• 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

• Bulletin of the Korean Chemical Society
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• v.32 no.7
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• pp.2358-2368
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• 2011

Density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations, employing the B3LYP method and the LANL2DZ, 6-31G$^*$(LANL2DZ for Tc), 6-31G$^*$(cc-pVDZ-pp for Tc) and DGDZVP basis sets, have been performed to investigate the electronic structures and absorption spectra of the technetium-99m-labeled methylenediphosphonate ($^{99m}Tc$-MDP) complex of the simplest diphosphonate ligand. The bonding situations and natural bond orbital compositions were studied by the Mulliken population analysis (MPA) and natural bond orbital (NBO) analysis. The results indicate that the ${\sigma}$ and ${\pi}$ contributions to the Tc-O bonds are strongly polarized towards the oxygen atoms and the ionic contribution to the Tc-O bonding is larger than the covalent contribution. The electronic transitions investigated by TDDFT calculations and molecular orbital analyses show that the origin of all absorption bands is ascribed to the ligand-to-metal charge transfer (LMCT) character. The solvent effect on the electronic structures and absorption spectra has also been studied by performing DFT and TDDFT calculations at the B3LYP/6-31G$^*$(cc-pVDZ-pp for Tc) level with the integral equation formalism polarized continuum model (IEFPCM) in different media. It is found that the absorption spectra display blue shift in different extents with the increase of solvent polarity.

• 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.

• Elastomers and Composites
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• v.49 no.3
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• pp.239-244
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• 2014

Reaction between silica and silane coupling agent without solvent was investigated using transmission mode Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Bis[3-(triethoxysilylpropyl) tetrasulfide] (TESPT) was used as a silane coupling agent. After removing the unreacted TESPT, formation of chemical bonds was analyzed using FTIR and content of reacted TESPT was determined using TGA. Content of the coupling agent bonded to silica increased with increase in the coupling agent content, but the oligomers were formed by condensation reaction between coupling agents when the coupling agent was used to excess. In order to identify bonds formed among silica, coupling agent, and rubber, a silica-coupling agent-BR model composite was prepared by reaction of the modified silica with liquid BR of low molecular weight and chemical bond formation of silica-coupling agent-BR was investigated. Unreacted rubber was removed with solvent and analysis was performed using FTIR and TGA. BR was reacted with the coupling agent of the modified silica to form chemical bonds. Polarity of silica surface was strikingly reduced and particle size of silica was increased by chemical bond formation of silica-coupling agent-BR.

• Journal of the Korean Chemical Society
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• v.34 no.6
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• pp.509-516
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• 1990

1H-nmr chemical shifts and lineshapes of amino-protons of acetamide (AA) in n-alcohols were determined. The chemical shifts are discussed by the Reichardt's solvent polarity parameter, E$_{T}$(30). The following relationship between $\delta$obs and E$_{T}$(30) was obtained. ${\delta}_{obs}$ = ${\delta}_{o}$ ＋ aE$_{T}$ (30) ＋ b[E$_{T}$(30)]$^2$ where ${\delta}_{o}$ is the chemical shift of the solute in gaseous state or at $E_{T}$(30) = 0, a is a characteristic constant for the protons of AA in n-alcohol solutions and b is a constant for the solute (AA)-solvent (n-alcohols) interaction. The barrier of the hindered rotation about the N-C(O) bond in AA was obtained by analysis of the lineshapes of the amino-protons in AA. The behavior of the internal rotation as well as chemical shifts of the amino-protons in AA has been found to be closely related to the $E_{T}$(30) of n-alcohols.

• Polymer(Korea)
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• v.36 no.1
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• pp.16-21
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• 2012

Organic-inorganic hybrid coating film using 1,2-bis(2,4-dimethyl-5-phenyl-3-thienyl)-3,3,4,4,5,5-hexafluoro-1-cyclopentene (BTHFC) as a photochromic material was prepared under various reaction conditions such as the amounts of tetramethoxysilane (TMOS), various silane coupling agents, and solvent. It was found that color-fading speed and absorbance of the coating film was strongly dependent upon the polarity of silane coupling agent and solvent. In addition, the mole ratio of TMOS and methacryloyloxypropyltrimethoxysilane (MPTMS) was an important factor to determine color-fading speed and absorbance of the coating film. With increasing TMOS contents in coating film, the pencil hardness was increased. On the other hands, the transmittance of coating film was relatively decreased with the increase of TMOS.

