• Bulletin of the Korean Chemical Society
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• 제23권8호
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• pp.1089-1096
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• 2002

Solvolyses rate constants of trimethylacetyl chloride (2), isobutyryl chloride (3), diphenylacetyl chloride (4) and p-methoxyphenylacetyl chloride (5) in 2,2,2-trifluoroethanol (TFE)-water, 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)-water and TFE-et hanol solvent systems at $10^{\circ}C$ are determined by a conductimetric method. Kinetic solvent isotope effects (KSIE) are reported from additional kinetic data for methanolyses of various substituted acetylchlorides in methanol According to the results of those reactions analyzed in terms of rate-rate profiles,extended Grunwald-Winstein type correlations, application of a third order reaction model based a general base catalyzed (GBC) and KSIE values. Regardless of the kind of neighboring groups (CH3- or Ph-groups) of reaction center, for aqueous fluorinated alcohol systems, solvolyses of 2, 3, 4, and 5 were exposed to the reaction with the same mechanism (a loose SN2 type mechanism by electrophilic solvation) controlled by a similarity of solvation of the transition sate (TS). Whereas, for TFE-ethanol solvent systems, the reactivity depended on whether substituted acetyl chloride have aromatic rings (Ph-) or alkyl groups (CH3-); the solvations by the predominant stoichiometric effect (third order reaction mechanism by GBC and/or by push-pull type) for Ph- groups (4 and 5) and the same solvation effects as those shown in TFE-water solvent systems for CH3- groups (2 and 3) were exhibited Such phenomena can be interpreted as having relevance to the inductive effect ( $\sigmaI)$ of substituted groups; the plot of log (KSIE) vs. ${\sigma}I$ parameter give an acceptable the linear correlation with r = 0.970 (slope = 0.44 $\pm$ 0.06, n = 5).

• 한국정보디스플레이학회:학술대회논문집
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• 한국정보디스플레이학회 2004년도 Asia Display / IMID 04
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• pp.1072-1075
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• 2004

Ion shower doping using a source gas of $PH_3/H_2$ was conducted on excimer-laser-annealed (ELA) Poly-Si. As-implanted damage is accumulated more and more with the increase of an acceleration voltage and a doping time. In this study we found that dopant-activation is relatively a rapid kinetic-process while damage-recovery is not.

• Environmental Analysis Health and Toxicology
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• 제13권3_4호
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• pp.71-75
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• 1998

Carbendazim, which is widely used fungicide, was investigated for rat hepatocarcinogenesis using a medium-term carcinogenicity bioassay. All rats were initially given a single dose (200mg/kg) of diethylnitrosamine (DEN) i.p. and then, starting 2 weeks later, carbendazim treatment group and positive control group received carbendazim (7 mg/kg/ day) and 2-acetylaminofluorene (2-AAF, 1%), respectively, in the diet for 6 weeks. All rats were subjected to two-thirds partial hepatectomy (PH) at week 3 and sacrificed at week 8. Carcinogenic potential was scored by comparing the number and area per cm$^2$ of induced glutathione-S-transferase placental form (GST-P) positive foci in the liver. Carbendazim had no effect in the increase of body weight, hematological and biochemical values, and the number and area of GST-P positive loci. These results suggest that this bioassay using DEN-PH method can be useful for detection of hepatocarcinogenic potentials of pesticide.

• 대한기계학회:학술대회논문집
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• 대한기계학회 2008년도 추계학술대회B
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• pp.2385-2389
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• 2008

This is the experimental research that tries to explain a variety of RH is how to affect the cell performance and the flooding phenomenon of proton exchange membrane fuel cell (PEMFC). A value of PH changes to 0%, 50% and 90% as its variation, either stoichiometric flow rate changes to 1.5, 2 and 4. Into the comparison between theoretical and experimental value, this study analyzes that a variety of PH is how 10 affect flooding in the cathode of the proton exchange membrane fuel cell. The effect of air stoichiometry, air humidity and different flow fields are also discussed in this paper This study has accomplished the measurement of performance as the variety of RH in the cathode of proton exchange membrane fuel cell, moreover it has recorded the visualization of flooding in the cathode with a high-speed micro camera.

