• 한국응용과학기술학회지
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• 제8권2호
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• pp.175-181
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• 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
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• 제9권1호
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• pp.1-4
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• 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.

• 한국재료학회지
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• 제10권9호
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• pp.593-600
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• 2000

본 연구에서는 도핑하지 않은 다이아몬드 박막에서의 전류전도 경로를 체계적으로 규명하고 다이아몬드 박막의 전도기구에 대해 조사하였다. 도핑되지 않은 다결정 다이아몬드 박막에서 두께와 측정방향에 따른 교류 임피던스법에 의해 측정된 저향값이 기존의 표면전도 모델과는 일치하지 안니하였다. 다이아몬드 박막에 구리를 전기도금한 결과 구리는 결정립계에만 불연속적으로 도금되었고 다이아몬드 박막 위에 은을 증착한 후 전지에칭을 한 결과 결정립계가 우선 에칭이 되어 전류가 결정립계를 통하여 흐름을 확인하였다. 또, 리본형 다이아몬드 박막의 표면을 절연층으로 형성시킨 후 박막 내부의 결정립계를 통하여 전류가 흘러 전기도금이 되는 것으로부터 다결정 다이아몬드 박막의 주요 전기전도 경로는 결정립계임을 확인하였다. 높은 전기전도도를 보여주는 다이아몬드 박막은 전도 활성화 에너지가 45meV 정도이었고 dangling bond 밀도는 낮았다. 그러나 산소 열처리나 수소플라즈마처리가 Si passivation 이론과는 반대로 dangling bond 밀도를 증가시키면서 전기전도성을 떨어뜨렸다. 이 결과들과 표면의 탄소화학결합을 연결시켜 높은 전도성을 야기시키는 결합은 H-C-C-H 결합임을 추론하였다.

• Bulletin of the Korean Chemical Society
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• 제26권4호
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• pp.641-644
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• 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.

• 한국강구조학회 논문집
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• 제14권4호
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• pp.481-487
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• 2002

콘크리트충전 강관기둥의 외다이아프램 접합부형식에서, 철골보의 하중이 내부의 콘크리트로 전달되는 하중전달 메카니즘이 아직 명확하게 규명되지 않았다. 여기서 각 층에서 철골보의 전단력은 외부의 강관과 내부의 콘크리트 사이의 부착응력에 의해 전달된다고 본다. 따라서 본 연구는 콘크리트충전 강관기둥의 부착응력을 파악하기 위해, 콘크리트면에만 하중을 가하는 단순가력실험을 실시하였다. 콘크리트 종류, 강관의 형상/길이, 이음부의 유무/뒷댐재의 두께 등을 변수로 총 30개의 실험체를 제작하여 실험을 실시했으며, 각 변수에 따른 실험결과를 비교/분석하고자 했다.

• 한국구조물진단유지관리공학회 논문집
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• 제24권5호
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• pp.1-8
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• 2020

이 연구에서는 철근콘크리트 부재의 전단파괴가 휨-전단 메커니즘에 지배된다는 가정을 바탕으로 인장측과 압축측에 대한 2개의 전단요구곡선들과 이에 대응되는 잠재전단강도곡선들을 각각 도출하였으며, 이를 기반으로 전단강도 산정모델을 제안하였다. 제안모델에서는 철근과 콘크리트의 부착거동을 고려하여 휨균열폭과 철근의 국부응력증가분을 산정하였다. 또한, 휨균열로부터 발전되는 지배전단균열의 생성과 균열진전거동을 이론적으로 모사하기 위하여 균열집중계수를 도입하였으며, 이를 통해 단면높이가 큰 철근콘크리트 부재에서 관측되는 크기효과를 반영하였다. 또한, 기존의 해석모델과는 다르게 전단철근과 콘크리트의 전단기여분 사이의 상호작용을 고려할 수 있는 새로운 형태의 수식을 개발하였다. 제안모델의 검증을 위하여 방대한 전단실험체들을 기존문헌으로부터 수집하였으며, 이를 통해 해석모델을 검증한 결과는 제안모델이 실험체들의 재료, 크기 및 철근의 부착특성에 관계없이 실험결과를 정확하게 평가할 수 있음을 보여주었다.

• Bulletin of the Korean Chemical Society
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• 제35권5호
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• pp.1479-1484
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• 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.

• 한국구조물진단유지관리공학회 논문집
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• 제21권5호
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• pp.125-133
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• 2017

도심지 주차문제 해결에 있어 공작물 주차장이 주목을 받고 있다. 그러나 공작물 주차장은 전체 높이 8 m 이하로 건설되도록 규정되어 있다. 이에 본 연구에서는 층고 절감 및 장스팬화가 가능한 와이드 합성보를 대상으로 휨 및 전단성능을 평가하였다. 실험결과 보강철근(트러스 철근)은 휨강도에 영향을 미치지 않았다. 그러나, 보강철근이 없는 실험체의 경우 항복강도의 70%에서 슬립이 발생하여 기계적 부착능력이 저하되었다. 전단부착 실험결과 전단연결재가 없는 모든 실험체는 기계적 부착만으로 충분한 전단부착 성능을 가지지 못하므로, Flat Bar를 최소 2개 이상 설치하여야 한다.

• Molecules and Cells
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• 제27권6호
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• pp.673-680
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• 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.

• Geomechanics and Engineering
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• 제12권3호
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• pp.541-560
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• 2017

In this research, experimental and numerical simulations were adopted to investigate the effects of ligament angle on compressive strength and failure mode of rock-like material specimens containing two non-coplanar filled fissures under uniaxial compression. The experimental results show that with the increase of ligament angle, the compressive strength decreases to a nadir at the ligament angle of $60^{\circ}$, before increasing to the maximum at the ligament angle of $120^{\circ}$, while the elastic modulus is not obviously related to the ligament angle. The shear coalescence type easily occurred when ${\alpha}$ < ${\beta}$, although having the same degree difference between the angle of ligament and fissure. Numerical simulations using $PFC^{2D}$ were performed for flawed specimens under uniaxial compression, and the results are in good consistency with the experimental results. By analyzing the crack evolution process and parallel bond force field of rock-like material specimen containing two non-coplanar filled fissures, we can conclude that the coalescence and propagation of crack are mainly derived from parallel bond force, and the crack initiation and propagation also affect the distribution of parallel bond force. Finally, the displacement vectors in ligament region were used to identify the type of coalescence, and the results coincided with that obtained by analyzing parallel bond force field. These experimental and numerical results are expected to improve the understanding of the mechanism of flawed rock engineering structures.