• Bulletin of the Korean Chemical Society
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• v.27 no.12
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• pp.2023-2027
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• 2006

Dibenzyl sulfide was oxidized at the a-carbon to yield benzaldehyde in the presence of $Pd(NO_3)_2$. Oxygen itself could not oxidize the sulfide directly, instead the nitrato ligand of the palladium complex transferred oxygen to dibenzyl sulfide to form benzaldehyde. The X-ray crystal structure of the intermediate complex, cis-[$Pd(NO_3)_2${$S(CH_2C_6H_5)_2$}$_2$], revealed that the nitrato ligand was unidentate. Para-substituted dibenzyl sulfides I, $(YC_6H_4CH_2)_2S $wherein Y = $OCH_3$, $CH_3$, Cl, CN, or $NO_2$, were synthesized and reacted with palladium nitrate, and those with electron-donating substituents (Y = $OCH_3$ and $CH_3$) were good substrates for the oxidation reaction with palladium nitrate. Thus, the reaction mechanism of the oxygen transfer was proposed to include nucleophilic benzylic carbon.

• Bulletin of the Korean Chemical Society
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• v.31 no.4
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• pp.829-834
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• 2010

Ligand variation was carried out on a cobalt(III) complex of Salen-type ligand comprised of 1,2-cyclohexenediamine and salicylaldehyde bearing a methyl substituent on 3-position and -[$CMe(CH_2CH_2CH_2N^+Bu_3)_2$] on 5-position, which is a highly active catalyst for $CO_2$/propylene oxide copolymerization. Replacement of the methyl substituent with bulky isopropyl group resulted in alteration of the binding mode, consequently lowering turnover frequency significantly. Replacement with an ethyl group preserved binding mode and activity. Replacement of the tributylammonium unit with trihexylammonium or trioctylammonium, or replacement of 1,2-cyclohexenediamino unit with -$NC(Me)_2CH_2N$- decreased activity, even though the binding mode was unaltered.

• Bulletin of the Korean Chemical Society
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• v.30 no.4
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• pp.846-848
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• 2009

Two modifications of the ${\alpha}\;and\;{\beta}$ forms of propyl mercaptan nickel(II) cluster, [$Ni_6(SCH_2CH_2CH_3)_{12}$], have been synthesized and their crystal structures have been determined by single-crystal X-ray diffraction. The alkyl groups are away from $Ni_6$ ring in $\alpha$ form whereas they are near to the Ni atom in $\beta$ form. The distance of Ni-H in $\beta$ form [2.576(5) $\AA$] is much shorter than that in $\alpha$ form [3.101(2) $\AA$]. In the crystal lattice of $\beta$ form, the whole structure forms a flower shape.

• Journal of Preventive Medicine and Public Health
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• v.25 no.1 s.37
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• pp.13-25
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• 1992

