• Bulletin of the Korean Chemical Society
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• v.29 no.2
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• pp.431-437
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• 2008

The solvent effects on the relative free energies of binding of K+ and Na+ ions to 12-crown-4 and Dlog Ks (the difference of stability constant of binding) have been investigated by a Monte Carlo simulation of statistical perturbation theory (SPT) in several solvents. Comparing the relative free energies of binding of K+ and Na+ ions to 12-crown-4, in CH3OH of this study with experimental works, there is a good agreement among the studies. We have reported here the quantitative solvent-polarity relationships (QSPR) studied on the solvent effects the relative free energies of binding of K+ and Na+ ions to 12-crown-4. We noted that DN(donor number) dominates the differences in relative solvation Gibbs free energies of K+ and Na+ ions and DN dominates the negative values in differences in the stability constant (Dlog Ks) as well as the relative free energies of binding of K+ and Na+ ions to 12-crown-4 and p* (Kamlet-Tafts solvatochromic parameters) dominates the positive values in differences in the stability constant (Dlog Ks) as well as the relative free energies of binding of K+ and Na+ ions to 12-crown-4.

• Journal of the Korean Chemical Society
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• v.29 no.1
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• pp.45-51
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• 1985

Rate constants and activation parameters for the methanolysis of t-butyl halide (t-BuCl, t-BuBr, t-BuI) in various MeOH-DMSO mixtures were measured by conductometric method. Taft's solvatochromic parameters, such as polarity-polarizability(SPP's), ${\pi}^{\ast}$, hydrogen bond donor (HBD) acidity, ${\alpha}$, and hydrogen bond acceptor (HBA) basicity, ${\beta}$ of the solvents, were determined by the so called solvatochromic method using five indicators. The variation of methanolysis rate with the solvent composition was discussed on the basis of the activation parameters and the correlation of the rates with the solvatochromic parameters. It is concluded that the polarity-polarizability, HBD acidity and HBA basicity of the mixtures had an effect on the ionization of t-butyl halide cooperatively, also that the specific interaction between the leaving groups and the solvents, such as ion-dipole and hydrogen bond acceptor-donor interaction, is the most important factor of solvent effects on the stabilization of transition states.

• Journal of the Korean Chemical Society
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• v.15 no.5
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• pp.219-222
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• 1971

The kinetics of the solvolysis of benzyl and p-or m-substituted benzyl bromides in various alcohols have been determined by an electric conductivity method. From these reactions, a curved Hammett plot is obtained and a mechanism is proposed to account for the nonlinear behavior observed. In addition, effects of solvent polarity on the activation parameters for the solvolysis of benzyl bromides are discussed.

• Textile Coloration and Finishing
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• v.9 no.5
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• pp.10-18
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• 1997

In order to study the properties of safflower yellow colors, thermodynamic parameters and dyeing properties on the silk in several dyeing conditions were investigated. The uv-visible spectra of safflower yellow colors in several solvents show hypsochromic shift with the polarity of solvent but bathochromic shift with increasing acidity of solution. The apparent diffusion coefficients and standard affinities of dyeing increased with the increase of dyeing temperature. The standard heat of dyeing(${\Delta}H^0$), entropy change(${\Delta}S^0$) and activation energy($E_{act}$) were calculated to be - 1.144kcal/mol, -7.498(5$0^{\circ}C$)~-3.804(9$0^{\circ}C$)cal/molㆍdeg and 0.123kcal/mol, respectively. The concentration of safflower yellow colors in the silk fiber increased with dyeing temperature, time, concentration of colors and acidity of initial dyebath. Silk fabrics were dyed bright yellow by pre-mordanting with tin chloride. Lightfastness of silk fabrics pre-mordanted by tin chloride was not excellent.

• Archives of Pharmacal Research
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• v.20 no.1
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• pp.1-6
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• 1997

We determined the microviscosity of synaptosomal plasma membrane vesicles (SPMV) isolated from bovine cerebral cortex and liposomes of total lipids (SPMTL) and phospholipids (SPMPL) extracted from SPMV. Changes in the microviscosity induced by the range and rate of lateral diffusion were measured by the intramolecular excimerization of 1, 3-di(1-pyrenyl)propane (Py-3-Py). The microviscosity values of the direct probe environment in SPMV, SPMTL and SPMPL were 38.17, 31.11 and 27.64 cP, respectively, at$37^{\circ}C$and the activation energies $(E_a)$ of the excimer formation of Py-3-Py in SPMV, SPMTL and SPMPL were 8.236, 7.448 amd 7.025 kcal/mol, respectively. Probe location was measured by polarity and polarizability parameters of the probe Py-3-Py and probe analogues, pyrene, 1-pyrenenonanol and 1-pyrenemethyl-3${\beta}$-hydroxy-22, 23-bisnor-5-cholenate (PMC), incorporated into membranes or solubilized in reference solvents. There existed a good linear relationship between the first absorption peak of the $^1_a$ band and the polarizability parameter $(n^{2}-1)/(2n^{2}+1)$.The calculated refractive index values for SPMV, SPMTL and SPMPL were close to 1.50, which is higher than that of liquid paraffin (n=l.475). The probe location was also determined by using a polarity parameter $(f-1/2f^{I})$. Here f=$({\varepsilon}-1)/(2{\varepsilon}+1)$ is the dielectric constant function and $f^I=(n^2-1)/(2n^2+1)$ is the refractive index function. A correlation existed between the monomer fluorescence intensity ratio and the solvent polarity parameter. The probes incorporated in SPMV, SPMTL, and SPMPL report a polarity value close to that of 1-hexanol $({\varepsilon}=13.29)$. In conclusion, Py-3-Py is located completely inside the membrane, not in the very hydrophobic core, but displaced toward the polar head groups of phospholipid molecules, e.g., central methylene region of aliphatic chains of phospholipid molecules.

