• Journal of the Korean Chemical Society
• /
• v.34 no.1
• /
• pp.10-18
• /
• 1990

Solvolyses of p-substituted benzyl bromides have been studied in dimethylsulfoxide-water and N,N-dimethylformamide-water mixtures by kinetic method. To determine the ionizing power, Y and the nucleophilicity, $N_{BS}$, the solvolyses of 1-adamantyl halides, t-butyl halides, and methyl tosylate in the same solvent mixtures have been investigated. The solvatochromic parameters for each dimethylsulfoxide-water mixtures have been determined by substituting into the Taft's linear solvatochromic energy relationships with measured $ν_{max}$. The solvolyses of p-substituted benzyl bromides have been found to proceed by borderline mechanism in which bond formation is more advanced than bond cleavage in the transition state based on the m, l values and ${\beta},{\rho}_s$, values.

• Journal of the Korean Applied Science and Technology
• /
• v.8 no.2
• /
• pp.175-181
• /
• 1991

The kinetics of the addition of 1-benzylindole-3-(p-substituted) acetophenone derivatives was investigated by ultraviolet spectrophotometery in 30% dioxane -$H_2O\;at\;25^{\circ}C$. A rate equation which can be applied over wide pH range was obtained. The Substituent effects on 1-benzylindole-3-(p-substituted) acetophenone derivatives were studied, and addition were facilitated by electron attracting groups. On the base of the rate equation, substituent effect, and general base effect the plausible addition mechanism was proposed : Below pH 3.0, only neutral thiourea molecule was added to the carbon-carbon double bond, and in the range of pH 0.0${\sim}$14.0, netural thiourea molecule and thiourea anion competitively attacted the double bond. By contrast, above pH 10.0, the reaction was dependent upon only the addition of thiourea anion.

• Bulletin of the Korean Chemical Society
• /
• v.9 no.1
• /
• pp.1-4
• /
• 1988

Rates of solvolysis of trans-[Co$(N-eten)_2Cl_2$]$^+$ have been investigated using spectrophotometric method at various pressures and temperatures in the mixtures of water with the t-butyl alcohol which possesses a high structure inducing capacity in water. The values of ${\Delta}V^{\neq}$ obtained from pressure effect on the rate constants were 2.55∼ 5.83 $cm^3mol^{-1}$. These values were discussed in terms of dissociative mechanism. Extrema found in the variation of ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$ with solvent composition correlated with extrema in the variation of the physical properties of the mixtures. The logarithms of rate constants correlated linearly with both Grunwald-Winstein parameter and the reciprocal of dielectric constant ($Ds^{-1}$). The gradient, m of Grunwald-Winstein plot for the trans-[Co$(N-eten)_2Cl_2$]$^+$ was 0.09, which is significantly lower than those for the other cobalt (Ⅲ)-dichloro complexes. It was suggested that the reaction is an Id mechanism with long extension of Co-Cl bond in the transition state, as found for the C-Cl bond in the transition state for the solvolysis of t-butyl chloride.

• Korean Journal of Materials Research
• /
• v.10 no.9
• /
• pp.593-600
• /
• 2000

This paper investigated the conduction path and conduction mechanism in undoped polycrystalline diamond thin films deposited by microwave chemical vapor deposition. The resistances measured by ac impedance spectroscopy with different directions can not be explained by the previously-known surface conduction model. The electrodeposition of Cu and electroetching of Ag experiments showed that the conduction path is the grain boundaries within the diamond films. The electodeposition of Cu with an insulating surface layer further proved that the main conduction path in polycrystalline films in the grain boundaries. The film with high electrical conductivity has low activation energy of 45meV and higher dangling bond density. By considering the results and surface C chemical bonds, the H-C-C-H bonds at surface and in grain boundaries might be the origin of high conductivity in undoped diamond films.

• Bulletin of the Korean Chemical Society
• /
• v.26 no.4
• /
• pp.641-644
• /
• 2005

Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)\;to\;{\beta}$-cyanostilbenes ($YC_6H_4CH=C(CN)C_6H_4$Y’) have been studied in acetonitrile at 30.0 oC. A greater degree of N-$C_{\alpha}$ bond formation (larger ${\beta}_X$) is obtained with a stronger electron-withdrawing substituent in either ${\alpha}-\;(\delta\sigma_Y\;{\gt}\;0)\;or\;{\beta}-ring\;(\delta\sigma_{Y'}\;{\gt}$ 0). A stronger charge development is observed in the TS on $C_{\beta}\;(\rho_{Y'}$= 1.06 for X=Y=H) rather than on $C_{\alpha}\;(\rho_{Y}$ = 0.62 for X=Y’H) indicating the lag in the resonance development into the activating group (CN) on $C_{\beta}$ in the transition state. Similarly, the magnitude of $\rho$$_{XY'}$(−0.72) is greater than $\rho_{XY}$ (−0.66) due to a stronger interaction of the nucleophile with $\beta$-ring than $\alpha$-ring. The positive sign of $\rho_{YY'}$correctly reflects $\pi$ bond cleavage between the two rings in the TS. Relatively large kinetic isotope effects ($k_H/k_D\;{\geq}$ 2.0) involving deuterated nucleophiles ($XC_6H_4CH_2ND_2$) suggest a four-membered cyclic TS in which concurrent N-C$_{\alpha}$ and H(D)-C$_{\beta}$ bond formation occurs.