This study was conducted to investigate the mechanism of protective effect by sodium selenite in methylmercuric chloride neurotoxicity, increasing intracellular $Ca^{2+}$concentration of the neuron. Methylmercuric chloride of 3mg/kg of body weight was administered simultaneously with sodium selenite of 5mg/kg and pretreatment of sodium selenite via intraperitoneal injection to rats. Also, effect of methylmercuric chloride($25{\mu}M,\;50{\mu}M,\;100{\mu}M$) and sodium selenite($200{\mu}M$) on free intrasynaptosomal $Ca^{2+}$ concentration were studied using the fluorescent $Ca^{2+}$ indicator fura -2 in vitro. After the treatment, at 6, 24, and 48 hours later, mercury in the cerebral cortex, liver and kidney tissues, succlnic dehydrogenase activities, adenosin-5'-triphosphate concentration, acetylcholinesterase activities, and intracellular $Ca^{2+}$ concentration in the cerebral cortex were determined in vivo. Cerebral synaptosomes of rats were incubated with methylmercuric chloride and sodium selenite in Hepes buffer for 10 minutes and free intrasynaptosomal $Ca^{2+}$ concentration were measured with fura-2 in vitro. The results were summarized as follows ; 1. The combined administration of $CH_3HgCl$ and $Na_2SeO_3$ and pretreatment of $Na_2SeO_3$ according to time significantly more increased in the cerebral cortex and decreased in the liver, kidney mercury concentrations compared to the administration of $CH_3HgCl$ only. 2. The combined administration of $CH_3HgCl$ and $Na_2SeO_3$ and pretreatment of $Na_2SeO_3$ increased more succinic dehydrogenase and acetylcholinesterase activities compared to the administration of $CH_3HgCl$ only. Particularly pretreatment of $Na_2SeO_3$ significantly more compared to the administration of $CH_3HgCl$ only. The concentration of adenosine-5'-triphosphate in $Na_2SeO_3$ treatment groups revealed a favourable effect compared to the administration of $CH_3HgCl$ only. 3. Intracellular $Ca^{2+}$ concentration in administration of $CH_3HgCl$ only was increased significantly more than control group in all test hours but was increased significantly more at 48 hours only after treatment in combined administration of $CH_3HgCl$ and $Na_2SeO_3$ and pretreatment of $Na_2SeO_3$ according to time interval more decreased significantly intracellular $Ca^{2+}$ concentration compared to the administration of $CH_3HgCl$ only. 4. Free intrasynaptosomal $Ca^{2+}$ concentration in the combined administration of $CH_3HgCl$ and $Na_2SeO_3$ was decreased ($24%{\sim}40%$) significantly more than the administration of $CH_3HgCl$ only. From the above results, the specific dosage of $Na_2SeO_3$ decreased increment of intracellular $Ca^{2+}$ concentration induced by administration of $CH_3HgCl$. These findings suggest the protective mechanism of $Na_2SeO_3$ on the neurotoxicity of $CH_3HgCl$.

• Journal of the Korean Chemical Society
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• v.22 no.3
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• pp.150-157
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• 1978

The rate constants for the hydrolysis of the derivatives of N-(p-nitrophenyl)-benzohydrazonyl azide (p-$CH_3,\;p-CH_3O,\;p-NO_2$, p-Cl, p-Br) have been determined by UV spectrophotometry in 50% dioxane-water at $25^{\cicr}C$ and a rate equation which can be applied over wide pH range was obtained. Below pH 5, the rate of hydrolysis of hydrazonyl azides is accelerated by electron-donating group ($\rho$ = -0.47), whereas at the pH values greater than 7, the $\rho$-value is 0.68. The effect of salt, solvent, substituent and azide ion on the rate of hydrolysis are rationalized in terms of $S_N1$ and $S_N2$ mechanism; below pH 5, the hydrolysis proceed through $S_N1$, however, above pH 7, the hydrolysis is started by the attack of hydroxide ion and in the range of pH 5∼7, these two reactions occur competitively.

• Journal of Korean Society for Atmospheric Environment
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• v.20 no.6
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• pp.783-792
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• 2004

In this study, a thick-film semiconductor odor gas sensor for the detection of $CH_3$SH was developed using SnO$_2$ as the main substrate and was investigated in terms of its sensitivity and reaction time. In the process of manufacturing the sensor, Taguchi's design of experiment (DOE) was applied to analyze the effects of a variety of parameters, including the substrate, the additives and the fabrication conditions, systematically and effectively. Eight trials of experiments could be possible using the 27 orthogonal array for the seven factors and two levels of condition, which originally demands 128 trials of experiments without DOE. The additives of Sb$_2$O$_{5}$ and PdCl$_2$ with the H$_2$PtCl$_{6}$ ㆍ6$H_2O$ catalyst were appeared to be important factors to improve the sensitivity, and CuO, TiO$_2$, V$_2$O$_{5}$ and PdO were less important. In addition, TiO$_2$, V$_2$O$_{5}$ and PdO would improve the reaction time of a sensor, and CuO, Sb$_2$O$_{5}$, PdCl$_2$ and H$_2$PtCl$_{6}$ㆍ6$H_2O$ were negligible. Being evaluated simultaneously in terms of both sensitivity and reaction time, the sensor showed the higher performance with the addition of TiO$_2$ and PdO, but the opposite results with the addition of CuO, V$_2$O$_{5}$, Sb$_2$O$_{5}$ and PdCl$_2$. The amount of additives were superior in the case of 1% than 4%. H$_2$PtCl$_{6}$ㆍ6$H_2O$ would play an important role for the increase of sensor performance as a catalyst.nce as a catalyst.

