• Bulletin of the Korean Chemical Society
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• 제27권12호
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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.

• Bulletin of the Korean Chemical Society
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• 제24권6호
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• pp.751-756
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• 2003

We have investigated the solvent effects on Δlog $K_s$ (the difference of stability constant of binding) and the relative free energies of binding of $La^{3+} and Nd^{3+}$ ions to 18-crown-6 by a Monte Carlo simulation of statistical perturbation theory (SPT) in diverse solvents. We compared relative binding Gibbs free energies and the differences in stability constant (Δlog $K_s$) of binding of $La^{3+} and Nd^{3+}$ ions to 18-crown-6 in $CH_3OH$ in this study with the experimental. There is a good agreement between our study and the experimental. We noted that Borns function of the solvents, the electron pair donor properties of the solvent, the radii of host and guest and the differences in solvation dominate the differences in the stability constant (Δlog $K_s$) as well as the relative free energies of binding of TEX>$La^{3+} to Nd^{3+}$ ions to 18-crown-6. The results of this study appear promising for providing the association properties of crown ethers with alkaline earth metals among polar solvents and the less polar or non-polar solvents.

• Bulletin of the Korean Chemical Society
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• 제29권2호
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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.

• Bulletin of the Korean Chemical Society
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• 제14권5호
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• pp.631-635
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• 1993

The polarizability and the transition state energy of a cephalosporin are assumed to be theoretical indices of the permeability through the outer membrane and of reactivity of ${\beta}$ -lactam ring with penicillin binding proteins, respectively, in Gram-negative bacteria. They are computed by AM1 method and used as variables of quantitative structure-activity relationship study. The results justify quadratic dependence of the activity on the variables. The intersection of difference volumes between $\beta-lactamase$ stable cephalosporins and unstable ones manifests that the steric hindrance of 7-side chain is responsible for the ${\beta}$ -lactamase stability.

• Bulletin of the Korean Chemical Society
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• 제34권12호
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• pp.3727-3732
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• 2013

The interaction between metalloporphyrins and diazine tautomers was investigated using quantum chemistry method. The results showed that the metal atom in the metalloporphyrin was not coplanar with porphin ring, and zinc porphyrin has the most extent of its non-coplanar nature. The most stable complex in nine complexes was iron porphyrin. NBO analysis indicated that the interaction between the lone pair of electrons on the nitrogen atom and the unoccupied lone pair orbital of metal contributes significantly to the stability of the complexes. Through the conceptual DFT parameter and Fukui dual descriptor, the thermodynamic stability and reactivity of complexes were analyzed. The density difference function (DDF) analyzes were performed to explore the rearrangement of electronic density after the coordination interaction. NICS calculation indicated that metalloporphyrin aromaticity was reduced after the coordination interaction, and aromaticity of diazine tautomer was increased along direction vector of the coordination interaction force.

• Bulletin of the Korean Chemical Society
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• 제16권7호
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• pp.591-594
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• 1995

The influence of protecting groups on the β-sheet-structure-stability of protected peptides was studied in organic solvents. α-amino groups, carboxyl groups and side chain functional groups of model peptides were protected by suitable groups commonly used in peptide synthesis. The difference of the solubilities of model peptides was investigated by the solvent-titration method by using IR absorption spectra. The β-sheet structure of model peptide in CH2Cl2 was easily disrupted by increasing the amounts of DMSO. The β-sheet-structure-stabilizing potentials of each protecting group showed similar behaviors except Npys, Mts and Z2. The result exhibits that the < SPβ > values of protected peptides are almost independent of the kinds of their protecting groups.

• Macromolecular Research
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• 제17권8호
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• pp.609-615
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• 2009

Two types of nano composite were obtained by in situ chemical method in polyaniline (PANI)/dodecyl-benzenesulfonic acid (DBSA) system depending on the use of either ammonium persulfate (APS) or ferric chloride ($FeCl_3$) as the oxidant. In order to study the difference of the two composites in the surface characteristics, thermal stability, and electric properties, the composite films were studied by transmission electron microscopy (TEM), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and temperature dependent DC electrical conductivity. The results revealed a large difference in the surface morphology, thermal stability, and the microstructure properties between the two composites, and these differences were considered responsible for the molecular order and conductivity.

