• Bulletin of the Korean Chemical Society
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• v.33 no.2
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• pp.663-669
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• 2012

The nucleophilic substitution reactions of dibutyl chlorophosphate (3) with substituted anilines ($XC_6H_4NH_2$) and deuterated anilines ($XC_6H_4ND_2$) are investigated kinetically in acetonitrile at $55.0^{\circ}C$. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse ($k_H/k_D$ = 0.86-0.97) with the strongly basic anilines while primary normal ($k_H/k_D$ = 1.04-1.10) with the weakly basic anilines. The DKIEs, steric effects of the two ligands, activation parameters, cross-interaction constants, variation trends of the kH/kD values with X, and mechanism are discussed for the anilinolyses of the nine ($R_1O$)($R_2O$)P(=O)Cl-type chlorophosphates. A concerted mechanism is proposed with a backside nucleophilic attack transition state for the strongly basic anilines and with a frontside attack involving a hydrogen-bonded four-center-type transition state for the weakly basic anilines on the basis of the magnitudes, secondary inverse and primary normal, and variation trends of the $k_H/k_D$ values with X.

• Tunnel and Underground Space
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• v.16 no.6 s.65
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• pp.476-485
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• 2006

During blasting, both shock wave and gas are generated in detonation process of explosives and the generated wave and gas expansion may create new fractures and damage rock mass. In order to explain and understand completely the fracture mechanism by blasting, we have to consider both effects of the wave and gas expansion simultaneously. In this study, we use a discrete element code, PFC2D and develop an algorithm which is capable of modeling both detonation and gas pressures acting on blasthole wall and visualizing generated cracks within rock mass. Moreover, the gas-pressure modeling method which applies a corresponding external force of gas pressure to parent particles of radial fractures is adopted to simulate a coopting between rock mass and gas penetrating created radial fractures. The developed algorithm is verified by reproducing numerical simulations of a lab-scale test blast successfully.

• BMB Reports
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• v.33 no.3
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• pp.228-233
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• 2000

The steady-state investigation of the mechanism of Dhydroxyisovalerate dehydrogenase was performed in order to understand this type of kinetic patterns. The initial velocity was measured with various amounts of both substrates, NADPH and 2-ketoisovalerate. Double reciprocal plots gave patterns that conversed on or near the abscissa. Binding studies indicated that NADPH bound first to the enzyme. The product $NADP^+$ was found to be a competitive inhibitor with respect to NADPH at a constant concentration of 2-ketoisovalerate. However, it showed noncompetitive inhibition against 2-ketoisovalerate at a fixed amount of NADPH. Another product, D-hydroxyisovalerate, was a non-competitive inhibitor versus NADPH and 2-ketoisovalerate at constant levels of 2-ketoisovalerate and NADPH, respectively. These results were comparable with an ordered bi-bi mechanism, in which NADPH bound first to the enzyme, followed by the binding of 2- ketoisovalerate. $NADP^+$ is the last product to be released. The ordered reaction manner of D-hydroxyisovalerate dehydrogenase from 2-ketoisovalerate to D-hydroxyisovalerate allows the accurate regulation of valine metabolism and it may lead to the regulation of total biosynthesis of enniatins in the Fusarium species.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3811-3816
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• 2013

Nucleophilic substitution reactions of ethyl methyl (2), ethyl propyl (4) and diisopropyl (7) chlorothiophosphates with substituted anilines and deuterated anilines are investigated kinetically in acetonitrile at $55.0^{\circ}C$. A concerted mechanism is proposed based on the selectivity parameters. The deuterium kinetic isotope effects (DKIEs; $k_H/k_D$) are secondary inverse ($k_H/k_D=0.66-0.99$) with 2, primary normal and secondary inverse ($k_H/k_D=0.78-1.19$) with 4, and primary normal ($k_H/k_D=1.06-1.21$) with 7. The primary normal and secondary inverse DKIEs are rationalized by frontside attack involving hydrogen bonded, four-center-type transition state, and backside attack involving in-line-type transition state, respectively. The anilinolyses of ten chlorothiophosphates are examined based on the reactivity, steric effect of the two ligands, thio effect, reaction mechanism, DKIE and activation parameter.

