• Bulletin of the Korean Chemical Society
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• v.31 no.6
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• pp.1621-1627
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• 2010

The investigation of the catalytic activity of supported rhodium(I) complex [Rh(P-S)$(CO)_2$] (P-S; polymer anchored salicylic acid) toward the reductive carbonylation of nitrobenzene in DMF medium has been reported. Use of basic cocatalysts in the reaction medium enhanced the percentage of more useful phenyl carbamates. Spectroscopic studies indicate that the reaction proceeds through a dimer species [Rh(HS)(CO)(C(O)$OCH_3$)(${\mu}-OCH_3)]_2$ and phenyl isocyanate is formed as an intermediate. A plausible reaction mechanism based on the identification of reactive intermediates from the soluble rhodium variety has been proposed for the carbonylation process.

• Journal of the Korean Society of Food Science and Nutrition
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• v.26 no.6
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• pp.1252-1257
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• 1997

In order to investigate the immunomodulatory mechanism of white ginseng, the effects of total saponin of Ginsenoside Rb$_2$component on the phagocytosis and reactive oxygen intermediate(ROI) production of mouse peritoneal macrophages were studied. Both phagocytosis assay nitrobluetetrazolium reduction test showed 20$\mu\textrm{g}$/ml concentration of total saponin significantly increased the activity of phagocytosis and production of ROI. Also cytokine gene expression of the macrophages was analyzed using reverse transcription polymerase chain reaction. In the RT-PCR assay, 20$\mu\textrm{g}$/ml concentration of either total saponin or Ginsenoside Rb$_2$increased IL-1 and TNF expression of the macrophages.

• Bulletin of the Korean Chemical Society
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• v.35 no.8
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• pp.2448-2452
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• 2014

Second-order rate constants ($k_N$) have been measured spectrophotometrically for $S_NAr$ reactions of Y-substituted-phenoxy-2,4-dinitrobenzenes (1a-1g) with hydrazine and glycylglycine in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. Hydrazine is 14.6-23.4 times more reactive than glycylglycine. The magnitude of the ${\alpha}$-effect increases linearly as the substituent Y becomes a stronger electron-withdrawing group (EWG). The Br${\o}$nsted-type plots for the reactions with hydrazine and glycylglycine are linear with ${\beta}_{lg}=-0.21$ and -0.14, respectively, which is typical for reactions reported previously to proceed through a stepwise mechanism with expulsion of the leaving group occurring after rate-determining step (RDS). The Hammett plots correlated with ${\sigma}^{\circ}$ constants result in much better linear correlations than ${\sigma}^-$ constants, indicating that expulsion of the leaving group is not advanced in the transition state (TS). The reaction of 1a-1g with hydrazine has been proposed to proceed through a five-membered cyclic intermediate ($T_{III}$), which is structurally not possible for the reaction with glycylglycine. Stabilization of the intermediate $T_{III}$ through intramolecular H-bonding interaction has been suggested as an origin of the ${\alpha}$-effect exhibited by hydrazine.

• Journal of the Korean Ceramic Society
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• v.35 no.1
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• pp.23-32
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• 1998

Al2O3/Al composites were produced by immersing the sintered silica preform in molten aluminum which contained magnesium as impurity. Three distinct regions existed in the penetration behavior of molten me-tal with changing the reaction temperature. These regions are denoted as low temperature regime(75$0^{\circ}C$-85$0^{\circ}C$) intermediate regime(90$0^{\circ}C$-95$0^{\circ}C$) and high temperature regime(100$0^{\circ}C$$\leq$) In the low temperature regime the penetration speed of molten aluminum increased with increasing reaction temperature whereas it decreased in the intermediate regime due to the phase transition of alumina formed by displacement reac-tion. In the high temperature regime the penetration speed of molten aluminum was the highest at 100$0^{\circ}C$ which was 3.6 mm/hr But above 105$0^{\circ}C$ molten aluminum did not penetrate into the silica preform because of the formation of a dense spinel layer at the preform surface by magnesium in molten Al.

• Bulletin of the Korean Chemical Society
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• v.25 no.9
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• pp.1379-1384
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• 2004

Rearrangements of 1,3-oxathiolane sulfoxides 8 and 9 in the presence of base are described from a mechanistic viewpoint of sigmatropic and elimination reactions. In the presence of triethylamine the (Z)-sulfoxide 8 gave the corresponding thiolsulfinate 10 by way of dimerization of the sulfenic acid intermediate 2 at room temperature while the (E)-sulfoxide 9 was recovered even after refluxing in ethyl acetate by the reversal of the [2,3]-sigmatropic rearrangement of the sulfenic acid 4. Triethylamine promoted the developing charge separation in the transition state of the sigmatropic rearrangement of the (Z)-sulfoxide 8 to facilitate the ring opening to the sulfenic acid 2. The reason for more facile ring opening of the (Z)-sulfoxide 8 in comparison with the corresponding (E)-sulfoxide 9 is attributable to the differences in the reactivity of the hydrogen adjacent to the carbonyl group. Triethylamine was not strong base to deprotonate the carbonyl-activated methylene hydrogen of the (E)-sulfoxide 9 but enough to catalyze the sigmatropic process of the sulfoxides. The sulfenic acid 2 dimerized to the thiolsulfinate 10 while the sulfenic acid 4 proceeded the sigmatropic ring closure. In the presence of strong base such as potassium hydroxide, the elimination reaction was predominant over the sigmatropic rearrangement. In this reaction condition, both sulfoxides 8a and 9a gave a mixture of the disulfide 12, the isomeric disulfide 14, and the sulfinic acid 13. Under the strong alkaline condition an elimination of activated hydrogen from the carbon adjacent to the carbonyl group to furnish the sulfenic acid 2a and the isomeric sulfenic acid 18. The formation of the transient intermediate in the reaction was proven by isolation of the isomeric disulfide 14. The reactive entity was regarded as the sulfenic acid rather than sulfenate anion under these reaction conditions.

