• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1907-1911
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• 2011

A kinetic study is reported for nucleophilic substitution reactions of 4-pyridyl X-substituted benzoates 7a-e with a series of alicyclic secondary amines in H2O. The Br${\o}$nsted-type plot for the reactions of 4-pyridyl benzoate 7c is linear with ${\beta}_{nuc}$ = 0.71. The corresponding reactions of 2-pyridyl benzoate 6, which is less reactive than 7c, resulted in also a linear Br${\o}$nsted-type plot with ${\beta}_{nuc}$ = 0.77. The fact that the more reactive 7c results in a smaller ${\beta}_{nuc}$ value appears to be in accord with the reactivity-selectivity principle. The aminolysis of 7c has been suggested to proceed through a stepwise mechanism in which breakdown of the intermediate is the rate-determining step (RDS). The Hammett plot for the reactions of 7a-e with piperidine consists of two intersecting straight lines, i.e., ${\rho}_X$ = 1.47 for substrates possessing an electron-donating group (EDG) and ${\rho}_X$ = 0.91 for those possessing an electron-withdrawing group (EWG). In contrast, the corresponding Yukawa-Tsuno plot exhibits excellent linear correlation with ${\rho}_X$ = 0.79 and r = 0.56. Thus, it has been concluded that the nonlinear Hammett plot is not due to a change in the RDS but is caused by stabilization of the ground state of the substrates possessing an EDG through resonance interaction between the EDG and the C=O bond of the substrates.

• KCI Concrete Journal
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• 제12권2호
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• pp.85-93
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• 2000

Potentially significant mechanical improvements in tension can be achieved by the incorporation of randomly distributed, short discrete fibers in concrete. The improvements due to the incorporation fibers significantly influence the composite stress - strain ($\sigma$-$\varepsilon$) characteristics. In general incorporating fibers in a plain concrete has relatively small effect on its precracking behavior. It, however, alters its post-cracking behavior quite significantly, resulting in greatly improved ductility, crack controls, and energy absorption capacity (or toughness). Therefore, a thorough understanding the complete tensile stress - strain ($\sigma$-$\varepsilon$) response of fiber reinforced concrete is necessary for proper analysis while using structural components made with fiber reinforced concrete. Direct tensile stress applied to a specimen is in principle the simplest configuration for determining the tensile response of concrete. However, problems associated with testing brittle materials in tension include (i) the problem related to gripping of the specimen and (ii) the problem of ensuring centric loading. Routinely, indirect tension tests for plain concrete, flexural and split-cylinder tests, have been used as simpler alternatives to direct uniaxial tension test. They are assumed to suitable for fiber reinforced concrete since typically such composites comprise 98% by volume of plain concrete. Clearly since the post-cracking characteristics are significantly influenced by the reinforcing parameters and interface characteristics, it would be fundamentally incorrect to use indirect tensile tests for determining the tensile properties of fiber reinforced concrete. The present investigation represents a systematic look at the failure and toughening mechanisms and macroscopic stress - strain ($\sigma$-$\varepsilon$) characteristics of fiber reinforced concrete in the uniaxial tension test. Results from an experimental parametric study involving used fiber quantity, type, and mechanical properties in the uniaxial tension test are presented and discussed.

• Bulletin of the Korean Chemical Society
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• 제32권4호
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• pp.1165-1169
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• 2011

Second-order rate constants ($k_N$) have been measured spectrophotometrically for nucleophilic substitution reactions of 2,4-dinitrophenyl phenyl thionocarbonate 4 with a series of Z-substituted pyridines in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot for the reactions of 4 exhibits downward curvature (i.e., ${\beta}_1$ = 0.21 and ${\beta}_2$ = 1.04), indicating that the reactions proceed through a stepwise mechanism with a change in rate-determining step. It has been found that 4 is less reactive than its oxygen analogue, 2,4-dinitrophenyl phenyl carbonate 3, although the thionocarbonate is expected to be more electrophilic than its oxygen analogue. The $pK_a$ at the center of the Br${\o}$nsted curvature, defined as $pK_a^o$, has been analyzed to be 6.6 for the reactions of 4 and 8.5 for those of 3. Dissection of $k_N$ into the microscopic rate constants $k_1$ and $k_2/k_{-1}$ ratio has revealed that the reactions of 4 result in smaller $k_1$ values but larger $k_2/k_{-1}$ ratios than the corresponding reactions of 3. The larger $k_2/k_{-1}$ ratios have been concluded to be responsible for the smaller $pK_a^o$ found for the reactions of 4.

