• Bulletin of the Korean Chemical Society
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• 제18권11호
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• pp.1186-1191
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• 1997

Solvolyses of methanesulfonyl chloride (CH3SO2Cl) in water and methanol have been studied theoretically using ab initio self-consistent reaction field (SCRF) molecular orbital method. All stationary structures including transition state on the potential energy surface in solution have been found and compared with the gas phase structures. The overall reaction occurs via a concerted SN2 mechanism with a non-cyclic trigonal bipyramidal transition state, and the activation barrier is lowered significantly in solution. The transition state for the hydrolysis reaction is looser than that for the methanolysis reaction, and this is in accord with the experimental findings that an SN2 type mechanism, which is shifted toward an SN1 process or an SAN process in the hydrolysis and alcoholysis reaction, respectively, takes place. The catalytic role of additional solvent molecules appears to be a purely general-base catalysis based on the linear transition structures. Experimental barrier can be estimated by taking into account the desolvation energy of nucleophile in the reaction of methanesulfonyl chloride with bulk solvent cluster as a nucleophile.

• Steel and Composite Structures
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• 제43권3호
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• pp.363-373
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• 2022

As a key reinforcement connection between a tower and a substructure in offshore wind turbine system, the transition piece is inevitably subjected to cyclic dynamic environmental loads such as wind, current and wave. Therefore, well designed transition piece with high strength and good fatigue resistance is of great significance to the structural safety and reliability of offshore wind power systems. In this study, the structural behavior of the transition piece was studied by an extensive sets of finite element analyses. Three widely used types of transition piece were considered. The characteristics of stress development, fatigue life and weight depending on the type of the transition piece were investigated in the ultimate limit state (ULS) and the fatigue limit state (FLS) of a 5-MW offshore wind turbine to be placed in Korea. An optimal form of the transition piece was proposed based on this parametric study.

• 한국지능시스템학회논문지
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• 제16권4호
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• pp.396-401
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• 2006

순환결합형 신경회로망은 복수 개의 리미트사이클을 생성하며 따라서, 많은 동적 정보를 저장할 수 있는 메모리 시스템으로 사용할 수 있다는 것이 알려져 있다. 본 논문에서는 각 뉴런이 최근접 뉴런에만 이진화한 결합하중 ${\pm}1$로 연결된 연속 시간모델 순환결합형 신경회로망을 구현하였다. 그리고 이런 회로망을 통해 생성되는 리미트사이클의 수와 패턴을 시뮬레이션을 통하여 나타내었다. 또한 카오스 신호를 인가하여 리미트사이클 사이의 천이 가능성을 입증하였다. 특히, 카오스 신호 이외의 랜덤 노이즈를 이용한 해석을 통하여 동적 신경회로망에 카오스 노이즈를 인가하는 경우의 유효성을 검토하였다.

• Bulletin of the Korean Chemical Society
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• 제32권5호
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• pp.1539-1542
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• 2011

The aminolysis of O-methyl S-aryl thiocarbonates with benzylamines are studied in acetonitrile at -45.0$^{\circ}C$. The ${\beta}_X$(${\beta}_{nuc}$) values are in the range 0.62-0.80 with a negative cross-interaction constant, ${\rho}_{XZ}$ = -0.42, which are interpreted to indicate a concerted mechanism. The kinetic isotope effects involving deuterated benzylamine nucleophiles ($XC_6H_4CH_2ND_2$) are large, $k_H/k_D$ = 1.29-1.75, suggesting that the N-H(D) bond is partially broken in the transition state by forming a hydrogen-bonded four-center cyclic structure. The concerted mechanism is enforced by the strong push provided by the MeO group which enhances the nucleofugalities of both benzylamine and arenethiolate from the putative zwitterionic tetrahedral intermediate.

• Bulletin of the Korean Chemical Society
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• 제12권1호
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• pp.97-101
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• 1991

Gas-phase pyrolyses of carbonate esters, ${\alpha}$- and ${\beta}$-hydroxy esters and ${\beta}$-hydroxy ketones have been studied theoretically by the AM1 MO method. Carbonate esters were found to decompose by two types of processes; in the reaction pathway involving an intermediate, the decomposition of the intermediate was rate-limiting, but direct pyrolyses were also possible via a six-membered cyclic transition state in which the methoxy oxygen attacks a hydrogen atom on the ${\beta}$-carbon. The hydroxy esters and ketones were found to decompose in a concerted process involving a six-membered cyclic transition state. Successive methylation on the ${\alpha}$- and ${\gamma}$-carbon led to an increase in the reactivity in agreement with experiments.

