• Journal of the Korean Chemical Society
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• v.22 no.3
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• pp.158-163
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• 1978

The four 1,1-disubstituted 2-vinylcyclopropanes, 1,1-diphenyl-2-vinylcyclopropane (1a), 1,1-dicyano-2-vinylcyclopropane(1b), ethyl 1-cyano-2-vinylcyclopropanecarboxylate(1c), and diethyl 2-vinylcyclopropane-1,1-dicarboxylate(1d) rearranged below $300{\circ}C$ to the corresponding 4,4-disubstituted cyclopentenes, 4,4-diphenylcyclopentene(2a), 3-cyclopentene-1,1-dicarboxylate(2d). Diphenpyl derivative 1a rearranged almost quantitatively to 4,4-diphenylcyclopentene(2a) at the temperature of $250{\circ}C$. Although dicyano derivative 1b in solution underwent the thermal rearrangement at rather low temperature of $170{\circ}C$, the other vinylcyclopropanes, 1c and 1d, in solution rearranged thermally above $220{\circ}C$. In the thermal reaction of 1b, 1c, and 1d considerable amounts of polymers 3 were also produced. Also detected product was the ring-opened diene, ethyl 2-cyano-2,4-hexadienoate(4), in case of the pyrolysis of 1c. The observed facile rearrangement of disubstituted vinylcyclopropanes was explained by the radical stabilization effect of substituents on the diradical intermediates 5.

• Korean Chemical Engineering Research
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• v.45 no.5
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• pp.460-465
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• 2007

Endosulfan-${\alpha}$ endosulfan-${\beta}$ and endosulfan-sulfate, which are classified as pesticides, were degraded by use of UV energy and ultrasonic irradiation. The degradation residuals were analysed by gas chromatography with an electron capture detector and TOC (total oragnic carbon) analysis. The reactions were conducted in a quartz annular reactor equipped with a low pressure mercury multilamp (8Wx2) and a sonic generator. All the aqueous solutions were concentrated as 10 mg/L initially. Endosulfans were degraded each to result in 48.2% (${\alpha}$), 50.0% (${\beta}$) and 76.5% (sulfate) of removal efficiency by UV energy, and 66.9% (${\alpha}$), 55.8% (${\beta}$) and 72.7% (sulfate) by ultrasonic irradiation, respectively. In contrast to the results of the single-component solutions, degradation of the endosulfan-sulfate was greatly suppressed to result in the lowest degradation rate and removal efficiency in the three-component solutions. This finding suggests that there should be a reversible reaction with a substantially low equilibrium constant between endosulfan-${\alpha}$ or -${\beta}$ and -sulfate in the coexistence of the three endosulfans. TOC data showed the endosulfans were decomposed by 20%~40% toward complete mineralization, producing a quantity of intermediates induced by the radical reactions. We found that all the decay reactions considered in this study nicely fell into pseudo first-order rate.

• Korean Chemical Engineering Research
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• v.49 no.1
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• pp.56-61
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• 2011

Alkyl vinyl ethers such as methyl vinyl ether, propyl vinyl ether, isopropyl vinyl ether, butyl vinyl ether and isobutyl vinyl ether are usually used as industrial solvents and chemical intermediates in the chemical or pharmaceutical industry. Recently, they are popularly used as raw materials for polymer electrolyte membrane fuel cells and as cellulose dyeing assistants. However, very few investigations about process design and operation data were reported for alkyl vinyl ether compounds and there are no data for propyl vinyl ether(PVE) systems as far as we know. In this work, the isothermal VLE data are reported at 333.15 K for the ternary systems of {PVE + ethanol + benzene} by using headspace gas chromatography(HSGC) and these VLE data were correlated using Wilson, NRTL and UNIQUAC equations. The excess volumes($V^E$) and deviations in molar refractivity(${\Delta}R$) data are also reported for the sub binary systems {PVE + ethanol}, {ethanol + benzene} and {PVE + benzene} at 303.15 K. These data were correlated with Redlich-Kister equation. In addition, isoclines of $V^E$ and DR for ternary system {PVE + ethanol + benzene} were also calculated from Radojkovi equation.

• Korean Chemical Engineering Research
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• v.47 no.3
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• pp.292-302
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• 2009

The wet oxidation of phenol has been investigated at temperatures from 150 to $250^{\circ}C$ and oxygen partial pressures from 25.8 to 75.0 bar with initial pH of 1.0 to 12.0 and initial phenol concentration of 10 g/l. Chemical Oxygen Demand COD has bee measured to estimate the oxidation rate. Reaction intermediates have been identified and their concentration profiles have been determined using liquid chromatography. The destruction rate of phenol have shown the first-order kinetics with respect to phenol and the changes in COD during wet oxidation have been described well with the lumped model. The impact of various homogeneous catalysts, such as $Cu^{2+}$, $Fe^{2+}$, $Zn^{2+}$, $Co^{2+}$ and $Ce^{3+}$ ions, on the destruction rate of phenol and COD has also been studied. The homogeneous catalyst of $CuSO_4$ has been found to be the most effective for the destruction of phenol and COD during wet oxidations. The destruction rate of formic acid formed during wet oxidations of phenol have increased as increasing temperature and $CuSO_4$ concentration. The final concentrations of acetic acid which has been formed during wet oxidations and difficult to oxidize have increased with reaction temperature and with decrease in the catalyst load.