• Journal of Korean Society of Steel Construction
• /
• v.14 no.4
• /
• pp.481-487
• /
• 2002

Currently, the load transfer's mechanism from a beam to a column has yet to ve clarified in a concrete filled steel tubular (CFT) structure with a connection type of an exterior diaphragm. The loads for each floor are transferred to the concrete core from a steel beam through ha contacted face between an in-filled concrete and the interior surface of a steel tube. Thus, a Push-Out test was performed to investigate the load transfer mechanism. A total of 30 samples were tested to confirm the bond stress and/or axial load distribution between a steel tube and in-filled concrete for CFT column. The main parameters considered for this study included concrete type, steel tube-shape/length, and the effect of a weld joint wit ha backing strip for a column splice. Test results were summarized to confirm load transfer behavior between a concrete and steel tube for each experimental parameter, using the analytical approach to verify experimental results.

• Journal of the Korea institute for structural maintenance and inspection
• /
• v.24 no.5
• /
• pp.1-8
• /
• 2020

This study presents a shear strength estimation model, in which the shear failure of a reinforced concrete (RC) member is assumed to be governed by the flexure-shear mechanism. Two shear demand curves and corresponding potential capacity curves for cracked tension and uncracked compression zones are derived, for which the bond mechanism developed between reinforcing bars and surrounding concrete is considered in flexural analysis. The shear crack concentration factor is also addressed to consider the so-called size effect induced in large RC members. In addition,unlike exising methods, a new formulation was addressed to consider the interaction between the shear contributions of concrete and stirrup. To verify the proposed method, an extensive shear database was established, and it appeared that the proposed method can capture the shear strengths of the collected test specimens regardless of their material properties, geometrical features, presence of stirrups, and bond characteristics.

• Bulletin of the Korean Chemical Society
• /
• v.35 no.5
• /
• pp.1479-1484
• /
• 2014

Based on the full optimized molecular geometric structures at B3LYP/cc-pvtz method, a new designed compound, 4,6,8-trinitro-4,5,7,8-tetrahydro-6H-furazano[3,4-f ]-1,3,5-triazepine was investigated in order to look for high energy density compounds (HEDCs). The analysis of the molecular structure indicates that the seven-membered ring adopts chair conformation and there exist intramolecular hydrogen bond interactions. IR spectrum and heat of formation (HOF) were predicted. The detonation velocity and pressure were evaluated by using Kamlet-Jacobs equations based on the theoretical density and condensed HOF. The bond dissociation energies and bond orders for the weakest bonds were analyzed to investigate the thermal stability of the title compound. The results show that $N_1-N_6$ bond is the trigger bond. The crystal structure obtained by molecular mechanics belongs to $Pna2_1$ space group, with lattice parameters Z = 4, a = 15.3023 ${\AA}$, b = 5.7882 ${\AA}$, c = 11.0471 ${\AA}$, ${\rho}=2.06gcm^{-3}$. In addition, the analysis of frontier molecular orbital shows the title compound has good stability and high chemical hardness.

• Journal of the Korea institute for structural maintenance and inspection
• /
• v.21 no.5
• /
• pp.125-133
• /
• 2017

A parking structure has been on the spotlight to solve the parking problem in downtown area. However, the overall height of parking structure is stipulated less than 8m. Therefore, in this research, the flexural and shear capacity of 'wide composite beam' which can reduce story height and have long span, is evaluated. Based on test result, the rebar in truss did not affect its flexural strength. However, in the case of the specimen without the rebar, the mechanical bond strength decreased due to slip occurrence at 70% of the flexural yield strength. Based on the test of shear-bond behavior, all specimen without shear connector should be reinforced with 2 or more flat bar, because it did not have enough shear bond strength resisted by the mechanical bond mechanism.

• Molecules and Cells
• /
• v.27 no.6
• /
• pp.673-680
• /
• 2009

Conversion of the normal soluble form of prion protein, PrP ($PrP^C$), to proteinase K-resistant form ($PrP^{Sc}$) is a common molecular etiology of prion diseases. Proteinase K-resistance is attributed to a drastic conformational change from ${\alpha}$-helix to ${\beta}$-sheet and subsequent fibril formation. Compelling evidence suggests that membranes play a role in the conformational conversion of PrP. However, biophysical mechanisms underlying the conformational changes of PrP and membrane binding are still elusive. Recently, we demonstrated that the putative transmembrane domain (TMD; residues 111-135) of Syrian hamster PrP penetrates into the membrane upon the reduction of the conserved disulfide bond of PrP. To understand the mechanism underlying the membrane insertion of the TMD, here we explored changes in conformation and membrane binding abilities of PrP using wild type and cysteine-free mutant. We show that the reduction of the disulfide bond of PrP removes motional restriction of the TMD, which might, in turn, expose the TMD into solvent. The released TMD then penetrates into the membrane. We suggest that the disulfide bond regulates the membrane binding mode of PrP by controlling the motional freedom of the TMD.