• Bulletin of the Korean Chemical Society
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• v.26 no.4
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• pp.641-644
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• 2005

Nucleophilic addition reactions of benzylamines $(XC_6H_4CH_2NH_2)\;to\;{\beta}$-cyanostilbenes ($YC_6H_4CH=C(CN)C_6H_4$Y’) have been studied in acetonitrile at 30.0 oC. A greater degree of N-$C_{\alpha}$ bond formation (larger ${\beta}_X$) is obtained with a stronger electron-withdrawing substituent in either ${\alpha}-\;(\delta\sigma_Y\;{\gt}\;0)\;or\;{\beta}-ring\;(\delta\sigma_{Y'}\;{\gt}$ 0). A stronger charge development is observed in the TS on $C_{\beta}\;(\rho_{Y'}$= 1.06 for X=Y=H) rather than on $C_{\alpha}\;(\rho_{Y}$ = 0.62 for X=Y’H) indicating the lag in the resonance development into the activating group (CN) on $C_{\beta}$ in the transition state. Similarly, the magnitude of $\rho$$_{XY'}$(−0.72) is greater than $\rho_{XY}$ (−0.66) due to a stronger interaction of the nucleophile with $\beta$-ring than $\alpha$-ring. The positive sign of $\rho_{YY'}$correctly reflects $\pi$ bond cleavage between the two rings in the TS. Relatively large kinetic isotope effects ($k_H/k_D\;{\geq}$ 2.0) involving deuterated nucleophiles ($XC_6H_4CH_2ND_2$) suggest a four-membered cyclic TS in which concurrent N-C$_{\alpha}$ and H(D)-C$_{\beta}$ bond formation occurs.

• Bulletin of the Korean Chemical Society
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• v.34 no.9
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• pp.2697-2701
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• 2013

The solvolysis rate constants of piperonyloyl chloride (1) in 27 different solvents are well correlated with the extended Grunwald-Winstein equation, using the $N_T$ solvent nucleophilicity scale, $Y_{Cl}$ solvent ionizing scale, and I aromatic ring parameter with sensitivity values of $0.30{\pm}0.05$, $0.71{\pm}0.02$, and $0.60{\pm}0.04$ for l, m, and h, respectively. The solvent kinetic isotope effect values (SKIE, $k_{MeOH}/k_{MeOD}$ and $k_{50%MeOD-50%D2O}$) of 1.16 and 1.12 were also in accord with the values for the $S_N1$ mechanism and/or the dissociative $S_N2$ mechanism. The product selectivity values (S) for solvolysis of 1 in alcohol/water mixtures were in the range of 0.5 to 1.9, which is also consistent with the proposed unimolecular ionization mechanism.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.17 no.2
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• pp.120-129
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• 2012

We investigated seasonal variation of sediment-water oxygen and inorganic nitrogen fluxes, and denitrification at tidal flat sediments located in the Nakdong River Estuary from July 2005 to September 2006. Net oxygen fluxes, measured with sediment incubations at in situ temperature, varied from -37.0 to $0.5mmol\;O_2\;m^{-2}\;d^{-1}$. Oxygen fluxes into the sediments from the overlying water increased due to the increased water temperature. Denitrification rate ($4{\sim}2732{\mu}mol\;N\;m^{-2}\;d^{-1}$) in this study was higher compared to the other Korean coast measured with the same method. Denitrification showed the same seasonal variation as oxygen fluxes. Denitrification rate based on $^{15}N$-nitrate showed a strong correlation with nitrate flux into the sediments from the overlying water. Denitrification via "water column supplied nitrate ($D_w$)", calculated from Isotope pairing technique, also correlated well with nitrate flux into the sediments. Nitrate from water column seems to account for seasonal variation of denitrification in Nakdong River Estuary. To understand general patterns and trends of biogeochemical processes of sediments in the Nakdong River Estuary, we categorized biogeochemical fluxes measured in this study according to direction and sizes of fluxes. Type 1(high oxygen and inorganic nitrogen fluxes into the sediments and high denitrification) occurred in summer, whereas Type 2(low oxygen and inorganic nitrogen fluxes into the sediments and low denitrification) occurred in rest of the season. Intertidal flat sediments seem to react sensitively to influence of freshwater from the Nakdong River.

• Analytical Science and Technology
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• v.25 no.1
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• pp.25-32
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• 2012

Isotope dilution mass spectrometry (ID-MS) based on liquid chromatography tandem mass spectrometry (LC/MS/MS) was developed for the accurate determination of sorbic acid in tea-drink. An isotope analogue of sorbic acid, $^{13}C_2$-sorbic acid, was obtained by custom synthesis. MS was operated in the negative mode with selected reaction monitoring (SRM) mode of $[M-H]^-$ ${\rightarrow}$ $[M-CO_2H]^-$ channel at m/z 111 ${\rightarrow}$ 67 for sorbic acid and at m/z 113 ${\rightarrow}$ 68 for its isotope analogue. Chromatographic separation was accomplished with a C18 column and an isocratic mobile phase of 55% of 50 mM ammonium acetate (pH 4.5) and 45% of methanol. Homogeneous reference materials were prepared for validation of this method, including repeatability and reproducibility tests, by fortifying tea-drink with sorbic acid in our laboratory. Repeatability and reproducibility studies showed that the ID-LC/MS method is a reliable and reproducible method which provides less than 3.8% of relative standard deviation (RSD) for the analysis of sorbic acid.