• Bulletin of the Korean Chemical Society
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• 제30권8호
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• pp.1887-1890
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• 2009

• Bulletin of the Korean Chemical Society
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• 제32권6호
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• pp.1951-1956
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• 2011

A kinetic study is reported on nucleophilic substitution reactions of 4-nitrophenyl nicotinate 5 and isonicotinate 6 with alkali metal ethoxide EtOM (M = K, Na, and Li) in anhydrous ethanol at $25.0{\pm}0.1^{\circ}C$. Plots of pseudo-first-order rate constant $k_{obsd}$ vs. EtOM concentration exhibit upward curvature for the reactions of 5 and 6 with EtOK and EtONa but are almost linear for those with EtOLi. Dissection of $k_{obsd}$ into $k_{EtO^-}$ and $k_{EtOM}$ (i.e., the second-order rate constant for the reaction with dissociated $EtO^-$ and ion-paired EtOM, respectively) has shown that $k_{EtOK}$ ${\geq}$ $k_{EtONa}$ > $k_{EtO^-}$ but $k_{EtOLi}$ < $k_{EtO^-}$. It has been concluded that $K^+$ and $Na^+$ ions catalyze the reactions by increasing the electrophilicity of the carbonyl carbon atom through formation of a 4-membered cyclic transition state $TS_3$ or $TS_4$. However, $M^+$ ion catalysis has been found to be much less significant for the reactions of 5 and 6 than for the corresponding reactions of 4-nitrophenyl picolinate 4, which was reported to proceed through a 5-membered cyclic transition state $TS_2$. Although 5 and 6 are significantly more reactive than 4-nitrophenyl benzoate 3, the reactions of 5 and 6 result in smaller $k_{EtOK}/k_{EtO^-}$ ratios than those of 3. The electron-withdrawing ability of the nitrogen atom in the acyl moiety of 5 and 6 has been suggested to be responsible for the increase in reactivity and the decrease in the $k_{EtOK}/k_{EtO^-}$ ratio.

• 한국해양공학회지
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• 제6권1호
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• pp.78-86
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• 1992

The creep behaviors of 1%Cr-Mo-V and 12%Cr steam turbine rotor steels under static or cyclic load were examined at 600 and $700^{\circ}C$. The relationship between these two kinds of phenomena was studied and the experimental results were summarized as follows: 1) It is confirmed that the cyclic creep strain dependent on time is more available for creep, behavior analysis according to frequency change than that dependent on number of cycles, and the static creep, the special case of cyclic creep with stress ratio of 1 can be also more effectively analyzed by time-dependence. 2) The steady cyclic creep rate vs. the steady static creep rate, increases according to the increase of stress ratio, and this phenomena may occur on occasion of the decrease of the internal stress. 3) The initial strain affects on all the creep properties of the transient region, the steady state region and the rupture time in cyclic creep as well as static creep, and the quantitative relationships among them exist.

• Bulletin of the Korean Chemical Society
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• 제26권6호
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• pp.935-938
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• 2005

Nucleophilic addition reactions of benzylamines (BA; $XC_6H_4CH_2NH_2$) to $\alpha-cyano-\beta$-phenylacrylamides (CPA; $YC_6H_4CH=C(CN)CONH_2$) have been investigated in acetonitrile at 25.0 ${^{\circ}C}$. The rate is first order with respect to BA and CPA and no base catalysis is observed. The addition of BA to CPA occurs in a single step in which the addition of BA to $C_{\beta}$ of CPA and proton transfer from BA to $C_{\alpha}$ of CPA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($\rho_X$) and Bronsted ($\beta_X$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the crossinteraction constant, $\rho_XY$ (= −D0.26), is comparable to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($k_H/k_D\;{\gt}$ 1.0) and relatively low ${\Delta}H^{\neq}$ and large negative ${\Delta}S^{\neq}$ values are also consistent with the mechanism proposed.

• BMB Reports
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• 제55권8호
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• pp.370-379
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• 2022

Human pregnancy is a delicate and complex process where multiorgan interactions between two independent systems, the mother, and her fetus, maintain pregnancy. Intercellular interactions that can define homeostasis at the various cellular level between the two systems allow uninterrupted fetal growth and development until delivery. Interactions are needed for tissue remodeling during pregnancy at both fetal and maternal tissue layers. One of the mechanisms that help tissue remodeling is via cellular transitions where epithelial cells undergo a cyclic transition from epithelial to mesenchymal (EMT) and back from mesenchymal to epithelial (MET). Two major pregnancy-associated tissue systems that use EMT, and MET are the fetal membrane (amniochorion) amnion epithelial layer and cervical epithelial cells and will be reviewed here. EMT is often associated with localized inflammation, and it is a well-balanced process to facilitate tissue remodeling. Cyclic transition processes are important because a terminal state or the static state of EMT can cause accumulation of proinflammatory mesenchymal cells in the matrix regions of these tissues and increase localized inflammation that can cause tissue damage. Interactions that determine homeostasis are often controlled by both endocrine and paracrine mediators. Pregnancy maintenance hormone progesterone and its receptors are critical for maintaining the balance between EMT and MET. Increased intrauterine oxidative stress at term can force a static (terminal) EMT and increase inflammation that are physiologic processes that destabilize homeostasis that maintain pregnancy to promote labor and delivery of the fetus. However, conditions that can produce an untimely increase in EMT and inflammation can be pathologic. These tissue damages are often associated with adverse pregnancy complications such as preterm prelabor rupture of the membranes (pPROM) and spontaneous preterm birth (PTB). Therefore, an understanding of the biomolecular processes that maintain cyclic EMT-MET is critical to reducing the risk of pPROM and PTB. Extracellular vesicles (exosomes of 40-160 nm) that can carry various cargo are involved in cellular transitions as paracrine mediators. Exosomes can carry a variety of biomolecules as cargo. Studies specifically using exosomes from cells undergone EMT can carry a pro-inflammatory cargo and in a paracrine fashion can modify the neighboring tissue environment to cause enhancement of uterine inflammation.