• Journal of Digital Convergence
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• v.11 no.11
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• pp.233-242
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• 2013

Securing the appropriability strategy of R&D funding for technology innovation is very important because R&D needs a lot of time and money. Appropriability means the environmental factors that govern an innovator's ability to capture profits generated by an innovation. Generally appropriability mechanism has five kinds, including patent, secrecy, lead time advantage, complementary sales & service, complementary manufacturing. In this paper, we surveyed domestic software industry professionals about appropriability mechanism strategy, and presented a result of priority of each factor and difference between previous research and this study, using the pair-wise comparison method. The result of study showed that domestic IT manufacturing companies prefer patent better than other appropriability mechanism.

• Bulletin of the Korean Chemical Society
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• v.32 no.5
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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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• v.35 no.1
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• pp.111-116
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• 2014

The kinetics and mechanism of oxidation of sulfanilic acid by N-chloro-p-toluene sulfonamide (chloramine-T) have been studied in acid medium. The species of chloramine-T were analysed on the basis of experimental observations and predominantly reactive species was taken into account for proposition of most plausible reaction mechanism. The derived rate law (1) conforms to such a mechanism. $$-\frac{d[CAT]}{dt}=\frac{kK_1[RNHCl][SA]}{K_1+[H^+]}$$ (1) All kinetic parameters were evaluated. Activation parameters such as energy and entropy of activation were calculated to be $(61.67{\pm}0.47)kJmol^{-1}$ and $(-62.71{\pm}2.48)kJmol^{-1}$ respectively employing Eyring equation.

• Wind and Structures
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• v.10 no.5
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• pp.421-435
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• 2007

A two-dimensional flutter analysis method (2d-3DOF method) was developed to simultaneously investigate the relationship between oscillation parameters and aerodynamic derivatives of three degrees of freedom, and to clarify the coupling effects of different degrees of freedom in flutter instability. With this method, the flutter mechanism of two typical bridge deck sections, box girder section and two-isolated-girder section, were numerically investigated, and both differences and common ground in these two typical flutter phenomena are summarized. Then the flutter stabilization effect and its mechanism for long-span bridges with box girders by using central-slotting were studied by experimental investigation of aerodynamic stability and theoretical analysis of stabilizing mechanism. Possible explanation of new findings in the evaluation trend of critical wind speed through central vent width is finally presented.

• Journal of the Korean Society of Manufacturing Process Engineers
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• v.21 no.9
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• pp.78-84
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• 2022

An air circuit breaker (ACB) is an electrical protection device that interrupts abnormal fault currents that result from overloads or short circuits in a low-voltage power distribution line. The ACB consists of a main circuit part for current flow, mechanism part for the opening and closing operation of movable conductors, and arc-extinguishing part for arc extinction during the breaking operation. The driving mechanism of the ACB is a spring energy charging type. The faster the contact opening speed of the movable conductors during the opening process, the better the breaking performance. However, there is a disadvantage that the durability of mechanism decreases in inverse proportion to the use of a spring capable of accumulating high energy to configure the breaking speed faster. Therefore, to simultaneously satisfy the breaking performance and mechanical endurance of the ACB, its driving mechanism must be optimized. In this study, a dynamic model of the ACB was developed using the MDO(Mechanism Dynamics Option) module of CREO, which is widely used in multibody dynamics analysis. To improve the opening velocity, the Taguchi design method was applied to optimize the design parameters of an ACB with many linkages. In addition, to evaluate the improvement in the operating characteristics, the simulation and experimental results were compared with the MDO model and improved prototype sample, respectively.

• The KIPS Transactions:PartD
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• v.11D no.1
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• pp.61-68
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• 2004

Now, the representative researching trends of view managements for improving the query processing in multi-database system are focused on the materialized view mechanism and the signature view index mechanism. But when we compare with both mechanisms, the former mechanism's access time is faster than one of the latter's, and needs large space. The latter mechanism needs small space and the access time is slower than one of the former. These mechanisms are trade-off each other. Therefore, in case of query process using the view management, we are to improve the system performance and to reduce the access cost of disk input and output by suggesting a new mechanism mixing both the materialized view mechanism and the signature view index mechanism. We suggested that the structure of metadata and the algorithm about the new mired mechanism.