• The Journal of Engineering Geology
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• v.15 no.4 s.42
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• pp.391-405
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• 2005

Chemical and isotopic analysis for stream water, shallow groundwater, intermediate groundwater and deep groundwater was carried out to grasp hydrogeochemical characteristics of groundwater in the Heunghae area, Pohang city. Water type of stream water and shallow groundwaters is typified as Ca-Cl type, intermediate groundwater is $Na-HCO_3$, and deep groundwater is prominent in Wa-Cl type. $HCO_3^-\;and\;SiO_2$ in shallow groundwater are originated from weathering of silicate minerals, whereas those of deep groundwaters are resulted from weathering of carbonate minerals. Ca and Mg ions in both shallow and deep groundwaters are resulted from weathering of calcite and dolomite. $SO_4^{2-}$ in shallow groundwater is originated mainly from pyrite oxidation. As well depth increases, pH and TDS increase, but Eh and DO decrease. Alkali metal contents(K, Na, Li) increases as well depth increases, but alkali earth metal(Mg, Ca) and hi concentrations increase as well depth decreases. Anions, halogen elements(F, Cl, Br), and $HCO_3$ contents increase as well depth increases. The average stable isotope value of the groundwater of each depth is as follows; deep groundwater: ${\delta}^{18}O=-10.1\%o,\;{\delta}D=-65.8\%_{\circ}$, intermediate groundwater: ${\delta}^{18}O=-8.9\%_{\circ},\;{\delta}D=-59.6\%_{\circ}$, shallow groungwater : ${\delta}^{18}O=-8.0\%_{\circ},\;{\delta}D=-53.6\%_{\circ}$, surface water : ${\delta}^{18}O=-7.9\%_{\circ},\;{\delta}D=-53.3\%_{\circ}$ respectively.

• Proceedings of the Optical Society of Korea Conference
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• 2004.07a
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• pp.44-45
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• 2004

• Bulletin of the Korean Chemical Society
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• v.24 no.9
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• pp.1357-1360
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• 2003

• Bulletin of the Korean Chemical Society
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• v.20 no.9
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• pp.1017-1020
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• 1999

The aminolysis reactions of thiophenyl phenylacetates with benzylamines are investigated in acetonitrile at 55.0℃. Relatively large selectivity parameters, βx≒ 1.5, βz = -1.5~-1.8 and βxz = 0.92 together with the valid reactivity-selectivity principle are consistent with stepwise acyl transfer mechanism with rate limiting expulsion of the leaving group, thiophenolate anion, from the tetrahedral intermediate, T ± . The first order kinetics with respect to the benzylamine concentration and the realtively large secondary kinetic isotope effect (kH / kD = 1.2-1.7) involving deuterated benzylamine nucleophiles suggest a four center type transition state in which concurrent leaving group departure and proton transfer are involved.

• Bulletin of the Korean Chemical Society
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• v.20 no.5
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• pp.577-580
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• 1999

Solvolyses of phenyl chlorothionoformate in water, D2O, CH3OD, 50% D2O-CH3OD, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25.0℃. The Grunwald-Winstein plots of firstorder rate constants for phenyl chlorothionoformate with Ycl (based on 2-adamantyl chloride) show a dispersion phenomenon, and also the extended Grunwald-Winstein plots show a poor correlation for the solvolyses of phenyl chlorothionoformate. The ring parameter (I) has been shown to give considerable improvement when it is added as an hI term to the original and extended Grunwald-Winstein correlations. The dispersions in the Grunwald-Winstein correlations in the present studies are caused by the conjugation between the reaction center and the aromatic ring in the vicinity of the reaction center. This study has shown that the magnitude of l and m values associated with a change of solvent composition leads to predict the SN2 transition state. The kinetic solvent isotope effects determined in deuterated water and methanol are consistent with the proposed mechanism of the general base catalyzed SN2 mechanism.

• Korean Journal of Optics and Photonics
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• v.19 no.6
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• pp.435-438
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• 2008

D2O, which is used in nuclear power generation, is slightly different from $H_2O$. $D_2O$ consists of deuterium (D), which is an isotope of hydrogen (H) and has one more neutron than H. $D_2O$ is heavier by about 11% than $H_2O$, and $D_2O$ is present in water in natureat about 0.002%. Its melting point and boiling point are $3.81^{\circ}C$ and $101.42^{\circ}C$, respectively. $D_2O$ is harmful to the human body if it replaces water in the human body by more than $25%{\sim}50%$. We have measured the index of refractive and power absorption of 0%, 25%, 50%, 75%, and 100% of $D_2O$ in $H_2O$ using terahertz time-domain spectroscopy, and we have found that the refractive index decreases and power absorption also decreases as the concentration of $D_2O$ increases.