• 산업경영시스템학회지
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• 제30권1호
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• pp.33-40
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• 2007

A multi-server queueing system with finite buffer is considered. The input flow is the BMAP (Batch Markovian Arrival Process). The service time has the PH (Phase) type distribution. Customers from the BMAP enter the system according to the discipline of partial admission. Besides ordinary (positive) customers, the Markovian flow (MAP) of negative customers arrives to the system. A negative customer can delete an ordinary customer in service if the state of its PH-service process belongs to some given set. In opposite case the ordinary customer is considered to be protected of the effect of negative customers. The stationary distribution and the main performance measures of the considered queueing system are calculated.

• 한국표면공학회지
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• 제37권1호
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• pp.40-48
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• 2004

Hardness and internal stress are very important in nickel electroforming. Nickel sulfamate bath has been widely used in electroforming because of its low internal stress and moderate hardness. Nickel sulfamate bath without chloride was chosen to investigated the effect of plating variable such as temperature, PH, current density and sodium naphthalene trisulfonate as addition agent on the hardness and internal stress. It was found that hardness increased with increasing temperature and decreasing current density and ranged from 150∼310 DPH. The hardness was highest at $55^{\circ}C$ and 10∼40 mA/$\textrm{cm}^2$. The internal stress increased with increasing current density and decreasing temperature. It was minimum at PH 3.0∼3.8. Low internal stress within $\pm$1,500 psi was obtained at both $50^{\circ}C$ and $55^{\circ}C$ in 10-20 mA/$\textrm{cm}^2$. The addition of sodium naphthalene trisulfonate was found to be effective in refine columnar grains thus resulted in decreasing internal stress, increasing hardness and improving brightness.

• 한국동물학회지
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• 제8권2호
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• pp.28-32
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• 1965

It is well known that many kinds of chemical or metalic agent which were ionized or undissociated at toxified external medium and remarkable effect occurred to the fresh water fish. The effects of hydrogen ion concentration on serum protein of fresh water fish, (phycephalus argus CANTOR) had not been reported yet. In this point, authors attempted to study the changes of A/G ratio, total protein, hemoglobin, hematocrit, RBC , liver and kidney weight of snake head in the above environment. 95 snake heads were subjected to external medium with PH-4.5 and A/G ratio, hematocrit, hemoglobin, total protein, RBC, and liver & kidney weight were measured at 32.80, 15202000 and 272 hours respectively. In whole experimental period, L 1 and L2 globulin increased, on the other, albumin decreased as compare with control . Hence, the A/G ratio decreased remarkably . Though, total protein increased prominently through the whole experimental period, hematocrit, hemoglobin, RBC, increased only at 80 hours, and then decreased as compared to the control. Liver weight revealed distinctive increase at 80 hours, but no remarkable change could be seen there after. Hence, kidney weight revealed continuous rise. By these results, it may be said that as snake head were subjected to external medium with PH-4.5, this environmental factor influenced protein metabolism , blood component and organs.

• Bulletin of the Korean Chemical Society
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• 제24권9호
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• pp.1251-1255
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• 2003

Second-order rate constants have been determined spectrophotometrically for the reaction of phenyl 4-nitrophenyl carbonate with a series of primary amines in $H_2O$ containing 20 mol % DMSO at 25.0 ${\circ}$C. The Bronsted-type plot is linear with a ${\beta}_{nuc}\;0.69 {\pm} 0.04$, which is slightly smaller than the ${\beta}_{nuc}$ values for the reactions of 4-nitrophenyl acetate ( $\beta_{nuc}= 0.82 {\pm} 0.03$) and benzoate ( $\beta_{nuc} = 0.76 {\pm} 0.01$), indicating that the reaction proceeds through a tetrahedral zwitterionic intermediate $T^{\pm}$. The carbonate is more reactive than the corresponding acetate and benzoate. The changing Me (or Ph) to PhO has resulted in a decrease in the ${\beta}_{nuc}$ value without changing the reaction mechanism but an increase in the reactivity. The electronic effect of the substituent in the nonleaving group appears to be responsible for the enhanced reactivity of the carbonate compared with the corresponding acetate and benzoate.

