• Journal of the Korean Applied Science and Technology
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• v.15 no.2
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• pp.49-57
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• 1998

This study is to develop a new synthetic method for the nitroarenes via non-electrophilic substitution. Direct nitration at the C-1 position of isoquinoline has never been reported and substitution in isoquinoline under the normal nitration condition occurs at C-5 and C-8. We have demonstrated a facile one-step sythetic method for the nitration of isoquinolines at the C-1 position, which involves the electrophilic attack of a $DMSO-Ac_2O$ complex, followed by nucleophilic addition of nitrate ion to this intermediate. Since the reaction is simple and mild, this method has preparative merit since 1-nitroisoquinolines are not readily accessible by other methods. Application to the synthesis of poly nitroarenes from the corresponding anilines was also described.

• Bulletin of the Korean Chemical Society
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• v.33 no.2
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• pp.689-691
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• 2012

• Applied Chemistry for Engineering
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• v.10 no.7
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• pp.1092-1095
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• 1999

The well-known mixed-acid process for the aromatic nitration requires subsequent separation of spent acid, mainly dilute sulfuric acid. A novel nitration process using $HNO_3-NO_2-O_3$ was tested in a small pilot scale with 3 mol of p-nitrotoluene. Nitrogen dioxide(14.3 mol) was added three times in parts into the solution of p-nitrotoluene and $HNO_3$(6 mol) in dichloroethane. The nitration proceeded to more than 97% conversion within 5.5 h using 0.871 mol/h of ozone. As a clean process of aromatic nitration, this method is expected to replace the present process which causes the environmental problems.

• Applied Chemistry for Engineering
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• v.9 no.7
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• pp.1085-1089
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• 1998

The well-established nitric acid-sulfuric acid mixed acid process for the nitration of aromatic compounds has serious problems due to the large amount of waste acids and severe reaction conditions. Nitration of toluene can be conducted using nitrogen dioxide and ozone instead of mixed acid. We found that conc. nitric acid increased the reactivity as catalyst and the amount of nitrogen dioxide controlled the extent of nitration. Dinitration proceeded to more than 92 mole % conversion within 2 hr at $0^{\circ}C$ with 6 eq. of nitrogen dioxide and 2 eq./hr of ozone flow. Toluene completed mononitration within 30 min using 3 eq. of nitrogen dioxide, 3 eq. of nitric acid, and 1.5 eq./hr of ozone flow. As a clean process of aromatic nitration, this method is expected to replace the present process which causes the environmental problems.

• Journal of Microbiology and Biotechnology
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• v.27 no.2
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• pp.297-305
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• 2017

The use of peroxidase in the nitration of phenols is gaining interest as compared with traditional chemical reactions. We investigated the kinetic characteristics of phenol nitration catalyzed by horseradish peroxidase (HRP) in an aqueous-organic biphasic system using n-butanol as the organic solvent and ${NO_2}^-$ and $H_2O_2$ as substrates. The reaction rate was mainly controlled by the reaction kinetics in the aqueous phase when appropriate agitation was used to enhance mass transfer in the biphasic system. The initial velocity of the reaction increased with increasing HRP concentration. Additionally, an increase in the substrate concentrations of phenol (0-2 mM in organic phase) or $H_2O_2$ (0-0.1 mM in aqueous phase) enhanced the nitration efficiency catalyzed by HRP. In contrast, high concentrations of organic solvent decreased the kinetic parameter $V_{max}/K_m$. No inhibition of enzyme activity was observed when the concentrations of phenol and $H_2O_2$ were at or below 10 mM and 0.1 mM, respectively. On the basis of the peroxidase catalytic mechanism, a double-substrate ping-pong kinetic model was established. The kinetic parameters were ${K_m}^{H_2O_2}=1.09mM$, ${K_m}^{PhOH}=9.45mM$, and $V_{max}=0.196mM/min$. The proposed model was well fit to the data obtained from additional independent experiments under the suggested optimal synthesis conditions. The kinetic model developed in this paper lays a foundation for further comprehensive study of enzymatic nitration kinetics.

• Bulletin of the Korean Chemical Society
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• v.27 no.7
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• pp.1056-1058
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• 2006

• Bulletin of the Korean Chemical Society
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• v.35 no.4
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• pp.1241-1243
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• 2014

• Applied Chemistry for Engineering
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• v.7 no.3
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• pp.530-535
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• 1996

Nitrochlorobenezenes are used as intermediates for dyes, pharmaceuticals and perfumes. By far the most common industrial nitration process employs a mixture of nitric acid and sulfuric acid. Due to water formed in the reaction, the mixed acid nitration requires subsequent separation of spent acid, mainly dilute sulfuric acid. In the stream of ozone, nitrogen dioxide can be used as a nitrating agent for the nitration of chlorobenzene. With 6eq of $NO_2$ and 1.0eq/hr of ozone flow, the mononitration of chlorobenzene ended within 3hr at $0^{\circ}C$ while the dinitration of chlorobenzene did in 12hr. This method can be employed for the nitration of some aromatic compounds to reduce pollutants from the present mixed-acid process.

• Bulletin of the Korean Chemical Society
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• v.33 no.4
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• pp.1279-1284
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• 2012

Silica supported $Cs_{2.5}H_{0.5}PMo_{12}O_{40}$ catalyst was prepared through sol-gel method with ethyl silicate-40 as silicon resource and characterized by X-ray diffraction, infrared spectroscopy, scanning electron microscopy, nitrogen adsorption-desorption and potentiometric titration methods. The $Cs_{2.5}H_{0.5}PMo_{12}O_{40}$ particles with Keggin-type structure well dispersed on the surface of silica, and the catalyst exhibited high surface area and acidity. The catalytic performance of the catalysts for benzene liquid-phase nitration was examined with 65% nitric acid as nitrating agent, and the effects of various parameters were tested, which including temperature, time and amount of catalyst, reactants ratio, especially the recycle of catalyst was emphasized. Benzene was effectively nitrated to mononitro-benzene with high conversion (95%) in optimized conditions. Most importantly, the supported catalyst was proved has excellent stability in the nitration progress, and there were no any other organic solvent and sulfuric acid were used in the reaction system, so the liquid-phase nitration of benzene that we developed was an eco-friendly and attractive alternative for the commercial technology.

• Tribology and Lubricants
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• v.13 no.4
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• pp.33-39
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• 1997

In order to establish a new temperature criterion to prevent the pistons from ring sticking due to deposit formation, bench test and engine test were performed. The effects of oil degradation and temperature on deposit formation was studied by a modified panel coking test. Oil degradation was analyzed by FTIR. Oil oxidation and nitration were selected as a factors to evaluate oil degradation. Bench test results show that oil oxidation is more effective to the deposit formation than oil nitration. And the temperature increase accelerates deposit formation and deposit formation increase rapidly above 26$0^{\circ}C$. Especially, in case of degraded oil, the deposit formation increases so rapidly that ring sticking can occur. The effect of piston temperature on the deposit formation was confirmed by engine test.