• 대한화학회지
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• 제33권5호
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• pp.468-476
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• 1989

여러가지 피리딘 존재하에서 1-염화안트라센술포닐(1-ASC) 및 3-페난트렌술포닐(3-PSC)이 메탄올 속에서 각각 일으키는 반응의 메카니즘을 속도론적으로 논의하였다. 이들 반응에 대한 Bronsted계수(${\beta}$)는 $20^{\circ}C$에서 1-ASC : 0.55, 3-PSC : 0.43였고 Hammett 반응상수(${\rho}$ 온도에서 1-ASC : -3.5, 3-PSC : -2.6이었다. 두 반응계에 대한 반응성-선택성 원리를 검토한 결과, 등선택성 온도는 $34.3^{\circ}C$였으며 이보다 높은 온도에서는 이 원리가 성립하지 않음을 알았다. 활성화 파라미터와 함께 위의 결과로부터 이들 반응은 속도 결정단계에서 synchronous $S_n2$메카니즘에 의해 진행되는 것으로 결론 지어졌다.

• 지적과 국토정보
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• 제46권2호
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• pp.93-105
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• 2016

현행법상 28개 지목 중에서 가장 빈번하게 신설 또는 변경되는 지목은 '도로'이다. 타 지목에서와 마찬가지로, 도로의 경계는 관련 설정원칙과 법에 따라 엄격히 확정되고 있다. 그런데 이러한 경계설정기준 중 일부, 즉 지형지물을 이용한 경계설정의 원칙과 법규해석이 혼동되는 경우가 있는데, 이는 주로 도시계획 등 토지이용계획을 구상하는 단계에서 발생한다. 법적규정은 법의 제정취지가 중요한 데, 경계확정 규정의 제정취지를 잘 못 유권 해석함으로 인해 도로경계는 현실상황과 괴리되는 문제점을 발생시킨다. 이를 시급히 보완키 위해 일부 규정의 개정, 보완이 필수적이다. 법률용어인 '절토면'과 '경사면'의 적용이 통일되어야 하고, '구조물'이라는 용어는 '지형 지물'로 개선할 것을 제언한다.

• 의료법학
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• 제21권1호
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• pp.69-105
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• 2020

의료보장제도에서 진료수가는 의료보장체계의 근간을 이루는 매우 중요한 요소이다. 국민건강보험법은 진료수가의 결정방식에 관하여 계약제를 채택하였고, 그 계약의 내용은 상대가치점수에 대한 점수당 단가를 정하는 것이다. 그에 따라 건강보험 요양급여비용은 매년마다 물가상승이나 경제 상황의 변화에 따라 조정된다. 반면, 의료급여의 경우, 의료급여법에서는 진료수가의 결정방식에 관한 내용을 규정하지 않고, 모든 사항을 보건복지부 장관에게 위임하고 있다. 그에 따라 보건복지부 장관은 2001년부터 혈액투석 치료에 관하여 정액수가제를 채택하고 있다. 이러한 혈액투석 정액수가제에 대해서 2017년 헌법소원이 제기되었고, 헌법재판소는 2020년 헌법소원 심판 청구를 모두 기각하였다. 이 글에서는, 위 헌법소원 사건을 중심으로 진료수가제도의 의미와 내용을 살펴보고, 이에 대한 헌법적 한계로 3가지 원칙을 제시한다. 그 원칙의 첫째는 법률유보의 원칙, 둘째는 포괄위임금지의 원칙, 셋째는 비례의 원칙이다. 그러한 관점에서 검토해 보면, 혈액투석 정액수가제는 상당히 위헌적인 제도로 판단된다.

• Steel and Composite Structures
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• 제6권3호
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• pp.237-255
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• 2006