• Journal of the Korean Chemical Society
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• v.35 no.4
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• pp.368-373
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• 1991

Palladium(II) complexes of the type Pd(IEAA-NR)$_2$ (R = H, CH$_3$, C$_2$H$_5$, n-C$_3$H$_7$, n-C$_4$H$_9$, or CH$_2$C$_6$H$_5$), where IEAA-NR represents N-alkyl derivative of isonitrosoethylacetoacetate (H-IEAA) imine, have been prepared. And the structure of the complexes have been studied by elemental analyses, electronic, infrared, $^1$H and $^{13}$C-NMR spectra. It is proposed that both of IEAA-NR ligands coordinate to metal through nitrogens of imine and isonitroso groups to form 5-membered chelate rings in the complexes.

• Bulletin of the Korean Chemical Society
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• v.32 no.6
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• pp.1897-1901
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• 2011

This report shows the rates of solvolyses for phenyl methanesulfonyl chloride ($C_6H_5CH_2SO_2Cl$, I) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, 2,2,2-trifluroethanol (TFE) and 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) are reported. Three representative solvents, studies were made at several temperatures and activation parameters were determined. The thirty kinds of solvents gave a reasonably precise extended Grunwald-Winstein plot, coefficient (R) of 0.954. The sensitivity values (l = 0.61 and m = 0.34, l/m = 1.8) of phenyl methanesulfonyl chloride (I) were smaller than those obtained for benzenesulfonyl chloride ($C_6H_5SO_2Cl$, II; l = 1.01 and m = 0.61) and 2-propanesulfonyl chloride ($(CH_3)_2CHSO_2Cl$, III; l = 1.28 and m = 0.64). As with the two previously studied solvolyses, an $S_N2$ pathway with somewhat ionization reaction is proposed for the solvolyses of I. The activation parameters, ${\Delta}H^{\neq}$ and ${\Delta}S^{\neq}$, were determined and they are also in line with values expected for a bimolecular reaction mechanism. The kinetic solvent isotope effect of 2.34 in $CH_3OH/CH_3OD$ is in accord with a bimolecular mechanism, probably assisted by general-base catalysis.

• Journal of Korea Soil Environment Society
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• v.2 no.1
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• pp.63-72
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• 1997

This study presents a surveying of methane and carbon dioxide at sanitary landfills. The following results are obtained. (1) The majority of methane and the half of carbon dioxide pour out from vertical gas vents. (2) The quantity of carbon dioxide in cove. soil was greater than methane. (3) Even though gas extrusion in side slop area was small, the quantity of gas extrusion in side slop area was much greater than in coversoil area as especially carbon dioxide rate. (4) As were carried raw refuse layer, methane extrusion was trace, but carbon dioxide was large. (5) Gas extrusion quantity were changed by the compaction of soil, and the operating area of refuse. (6) Carbon dioxide portioned much larger in the whole landfill, but methane portioned much larger in gas vent and coversoil.

• Economic and Environmental Geology
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• v.29 no.3
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• pp.357-367
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• 1996

A total of 113 samples (basalts, tuffs, and siltstones from coal-bearing sediments) was collected from 14 sites of the Tertiary Changgi basin in southeastern Korea, and studied palaeomagnetically. Site-mean declination of the ChRM from 5 sites was found to be deflected clockwise about $30^{\circ}$. Other 5 sites showed no vertical-axis deflection of ChRM direction. In consideration of previous palaeomagnetic data from other Tertiary basins in the vicinity, it is interpreted that the deflection of ChRM directions has been caused by NNW-SSE simple shear associated with the opening of the East Sea, and the time of rotation should be about 16 Ma. Other 2 sites showed counterclockwise deflection of site-mean ChRM. These sites might be located among lager tectonic blocks which were rotating clockwise. AMS (anisotropy of magnetic susceptibility) study revealed $NE{\rightarrow}SW$ directed magnetic lineation at two tuffaceous sites. This might indicate flow direction of tuffs during the time of deposition. Most of the other sites showed load-foliation lying subparallel to the bedding plane. This must have been caused by gravitational loading acted vertically to the strata.