• Journal of the Korean Chemical Society
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• v.34 no.2
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• pp.123-129
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• 1990

The rate constants for the solvolysis of $trans-[Cr(en)_2Br_2]^+$ ion were determined by the spectrophotometric method in methanol-, ethanol-, acetone-, and acetonitrile-water mixtures, at 20, 25, 30, and 35$^{\circ}C$, respectively. The rate constants increased with increasing co-solvent compositions. The rate constant did not show any relation with the reciprocal of dielectric constant of the solvent-mixtures. The m values of Grunwald-Winstein equation for methanol-, ethanol-, acetonitrile-, and acetone-water mixtures are 0.109, 0.103, 0.101, and 0.095, respectively. A free energy cycle for the process from the initial state to the transition state in water and water + co-solvent mixtures shows that the change in solvation at the transition state has a dominant effect on the rate. From the above results, it is believed that the mechanism for the aquation of this complex is the Id mechanism.

• Journal of Environmental Science International
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• v.14 no.2
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• pp.241-249
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• 2005

This study deals with micellar effects on dephosphorylation of diphenyl-4- nitrophenylphosphate (DPNPPH), diphenyl-4-nitrophenylphosphinate (DPNPlN) and isopropylphenyl-4-nitrophenyl phosphinate (IPNPlN) mediated by $OH^\Theta$ or o-iodosobenzoate ion $(IB^\Theta)$ in aqueous and CTAX solutions. Dephosphorylation of DPNPPH, DPNPIN and IPNPIN mediated by $OH^\Theta$ or o-iodosobenzoate ion $(IB^\Theta)$ is relatively slow in aqueous solution. The reactions in CTAX micellar solutions are, however, much accelerated because CTAX micelles can accommodate both reactants in their Stem layer in which they can easily react, while hydrophilic $OH^\Theta\;(or\;IB^\Theta)$ and hydrophobic substrates are not mixed in water. Even though the concentrations $(>10^{-3}\;M)\;of\;OH^\Theta\;(or\;IB^\Theta)$ in CTAX solutions are much larger amounts than those $(6\times10^{-6}\;M)$ of substrates, the rate constants of the dephosphorylations are largely influenced by the change of concentration of the ions, which means that the reactions are not followed by the pseudo first order kinetics. In comparison to effect of the counter ions of CTAX in the reactions, CTACI is more effective on the dephosphorylation of substrates than CTABr due to easier expelling of $Cl^\Theta$ ion by $OH^\Theta\;(or\;IB^\Theta)$ ion from the micelle, because of easier solvation of $Cl^\Theta$ ion by water molecules. The reactivity of IPNPlN with $OH^\Theta\;(or\;IB^\Theta)$ is lower than that of DPNPlN. The reason seems that the 'bulky' isopropyl group of IPNPIN hinders the attack of the nucleophiles.

• Bulletin of the Korean Chemical Society
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• v.35 no.1
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• pp.51-56
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• 2014

The solvolysis rate constants of 2,4-dimethoxybenzenesulfonyl chloride (1) in 30 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale and $Y_{Cl}$ solvent ionizing scale, with sensitivity values of $0.93{\pm}0.14$ and $0.65{\pm}0.06$ for l and m, respectively. These l and m values can be considered to support a $S_N2$ reaction pathway. The activation enthalpies (${\Delta}H^{\neq}$) were 12.4 to $14.6kcal{\cdot}mol^{-1}$ and the activation entropies (${\Delta}S^{\neq}$) were -15.5 to -$32.3kcal{\cdot}mol^{-1}{\cdot}K^{-1}$, which is consistent with the proposed bimolecular reaction mechanism. The solvent kinetic isotope effects (SKIE) were 1.74 to 1.86, which is also in accord with the $S_N2$ mechanism and was possibly assisted using a general-base catalysis. The values of product selectivity (S) for solvolyses of 1 in alcohol/water mixtures was 0.57 to 6.5, which is also consistent with the proposed bimolecular reaction mechanism. Third-order rate constants, $k_{ww}$ and $k_{aa}$, were calculated from the rate constants ($k_{obs}$), together with $k_{aw}$ and $k_{wa}$ calculated from the intercept and slope of the plot of 1/S vs. [water]/[alcohol]. The calculated rate constants, $k_{calc}$ ($k_{ww}$, $k_{aw}$, $k_{wa}$ and $k_{aa}$), are in satisfactory agreement with the experimental values, supporting the stoichiometric solvation effect analysis.