This paper presents a novel analytical formulation for the analysis of composite beams with partial shear interaction stiffened by a bolted longitudinal plate accounting for time effects, such as creep and shrinkage. The model is derived by means of the principle of virtual work using a displacement-based formulation. The particularity of this approach is that the partial interaction behaviour is assumed to exist between the top slab and the joist as well as between the joist and the bolted longitudinal stiffening plate, therefore leading to a three-layered structural representation. For this purpose, a novel finite element is derived and presented. Its accuracy is validated based on short-and long-term analyses for the particular cases of full shear interaction and partial shear interaction of two layers for which solutions in closed form are available in the literature. A parametric study is carried out considering different stiffening arrangements to investigate the influence on the short-and long-term behaviour of the composite beam of the shear connection stiffness between the concrete slab and the steel joist, the stiffness of the plate-to-beam connection, the properties of the longitudinal plate and the concrete properties. The values of the deflection obtained from the finite element simulations are compared against those calculated using the effective flexural rigidity in accordance with EC5 guidelines for the behaviour of elastic multi-layered beams with flexible connection and it is shown how the latter well predicts the structural response. The proposed numerical examples highlight the ease of use of the proposed approach in determining the effectiveness of different retrofitting solutions at service conditions.

• EDISON SW 활용 경진대회 논문집
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• 제4회(2015년)
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• pp.304-307
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• 2015

Carbon nanotubes (CNTs) have been widely accepted and used as the enhancer for polymer nano-composites due to their remarkable mechanical properties. Understandably, the CNT fiber-polymer matrix interface plays a major role in determining the properties of the CNT-polymer nano-composites. Here, using the LCAODFT Lab tool available on the EDISON Nano-Physics site, we performed first-principles density-functional theory calculations to determine the atomic configurations and binding energies of the CNTs in contact with polymers. For the polymer matrixes, we chose poly(acrylonitrile) (PAN), which is one of the most well-known polymer matrixes for the carbon nanofiber nanocomposites. Different chiralities and diameters of pristine CNTs were considered, and several PAN-CNT configurations were prepared based on the atomistic positions and directions of cyano group in PAN. The most favorable configuration of PAN was obtained when the PAN bound parallel to the surface of CNT. Our finding indicates the binding configurations are determined by the direction of the cyano group dominantly rather than the atomistic position of PAN, or the symmetry of CNTs. The result of increasing the length of CNT diameter suggests that PAN is inclinable to align evenly on the surface of relatively large size of CNT with the configuration parallel to the surface. These results obtained in this study will provide the starting point for the design of improved PAN-CNT composites for the next-generation ultra-strong and ultra-light carbon nanofibers.

• Structural Engineering and Mechanics
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• 제83권2호
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• pp.259-272
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• 2022

The branch of electronics that uses an organic solar cell or conductive organic polymers in order to yield electricity from sunlight is called photovoltaic. Regarding this crucial issue, an artificial intelligence-based predictor is presented to investigate the vibrational behavior of the organic solar cell. In addition, the generalized differential quadrature method (GDQM) is utilized to extract the results. The validation examination is done to confirm the credibility of the results. Then, the deep neural network with fully connected layers (DNN-FCL) is trained by means of Adam optimization on the dataset whose members are the vibration response of the design-points. By determining the optimum values for the biases along with weights of DNN-FCL, one can predict the vibrational characteristics of any organic solar cell by knowing the properties defined as the inputs of the mentioned DNN. To assess the ability of the proposed artificial intelligence-based model in prediction of the vibrational response of the organic solar cell, the authors monitored the mean squared error in different steps of the training the DNN-FCL and they observed that the convergency of the results is excellent.

• Bulletin of the Korean Chemical Society
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• 제12권5호
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• pp.510-514
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• 1991

Second-order rate constants have been determined spectrophotometrically for reactions of S-p-nitrophenyl substituted thiobenzoates with various phenoxide ions and S-aryl substituted thiobenzoates with $HO^-$ ion. Thiol esters have been found to be more reactive than the corresponding oxygen esters toward phenoxide ions. The high reactivity of thiol esters relative to oxygen esters becomes insignificant as the basicity of the nucleophile increases. Furthermore, the highly basic $HO^-$ ion is less reactive toward thiol esters than oxygen esters. The significant dependence of the reactivity of thiol esters on the basicity of nucleophiles has been attributed to the nature of the HSAB principle. The present kinetic study has also revealed that the reactivity of thiol esters compared to oxygen esters is not so pronounced as expected based on the enhanced nucleofugicity of thiol esters. However, the effects of substituents in the nucleophile and in the acyl moiety of the substrate on rate appear to be significant. These kinetic results have led to a conclusion that the present reactions proceed via a rate-determining formation of a tetrahedral intermediate followed by a fast breakdown of it. The magnitude of the ${\beta}$ values shows no tendency either to increase or to decrease with the intrinsic reactivity of the reagents. The constancy of ${\beta}$ values in the present system is suggestive that the RSP should have limited applicability.