• Journal of the Mineralogical Society of Korea
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• v.16 no.1
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• pp.107-123
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• 2003

The objective of this study was to investigate mineral precipitates, which derived from the zero valent iron (ZVI) corrosion during TCE dechlorination and to find the controlling factors in mineral precipitates. A series of column experiemnts were conducted to evaluate the location of ZVI and the effects of electrode arrangements in electro-enhanced permeable reactive barrier (E2PRB) systems. Based on mineralogical study, ZVI samples near the influent port had more lepidocrocite, ferrihydrite or Fe (oxy)hydroxide, and (phospho)siderite while backward samples had more akaganeite, magnetite/maghemite, and intermediate green rust (GR) I and GR II. A suite of mineral distribution was preferabley related to the dissolved oxygen and the increased pH. Controlling factors of mineral precipitates in an E2PRB system were found to be (1) pH, (2) dissolved oxygen, (3) the types of Fe intermediates, and (4) anionic species to form complex strongly.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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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.

• Journal of Microbiology and Biotechnology
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• v.30 no.8
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• pp.1252-1260
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• 2020

(R)-2-(4-hydroxyphenoxy)propionic acid (HPOPA) is a key intermediate for the preparation of aryloxyphenoxypropionic acid herbicides (R-isomer). In order to improve the HPOPA production from the substrate (R)-2-phenoxypropionic acid (POPA) with Beauveria bassiana CCN-A7, static cultivation and H₂O₂ addition were attempted and found to be conducive to the task at hand. This is the first report on HPOPA production under static cultivation and reactive oxygen species (ROS) induction. On this premise, the cultivation conditions and fermentation medium compositions were optimized. As a result, the optimal carbon source, organic nitrogen source, and inorganic nitrogen source were determined to be glucose, peptone, and ammonium sulfate, respectively. The optimal inoculum size and fermentation temperature were 13.3% and 28℃, respectively. The significant factors including glucose, peptone, and H₂O₂, identified based on Plackett-Burman design, were further optimized through Central Composite Design (CCD). The optimal concentrations were as follows: glucose 38.81 g/l, peptone 7.28 g/l, and H₂O₂ 1.08 g/l/100 ml. Under the optimized conditions, HPOPA titer was improved from 9.60 g/l to 19.53 g/l, representing an increase of 2.03-fold. The results obtained in this work will provide novel strategies for improving the biosynthesis of hydroxy aromatics.

• Bulletin of the Korean Chemical Society
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• v.29 no.10
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• pp.1915-1919
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• 2008

Second-order rate constants ($k_N$) have been measured spectrophotometrically for reactions of 3,4-dinitrophenyl benzoates (5b) with a series of alicyclic secondary amines in 80 mol % $H_2O$/20 mol % DMSO at 25.0 ${\pm}$ 0.1 ${^{\circ}C}$. The kinetic data have been compared with the data reported previously for the corresponding reactions of 2,4- dinitrophenyl benzoates (5a) to investigate the effect of changing the nucleofuge from 2,4-dinitrophenoxide to 3,4-dinitrophenoxide on reactivity and mechanism. The kinetic results show that aminolyses of 5a and 5b proceed through the same mechanism, i.e., a zwitterionic tetrahedral intermediate ($T^{\pm}$) with a change in the rate-determining step (RDS). Substrate 5a is more reactive than 5b when breakdown of $T^{\pm}$ is the RDS but less reactive when formation of $T^{\pm}$ is the RDS. Dissection of kN values into the microscopic rate constants (e.g., $k_1$ and $k_2/k_{-1 }$ ratio) has revealed that 5a results in larger $k_2/k_{-1}$ ratios but smaller k1 values than 5b for all the amines studied. Since 2,4-dinitrophenoxide is less basic and a better nucleofuge than 3,4-dinitrophenoxide, the larger $k_2/k_{-1}$ ratios determined for the reactions of 5a than for those of 5b are as expected. The steric hindrance exerted by the ortho-nitro group on 5a contributes to the smaller k1 values found for the reactions of 5a than for those of 5b.

• Proceedings of the Korean Institute of Information and Commucation Sciences Conference
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• 2018.10a
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• pp.152-155
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• 2018

Over the past years, Link Flooding Attacks (LFAs) have been introduced as new network threats. LFAs are indirect DDoS attacks that selectively flood intermediate core links, while legacy DDoS attacks directly targets end points. Flooding bandwidth in the core links results in that a wide target area is affected by the attack. In the traditional network, mitigating LFAs is a challenge since an attacker can easily construct a link map that contains entire network topology via traceroute. Security researchers have proposed many solutions, however, they focused on reactive countermeasures that respond to LFAs when attacks occurred. We argue that this reactive approach is limited in that core links are already exposed to an attacker. In this paper, we present SDHoneyNet that prelocates vulnerable links by computing static and dynamic property on Software-defined Networks (SDN). SDHoneyNet deploys Honey Topology, which is obfuscated topology, on the nearby links. Using this approach, core links can be hidden from attacker's sight, which leads to effectively building proactive method for mitigating LFAs.