• Journal of the Korean Chemical Society
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• v.7 no.3
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• pp.216-224
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• 1963

Reaction of organic chlorine containing ester, alcohol, and acids with metallic tin and zinc in dimethyl formamide solvent gave a good yield of organo metallic complex. The same reaction under a mixed U.V. irradiation could not give an appreciable yield of the complex except in the case of an elevated reaction temperature. The solvation effect of dimethyl formamide of the metallic complex formation was markedetly increased as compared to the reaction in toluene and cyclohexane. In case of chlorine containing carboxylic acid, the formation of organo chloro zinc complex of the salt was observed. The reaction of organo zinc complex with a carbonyl precursor gave the addition product together with a dimerized product. Especially the aldehyde species enhanced the formation of zinc complex. The addition reaction was simple and convenient, but the yield was not high.(30-40% for the acid, 73% for the ester, 14.6% for alcohol). The result was discussed on basis of solvent effect and the procedures were described.

• Bulletin of the Korean Chemical Society
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• v.27 no.12
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• pp.2011-2018
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• 2006

We have investigated the solvent effects on $\Delta log\;K_s $(the difference of stability constant of binding) and the different free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6, i.e., the selectivity of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6 using a Monte Carlo simulation of statistical perturbation theory (SPT) in diverse solvents. The stability constant ($\Delta log\;K_s $) of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6, in $CH_3OH$ was calculated in this study as -1.06 agrees well with the different experimental results of -0.44~-0.6, respectively. We have reported here the quantitative solvent-polarity relationships (QSPR) studied on the solvent effects the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6. From the calculated coefficients of QSPR, we have noted that solvent polarity (ET) and Kamlet -Tafts solvatochromic parameters (b ) dominate the differences in relative solvation Gibbs free energies of $Nd^{3+}$ and $Eu^{3+}$ ions but basicity (Bj) dominates the negative values in differences in the stability constant ($\Delta log\;K_s $) as well as the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6 and acidity (Aj) dominates the positive values in differences in the stability constant ($\Delta log\;K_s $) as well as the relative free energies of binding of $Nd^{3+}$ and $Eu^{3+}$ ions to 18-crown-6.

• Journal of Photoscience
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• v.9 no.2
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• pp.122-125
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• 2002

Coherent oscillations in is fluorescence dynamics of W.-t. PYP and its site-directed mutants have been observed. Two oscillatory modes coupled with the ultrafast fluorescence due to the twisting of the excited chromophore were identified, a high ftequency mode (∼135 cm$\^$-1/) with ∼550 is damping time and a low frequency overdamped mode (-45 cm$\^$-1/) with ∼250 is damping time, respectively. Both modes disappear in the fluorescence dynamics of denatured PYP emphasizing the important role of the protein nanospace as the environment for photoreaction. The qualitative picture of fluorescence dynamics in site-directed mutants was rather similar to that in W.-t. PYP, i.e., similar oscillatory modes (∼130-140 cm$\^$-1/ and ∼40-70 cm$\^$-1/) have been observed. This indicates that the vibrational modes and electron-vibration couplings do not change dramatically due to the mutation though the damping time of low frequency mode a little decreases as the protein nanospace structure becomes looser and more disordered by mutation. On the other hand, in the case of some PYP analogues, the qualitative picture of fluorescence dynamics changes, showing the familiar picture of solvation effect whereas the oscillations are almost damped. Comparative analyses of these observations are presented.