• The Journal of the Korea Contents Association
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• v.10 no.4
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• pp.359-366
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• 2010

The purpose of this study is to examine the influence of the leisure constraint of a private security guard on his/her task stress and life satisfaction. The subjects of this study were chosen among the private security guards working in Seoul based private security firms in 2009, and by going through judgement sampling, 300 cases were applied in the final analysis. Collected data went through factor analysis, reliability analysis, regression analysis, and path analysis by using SPSSWIN 17.0. In reference with the reliability of the questionnaire, Cronbach's $\alpha$ was over .600. The conclusion of this study is as following. Firstly, the leisure constraint of a private security guard affects his/her task stress. In other words, when peripheral and individual constraint increase, task stress is intensified, while task stress winds down when interpersonal constraint decreases. Secondly, the leisure constraint of a private security guard affects life satisfaction. That is, when individual constraint goes down, life satisfaction is improved. Thirdly, the task stress of a private security guard affects life satisfaction. when compensation and career development increase, life satisfaction rises. On the other hand when task characteristic is weakened, life satisfaction gets lower. Fourthly, the leisure constraint of a private security guard has a causal influence on task stress and life satisfaction. Accordingly, it becomes apparent that the task stress is a significant variable which intermediates the relation between leisure constraint and life satisfaction.

• Journal of Korean Society of Environmental Engineers
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• v.27 no.8
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• pp.822-828
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• 2005

The photocatalytic degradation of methyl parathion was carried out using a circulating $TiO_2$/solar system. Under the photocatalytic condition, parathion was more effectively degraded than by the photolysis or $TiO_2$ only condition. The parathion degradation followed pseudo first-order kinetics. With photocatalysis, 10 mg/L parathion was completely degraded within 90 min with a TOC decrease exceeding 63% after 150 min. The nitrogen from parathion was recovered mainly as ${NO_2}^-$, ${NO_3}^-$, and ${NH_4}^+$, 80% of sulfur as ${SO_4}^{2-}$, and less than 5% of phosphorus as ${PO_4}^{3-}$ during photocatalysis. The organic intermediates 4-nitrophenol and paraoxon were also identified, and these were further degraded. Two different bioassays using V. fischeri and D. magna were employed to measure the toxicity reduction in the solutions treated by both photocatalysis and photolysis. Relative toxicity was reduced almost completely after 150 min in both organisms under the photocatalysis, whereas in photolysis, 76 and 57% reduction was achieved for V. fischeri and D. magna, respectively. The acute toxicity reduction pattern corresponded with the decrease in parathion and TOC concentrations.

• Journal of Korean Society of Environmental Engineers
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• v.30 no.10
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• pp.1039-1046
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• 2008

The combining process of UV irradiation and H$_2$O$_2$ was used to investigate characteristics of cefaclor decomposition in the aquatic environment. The separate mixing tank was used to minimize the decreasing effective of contact area caused by sampling. Four baffles were installed inside the UV reactor for the complete mixing of the sample and outside of the reactor was wrapped with aluminum foil to protect the emission of photon energy. Production of OH radical was measured using pCBA(p-Chlorobenzoic acid) indirectly and rate constants were withdrawn pseudo-frist order reaction. Optimum condition for the maximum production of OH radical was found to be pH 3, hydrogen peroxide of 5 mmol/L and recirculation rate of 400 mL/min. Pseudo-frist order reaction rate constant was 0.1051 min$^{-1}$. In the optimum condition, cefaclor was completely decomposed within 40 min and rate constant was 0.093 min$^{-1}$. Decomposition by OH radical producted intermediate anions such as chloride, nitrate, sulfite and acetic acid and phenylglycine. After 6 hr most cefaclor was decomposed by UV/H$_2$O$_2$ process and converted to CO$_2$ and H$_2$O, resulting of operation in the decrease of TOC and acetic acid and the disappearance of phenylglycine.