• Toxicological Research
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• v.14 no.2
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• pp.171-176
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• 1998

The biological effects of the water extracts of Rhus Verniciflua Stokes (RVS) were evaluated by protection against hydroxyl radicals. Antioxidative activities were measured using both 1,1-diphenyl-2-picrylhydrazyl (DPPH) and thiocyanate method. Also we used the Glucose oxidase (GO) 20 mU/$\textrm{m}{\ell}$ hydroxyl radical generating system in mouse forebrain cell culture. Water was used for ex-traction from RVS as a solvent which has high polarity especially. In DPPH method, the antioxidative activities of the crude water extract were stronger than any other extracts of low polar-solvents. In the antioxidative effects of mouse forebrain culture using 20 mU/$\textrm{m}{\ell}$ GO, cell viabilities were evaluated 65.6%, 68.8% at 1 $\mu\textrm{g}$. 5 $\mu\textrm{g}$ addition of crude water extracts (30 mg/$\textrm{m}{\ell}$) respectively. 10 $\mu\textrm{g}$ addition of crude water extracts had more than 86.1% cell viabilities, P<0.0l significantly, compared with the group treated with GO alone. In comparison with the antioxidative activities of several commercial antioxidants (ascorbic acid, $\alpha$-tocopherol, catalase, serum), 273 $\mu\textrm{g}$/$\textrm{m}{\ell}$ addition of crude water extracts (300 $\mu\textrm{g}$/$\textrm{m}{\ell}$) showed equivalent antioxidative effect to 25 uM ascorbic acid.

• Journal of the Korean Chemical Society
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• v.39 no.8
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• pp.589-597
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• 1995

In water-ethanol systems, the limiting equivalent conductances of electrolytes were obtained using conductometric method. Using TATB method, the limiting equivalent ionic conductances of Li+, Na+, K+, Cl-, and Br- ions were also obtained. The effective radii of corresponding ions were determined using Nightingale method. From the volume of the solvation shell, the four solvation numbers were suggested. The reasonable solvation numbers (hH2O+hO) were estimated by comparing the values obtained by from the various suggested methods. The isosolvation point of ion in water-ethanol estimated was found to be larger than that of in water-methanol. This result agree with ET (solvent polarity) values of solvents. From the reasonable solvation numbers of ions in water-ethanol, the selective solvents of corresponding ions in water-ethanol were obtained.

• Journal of the Korean Wood Science and Technology
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• v.48 no.6
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• pp.769-779
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• 2020

This study investigates the selective fractionation of lignin with uniform structures and lower molecular weight. Lignin solubilization was first performed using a solution of acetic acid (AA) and hydrogen peroxide (HP) (4:1, (v/v)) to form peracetic acid (PAA), which is a strong oxidant. After the PAA-induced solubilization that occurred at 80℃, totally soluble lignin was extracted by ethyl acetate (EA) and divided into organic- and water-soluble fractions. The EA fraction was then fractionated by open-column using three solutions (chloroform-ethyl acetate, methanol, and water) sequentially. With an increase in the solvent polarity during the fractionation step, the molecular weight of the lignin-derived compounds in the fraction increased. Remarkably, some lignin fractions did not have aromatic structures. These fractions were identified as carboxylic acid-containing polymers like poly-carboxylates. These results conclude that the selective production of lignin-derived polymers with specific molecular weight and structural characteristics could be possible through open-column fractionation.

• Proceedings of the Korean Society of Dyers and Finishers Conference
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• 2004.11a
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• pp.274-275
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• 2004

The majority of dyes belong to the chromophoric class known as donor-acceptor systems, the essential structural feature of such systems being the presence of one or more electron donating groups conjugated to one or more electron withdrawing groups via an unsaturated bridge. The indigo molecule may be formally divided into two identical electron donor/acceptor subsystems, each containing an add number of pi electrons, two subsystems being joined by carbon-carbon double bond. Indigoid type dyes which show a strong colour change on protonation or dissociation have many potential functional applications, for example as analytical pH indicators, solvent polarity indicators, and in various imaging and reprographic systems.