 mole ${\%}$ MeCN, and followed by a gradual increase upon further additions of MeCN. The change in solvent composition also influenced the magnitude of the ${\alpha}$-effect, i.e., the ${\alpha}$-effect increased as the mole ${\%}$ MeCN increased. The solvent dependent ${\alpha}$-effect for the present system appears to indicate that the differential solvation between the ${\alpha}$-effect nucleophile and the corresponding normal nucleophile is not solely responsible but the difference in the transition-state stabilization is also responsible for the ${\alpha}$ -effect in organic solvent-rich region.

• International Journal of Industrial Entomology and Biomaterials
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• 제27권2호
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• pp.326-328
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• 2013

Sericin undergoes gelation by the structural transition from random coil to b-sheet transition. In the present study, the gelation time of sericin solution was investigated in the presence of NaCl, KCl and $CaCl_2$. The addition of salts delayed the gelation time, and $CaCl_2$ had the most pronounced effect, which delayed about 8 h at maximum. The gelation time increased with the concentration of salt. The transition of secondary structure of sericin was retarded in the presence of salt. The effect of salts on the gelation time of sericin might be due to the solvation effect of relevant cation.

• Bulletin of the Korean Chemical Society
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• 제13권5호
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• pp.486-491
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• 1992

The rate constants for the reactions of p-nitrophenyl acetate with 6 different aryloxides and 2 benzohydroxamates have been measured spectrophotometrically in water containing various concentrations of cetyltrimethylammonium bromide (CTAB). The reactivity of the nucleophiles has been demonstrated to be significantly enhanced as the concentration of the surfactant increases up to a certain point. When the basicities of the aryloxides are comparable, the rate enhancement is more prominent for the aryloxide having larger binding constant to the micellar aggregate. Benzohydroxamates exhibitis significantly large ${\alpha}$-effect in the absence of the surfactant, although, the ${\alpha}$-effect nucleophiles are considered to be more solvated in water than the corresponding normal nucleophile. Thus, the solvation effect does not appear to be solely responsible for the ${\alpha}$-effect. Interestingly, the large ${\alpha}$-effect disappears in the presence of the surfactant. Therefore, one might attribute the disappearance of the ${\alpha}$-effect to solvent effect. However, a structural change of the reactive ${\alpha}$ -effect nucleophile into unreactive ones would also be considered to be responsible for the absence of the ${\alpha}$-effect in the present system.

• 공업화학
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• 제5권1호
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• pp.121-126
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• 1994

초산의 반응추출에 미치는 영향을 규명하기 위하여 추출제로 2급과 3급 아민 및 용매화 추출제, 용매로 n-butylacetate, modifier로 4-nonylphenol, TBP 및 isodecanol을 이용하였다. 그외에 수용액상의 pH와 온도의 영향을 연구하였다. 실험결과 초산의 추출에서 3급 아민인 tril-n-octyl과 tri-n-decylamine의 50% 혼합 추출제인 MODA가 추출도 및 선택도에서 가장 좋았다. Modifier로서는 4-nonylphenol이 우수하였다. 이외에도 수용액의 pH와 추출계의 온도가 낮을수록 추출도가 높았다.

• Bulletin of the Korean Chemical Society
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• 제22권8호
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• pp.877-882
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• 2001

The solvent effects on the relative free energies of Eu3+ to Yb3+ ion mutation in solution have been investigated using a Monte Carlo simulation of statistical perturbation theory (SPT). Our results agree well with available data that were obtained by others. Particularly, the results of water (SPC/E) solvent are almost identical with experimental data. For the present Eu3+ and Yb3+ ions, the relative free energies of solvation vs. Born’s function of bulk solvents decrease with increasing Born’s function of bulk solvents. There is also good agreement between the calculated structural properties in this study and the published works obtained by computer simulation and experimental work.