• Journal of the Korean Chemical Society
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• v.50 no.6
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• pp.440-446
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• 2006

ZnO nanoparticles were prepared by laser ablation of the ZnO powder dispersed in deionized water and surfactant solutions, and characterized using UV-VIS absorption spectroscopy, X-ray diffractometer and Transmission electron microscopy(TEM). ZnO nanoparticles produced show the pure ZnO crystal state without mixed state with Zn(OH)2 or Zn, and have the band gap energy of 3.35 eV, which is comparable to that of bulk ZnO. While ZnO nanoparticles prepared in SDS solution have the average diameter of 28nm with near spherical shape, those prepared in CTAB solution have the average size of 40 nm with mainly rod-like shape. ZnO colloidal solution of CTAB is more stable than that of SDS. These difference according to surfactants can be explained by difference of electrostatic interaction between surface charge of ZnO and surfactant molecules and by solvation effect in solution.

• Bulletin of the Korean Chemical Society
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• v.29 no.7
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• pp.1335-1343
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• 2008

Theoretical studies on the un-catalyzed and catalyzed aminations of ketene with $NH_3$ and $(NH_3)_2$, respectively, were studied using MP2 and hybrid density functional theory of B3LYP at the 6-31+G(d,p) and 6- 311+G(3df,2p) basis sets in the gas phase and in benzene and acetonitrile solvents. In the gas phase reaction, the un-catalyzed mechanism was the same as those previously reported by others. The catalyzed mechanism, however, was more complicated than expected requiring three transition states for the complete description of the C=O addition pathways. In the un-catalyzed amination, rate determining step was the breakdown of enol amide but in the catalyzed reaction, it was changed to the formation of enol amide, which was contradictory to the previous findings. Starting from the gas-phase structures, all structures were re-optimized using the CPCM method in solvent medium. In a high dielectric medium, acetonitrile, a zwitterions formed from the reaction of $CH_2$=C=O with $(NH_3)_2$, I(d), exists as a genuine minimum but other zwitterions, I(m) in acetonitrile and I(d) in benzene become unstable when ZPE corrected energies are used. Structural and energetic changes induced by solvation were considered in detail. Lowering of the activation energy by introducing additional $NH_3$ molecule amounted to ca. −20 $\sim$ −25 kcal/mol, which made catalyzed reaction more facile than un-catalyzed one.

• Journal of the Korean Chemical Society
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• v.40 no.5
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• pp.327-332
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• 1996

The rates of solvolylsis of methyl chloroformate, phenyl chloroformate and 1-adamantyl derivatives in binary solvent mixtures have been measured by conductometric method at various temperatures and pressures. The activation parameters were estimated from the rate constants. The activation volume (${\Delta}V_o^{\neq}$) and the activation entropy (${\Delta}S^{\neq}$) are both negative, but the activation enthalpy (${\Delta}H^{\neq}$) is positive. This behavior is discussed in terms of electrostriction of solvation. The reactivities of these reactions were also estimated from the correlation of the activation volumes with the activation entropies. From these results, it could be estimated that the solvolyses of 1-adamantyl fluoroformate (in aqueous TFE) and 1-adamantyl tosylate have pathway involving unimolecular reaction, while the reaction of methyl chloroformate, phenyl chloroformate and 1-adamantyl fluoroformate (in aqueous alcohol) proceed through a bimolecular reaction.

• Journal of the Korean Chemical Society
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• v.39 no.6
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• pp.440-445
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• 1995

The chemical compositions and stability constants, thermodynamic parameters for the neodymium(Ⅲ) complexes of substituted benzo-1,4,7,10,13-pentaoxacyclopentadecane(B15C5) have been determined by spectrophotometry and conductometry in methanol solution at various temperatures. As substituents, CH3, Br, CHO, NO2, and 3,4-(NO2)2 were used. In methanol solution the ratios of neodymium(Ⅲ) to the ligands in the complexes are 1 : 1. The stability constants were increased in order of B15C5-3,4-(NO2)2 < B15C5-NO2 < B15C5-CHO < B15C5-Br < B15C5 < B15C5-CH3. This observation can be explained in terms of the substituent effect. The order of stability constants was dimethylsulfoxide < acetone < acetonitrile in solution and the magnitudes were found to be inversely proportional to the solvents donicities. These results could be understood in terms of solvent basicity, ligand basicity, solvation of the cation, and entropy changes of complex formation.