• Analytical Science and Technology
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• v.18 no.3
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• pp.194-200
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• 2005

The N hyperfine coupling constants ($a_N$) of di-t-butyl nitroxide (DTBN) radicals in water-solvent system were measured with EPR spectroscopy. Various kinds of the solvents with different polarity such as acetone, dimethylsulfoxide (DMSO), methanol, ethanol and 1-propanol were applied and studied. Equilibrium constants for the solvation equilibrium and the solvent parameters ($E_T$, molar transition energy) of various water-solvent system were obtained from the experimental results and are presented. The $a_N$ values were plotted as a function of mole fraction of the solvent. In case of water-DMSO, water-ethanol and water-1-propanol system, slight negative deviations from the straight line were observed. In water-acetone system, the absorption wavelength (${\lambda}$) due to ${\eta}{\rightarrow}{\pi}^{\ast}$ transition increased linearly with the increase of mole fraction of acetone. The relationship between $a_N$ of DTBN and ${\lambda}$ due to ${\eta}{\rightarrow}{\pi}^{\ast}$ transition in water-acetone and water-DMSO system was examined. It was found that the electronic structure of the nitroxide radicals is stablized from the fact that the N hyperfine coupling constants of DTBN radicals are greatly unaffected in the environment of water-solvent system.

• Journal of the Korean Chemical Society
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• v.30 no.3
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• pp.265-272
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• 1986

Kinetic studies for the methanolysis of tert-butyl halides (t-BuCl, t-BuBr, t-BuI) were carried out in MeOH-1,1,2,2-tetrachloroethane mixtures. The solvatochromic comparison method was used with six indicators to analyze solvent effects on the ionizations of tert-butyl halides. It was shown that the cooperative effect of solvent polarity-polarizability was the most important factor influenced on the methanolysis rates of tert-butyl halides, but the electrophilic assistance for halide leaving group and the nucleophilic assistance for tert-butylium ion were considerably influential, too. And it was found that the electrophilic assistance caused by hydrogen bonding and the nucleophilic assistance for carbon center were stronger for more basic leaving group ($I^-) and more polarizable leaving group(t-BuCl

• Journal of the Korean Chemical Society
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• v.36 no.2
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• pp.174-179
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• 1992

Reaction of aniline and iodine in$CHCl_3,\;CH_2Cl_2 : CHCl_3$(1 : 1), and $CH_2Cl_2$ has been studied kinetically by using conductivity method, Pseudo first-order rate constants ($k_{obs}$) and second-order rate constants ($k_{obs}$/[aniline]) are dependent on the aniline concentration. Second-order rate constants obtained were increased with increasing aniline concentration. We analysed these results on the basis of formation of charge transfer complex as reaction intermediate. From the construction of react ion scheme and derivation of rate equation, we calculated equilibrium constants and activation parameters for the formation and transformation of charge transfer complex. The equilibrium constants were decreased by an increase in the dielectric constant of the solvent and the value is 1.7-3.7$M^{-1}$. The rate of transformation are markedly affected by the solvent polarity. ${\Delta}H^{\neq}$ is about 14.2kJ/mol, and ${\Delta}S^{\neq}$ is large negative value of -243J/mol K.

• Applied Chemistry for Engineering
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• v.16 no.4
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• pp.581-587
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• 2005

In order to obtain a highly purified p-dioxanone (PDX) as monomer of biodegradable polymer, suitable solvent must be selected. The selection was based on the solubility of impurities, and partial layer melt crystallization were carried out under the presence of solvent. The solubility of PDX in various solvents such as ethyl acetate, tetrahydrofuran, acetone, alcohols (methanol, ethanol, 1-propanol, 1-butanol and 1-pentanol) were measured over the temperature range of $-10{\sim}15^{\circ}C$. As solubility parameters, the mixing and dissolution enthalpy between the PDX and the solvents was studied based on empirical equations and the regular solution theory. The solubility and the temperature dependency of the solubility with the solvents of acetone, ethylacetate, and tetrahydrofuran of PDX were shown to have relatively high values compared to the alcohol type solvents. Also, in same alcohols, the smaller molecules and higher polarity gave higher solvency. In partial layer melt crystallization, small amount of ethylacetate selectively dissolved impurities and gave highly purified p-dioxanone, over 99.9% purity.

• Polymer(Korea)
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• v.38 no.4
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• pp.518-524
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• 2014

Electrospinning has gained interests as a polymer processing technique for nanofiber fabrications. It is well known that both polymer solutions and polymer melts can be electrospun. Among them, melt electrospinning is environmentally friendly technique due to the absence of solvent. However, the diameter of melt-electrospun fibers is typically thicker than solution-electrospun fibers. By using a home-made melt-electrospinning device, micron-sized fibers with smooth and even surfaces were electrospun successfully. We demonstrate that low-density polyethylene fibers can be reduced in diameter with a viscosity-reducing additive such as low molecular weight polyethylene monoalcohol and polyethylene wax. The diameter was further reduced by blending it with oxidized polyethylene wax due to polarity increment. Additionally, parameters affecting the diameter were analyzed such as an applied voltage and a spinning distance.