• Bulletin of the Korean Chemical Society
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• 제18권3호
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• pp.300-305
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• 1997

Effect of a nonionic surfactant, Tween 20 on the adsorption and kinetic mechanism for the hydrolysis of a microcrystalline cellulose, Avicel PH 101, by endoglucanase Ⅰ (Endo Ⅰ) and exoglucanase Ⅱ (Exo Ⅱ) isolated from Trichoderma viride were studied. The Langmuir isotherm parameters, amount of maximum adsorption (Amax) and adsorption equilibrium constant (Kad) for the adsorption, were obtained in the presence and the absence of nonionic surfactant. On the addition of Tween 20, the Kad and Amax values of Exo Ⅱ were decreased, while those of Endo Ⅰ were not affected. These indicate that the adsorption affinity of Exo Ⅱ on the cellulose is weakened by nonionic surfactant, and the surfactant enhanced desorption of Exo Ⅱ from insoluble substrate. The enzymatic hydrolysis of the cellulose can be described by two parallel pseudo-first order reactions using the percentages of easily (Ca) and hardly (Cb) hydrolyzable cellulose in Avicel PH 101 and associated rate constants (ka and kb). The Ca value was increased by adding Tween 20 for all enzyme samples (Exo Ⅱ, Endo Ⅰ and their 1:1 mixture) implying that the low-ordered crystalline fraction in the cellulose may be partly dispersed by surfactant. The ka value was not affect by adding Tween 20 for all enzyme samples (Exo Ⅱ, Endo Ⅰ and their 1:1 mixture). The kb value of Exo Ⅱ was increased by adding Tween 20, while that of Endo Ⅰ was not affected. This suggests that the surfactant helps the Exo Ⅱ desorb from microcrystalline cellulose, and increase the hydrolysis rate. These results were show that the increase of hydrolysis of cellulose by the nonionic surfactant is due to both the activation of Exo Ⅱ and partial defibrillation of the cellulose.

• Bulletin of the Korean Chemical Society
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• 제30권12호
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• pp.2913-2917
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• 2009

Second-order rate constants (k$_{Nu–}$) have been measured for nucleophilic substitution reactions of Y-substituted phenyl benzoates (1a-i) with butane-2,3-dione monoximate ($Ox^-\;an\;\alpha$-nucleophile) and Z-substituted phenoxides in 80 mol% H$_2$O/20 mol% DMSO at 25.0${\pm}$0.1$^{\circ}C$. Hammett plots correlated with ${\sigma}^o$ and ${\sigma}^-$ constants for reactions of 1a-h with Ox$^–$ exhibit many scattered points. In contrast, the Yukawa-Tsuno plot results in a good linear correlation with ${\rho}_Y$ = 2.20 and r = 0.45, indicating that expulsion of the leaving group occurs in the rate-determining step (RDS). A stepwise mechanism with expulsion of the leaving-group being the RDS has been excluded, since Y-substituted phenoxides are less basic and better nucleofuges than Ox$^–$. Thus, the reactions have been concluded to proceed through a concerted mechanism. Ox$^–$ is over 10$^2$ times more reactive than its reference nucleophile, 4-chlorophenoxide (4-ClPhO$^–$). One might suggest that stabilization of the transition-state (TS) through intramolecular general acid/base catalysis is responsible for the ${\alpha}$-effect since such general acid/base catalysis is not possible for the corresponding reactions with 4-ClPhO$^–$. However, destabilization of the ground-state (GS) of Ox$^–$ has been concluded to be mainly responsible for the ${\alpha}$-effect found in this study on the basis of the fact that the magnitude of the ${\alpha}$-effect is independent of the nature of the substituent Y.