• 한국응용과학기술학회지
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• 제6권1호
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• pp.9-14
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• 1989

Effectiveness of some natural antioxidants were investigated by measuring the physico-chemical charcteristics and fatty acid composition during thermal oxidation in palm oil. Tocopherol showed most enhanced thermal oxidation stabilities compared to the other natural antioxidants. AR spice was no good AOM stability and changes of acid value but the other parameters were obtained desirable results. The changes of linoleic aicd content was slightly decreased during thermal oxidation. Addition of rosemary and glycyrriza extract increased the stabilities of oil less than tocopherol and AR spice. Order of antioxdative effects was tocopherol, AR spice and others. There was no significiant difference in stability of rosemary and glycyrriza extract.

• 동아시아식생활학회지
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• 제4권2호
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• pp.51-57
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• 1994

Six sesame oils prepared from Korean and Chinese sesame were oxidized at 40$^{\circ}C$ for 16 weeks in a dark place. Effects of oxidative stability on tocopherols of those sesame oils were studied in related to chemical changes in the oils. All oil samples showed that the rate of tocopherol reduction was increased by the storage time. The changes of peroxide value, free fatty acid, carbonyl content were not caused in direct relation to the tocopherols oxidation. The amount of total tocopherol in the Korean sesame oil ranged from 48.7-50.3mg/100g and Chinese seseame oil ranged from 42.4-44.7 mg/100g According to the three individual tocopherols remaining content after 16weeks, ${\gamma}$-,${\alpha}$-,${\beta}$- tocopherol showed 70%, 30%, 20% of initial concentrations in the oils respectively. There was no significant difference between Korean and Chinese sesame oil except the higher total amount of the tocopherol in Korean sesame oil than that of Chinese.

• Bulletin of the Korean Chemical Society
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• 제11권6호
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• pp.521-527
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• 1990

The binding characteristics and analytical applications of anilinium ion complexes with 18-crown-6 were studied by polarography and NMR. First, the electrochemical reduction of the 10 species of mono and dimethylsubstituted anilinium ion complexes with 18-crown-6 as host in methanol are examined. The addition of 18-crown-6 to anilinium guest solution the polarographic waves remain well defined but shifted toward more negative potentials, indicating the complex formation. The values of formation constants, log Κ for 10 species of methylsubstituted anilinium ion complexes with 18-crown-6 varies from 2.7 to 4.8 in methanol at $25^{\circ}C$. The stability order of complexes for 18-crown-6 is anilinilum > 4-methyl > 3,4-dimethyl > 3-methyl > 3,5-dimethyl > 2,4-dimethyl > 2,5-dimethyl > 2,3-dimethyl > 2-methyl > 2,6-dimethylanilinium ion. The steric hindrance shows significant effect. Second, Proton NMR was used to elucidate their interaction characteristics. From the results of so called NMR titration techniques, the behaviors of binding sites on complexation, and the stoichiometry and stability order of complex were obtained. And the later results show the satisfactory agreement with the quantitative values obtained by polarography. Finally, the individual determinations of anilinium ion mixtures were also accomplished by addition of 18-crown-6. In some mixtures of methyl or dimethylanilinium ions the reduction peaks of differential pulse method appeared into one unresolved wave attributed to the small difference of half-wave potential, ${\Delta}E_{1/2}$. In the presence of 18-crown-6, the polarographic waves were resolved into individual maxima because of the shift toward more negative direction by the difference of selectivity of anilinium ions with 18-crown-6. It may be concluded that quantitative analysis of methylanilinium ion mixture make possible because the half-wave potential shift by the selectivity difference due to the steric hindrance between methyl group and 18-crown-6 on complexation.