• Korean Journal of Environmental Agriculture
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• v.10 no.2
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• pp.167-177
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• 1991

O-ethyl S-methyl ethylphosphonothioate [$LD_{50}$ (rat, oral) 4.6mg/kg ; $K_i$(bovine erythrocyte acetylcholinesterase) 303 $M^{-1\;min-1}$] was selected as a model compound to study the mode of action of O, S-dialkyl alkylphosphonothioates which have been hypothesized to be toxic via a bioactivation process. Two chemical oxidants, meta-chloroperoxybenzoic acid and monoperoxyphthalic acid, and rat liver microsomal oxidases were used to mimic the action of mixed function oxidases on the model compound. The formation of S-oxide, a very unstable active intermediate, was proposed based on the identification of metabolic products.Furthermore, a trapping experiment with ethanol showed that the unstable intermediate S-oxide had the ability to phosphorylate acetylcholinesterase which is an important enzyme in nerve systems. The S-oxide intermediates are presumed to be responsible for the toxicity of O,S-dialkyl alkylphosphonothioates.

• Toxicological Research
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• v.13 no.4
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• pp.339-347
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• 1997

Disulfiram (DSF) and diethyldithiocarbamate (DDC), a reduced form of DSF, protect the liver against toxicant-induced injury through inhibition of cytochrome P450 2E1. The effect of DSF and DDC on the levels of major hepatic microsomal epoxide hydrolase (mEH) and glutathione S-transferase (GST) expression was comparatively studied, given the view that these enzymes are involved in terminal detoxification events for high energy intermediates of xenobiotics. Treatment of rats with a single dose of DSF (20-200 mg/kg, po) resulted in 2- to 15-fold increases in the mEH mRNA level at 24 hr with the ED$_{50}$ value being noted as 60 mg/kg. The mEH mRNA level was elevated ~15-fold at 24 hr after treatment at the dose of 100 mg/kg, whereas the hepatic mRNA level was rather decreased from the maximum at the dose of 200 mg/kg, indicating that DSF might cause cytotoxicity at the dose. In contrast to the effect of DSF, DDC only minimally elevated the mEH mRNA level at the doses employed. DSF moderately increased the major GST mRNA levels in the liver as a function of dose, resulting in rGSTA2, rGSTA3/5 or rGSTM1 mRNA levels being elevated 3- to 4-fold at 24 hr post-treatment, whereas the rGSTM2 mRNA level was not altered. DDC, however, failed to stimulate the mRNA levels for major GST subunits, indicating that the reduced form of DSF was ineffective in stimulating the GST the expression. The effect of other organosulfides including aldrithiol, 2, 2'-dithiobis(benzothiazole) (DTB), tetramethylthiouram disulfide (TMTD) and allyl disulfide (ADS) on the hepatic mEH and GST mRNA expression was assessed in rats in order to further confirm the increase in the gene expression by other disulfides. Treatment of rats with aldrithiol (100 mg/kg, po) resulted in a 16-fold increase in the mEH mRNA level at 24 hr post-treatment. DTB, TMTD and ADS also caused 5-, 9- and 12-fold increases in the rnRNA level, respectively, as compared to control. Thus, all of the disulfides examined were active in stimulating the mEH gene in the liver. The organosulfides significantly increased the rGSTA2, rGSTA3, rGSTA5 and rGSTM1 mRNA levels at 24 hr after administration. In particular, aldrithiol was very efficient in stimulating the rGSTA and rGSTM genes among the disulfides examined. These results provide evidence that DSF and other sulfides effectively stimulate the mEH and major GST gene expression at early times in the liver and that DDC, a reduced form of DSF, was ineffective in stimulating the expression of the genes, supporting the conclusion that reduced form(s) of organosulfur compound(s) might be less effective in inducing the mEH and GST genes through the antioxidant responsive element(s).

• Applied Chemistry for Engineering
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• v.20 no.5
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• pp.486-492
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• 2009

Wet oxidations (WO) of quinoline in aqueous solution were carried out at $225^{\circ}C$ and $250^{\circ}C$. In the WO at $250^{\circ}C$, quinoline was degraded completely within 30 min and the reduction in total organic carbon (TOC) of 63% was achieved during 120 min. However, the rate of the reduction in TOC was only 13% within 240 min during the WO at $225^{\circ}C$. Nicotinic and acetic acid were found to be main intermediates formed during the oxidation of quinoline. With the addition of the homogeneous catalyst $CuSO_4$ or more easily oxidizable phenol, WOs of quinoline were also carried out under moderate conditions at $200^{\circ}C$. The catalytic WO with $CuSO_4$ of 0.20 g/L showed the destruction rates of quinoline and TOC comparable to those in the WO at $250^{\circ}C$. The WOs of quinoline-phenol mixture exhibited induction periods to degrade quinoline and phenol during which free radicals were produced to initiate WOs. With increasing initial concentrations of phenol at a given initial concentration of quinoline, the induction periods in the destructions of quinoline and phenol became shorter and the reduction in TOC increased from 60% to 75% during 180 min of the WOs. The reduction rate of an induction period decreased as increasing the initial concentration ratio of phenol to quinoline. On the other hand, phenol degradation in the WOs of quinoline-phenol mixtures required a longer induction period and proceeded slower compared to the case of the WO of phenol.