• Bulletin of the Korean Chemical Society
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• v.23 no.10
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• pp.1459-1462
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• 2002

The kinetics of the addition of X-substituted benzylamines (BA) to Y-substituted Benzylideneacetylacetones (BAA) have been investigated in acetonitrile at $25.0^{\circ}C$. The reaction is studied under pseudo-first-order conditions by keeping a large excess of BA over BAA. The addition of BA to BAA occurs in a single step in which the addition of BA to $C_\alpha$ of BAA and proton transfer from BA to $C_\beta$ of BAA take place concurrently with a four-membered cyclic transition state structure. The magnitude of the Hammett ($p_X$) and Bronsted ($\beta_x$) coefficients are rather small suggesting an early tansition state (TS). The sign and magnitude of the cross-interaction constant, $p_{XY}$ (= -0.49), is comparatible to those found in the normal bond formation processes in the $S_N2$ and addition reactions. The normal kinetic isotope effect ($K_H/K_D$ > 1.0) and relatively low $\Delta$H^{${\neq}$}$ and large negative $\Delta$S^{${\neq}$}$ values are also consistent with the mechanism proposed.

• Bulletin of the Korean Chemical Society
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• v.32 no.12
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• pp.4337-4340
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• 2011

The vitamin D receptor binding peptide, VDRBP, was overexpressed as a fused form with the ubiquitin molecule in Rosetta(DE3)pLysS, a protein production strain of Escherichia coli harboring an induction controller plasmid. The fusion protein was bound to the immobilized metal ions, and the denaturation and renaturation of the fusion protein were performed as a part of the purification procedure. After the elution of the fusion protein, the peptide hormone was released from its fusion partner by using yeast ubiquitin hydrolase (YUH), and subsequently purified by reverse phase chromatography. The purity of the resulting peptide fragment was checked by MALDI-TOF mass and NMR spectroscopy. The final yields of the target peptide were around 5 and 2 mg per liter of LB and minimal media, respectively. The recombinant expression and purification of this peptide will enable structural and functional studies using multidimensional NMR spectroscopy and X-ray crystallography.

• Analytical Science and Technology
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• v.10 no.4
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• pp.240-245
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• 1997

An accurate analysis method for the determination of lead in whole blood by ICP/MS was developed. Whole blood samples were decomposed in microwave digestion system without any contamination and loss of lead. The 96 samples were analyzed by ICP/MS using mass$^{208}$ isotope of lead. Lead concentrations of human whole blood were ranged of $2.50{\sim}22.8{\mu}g/dL$. The accuracy of this analysis method was verified by analyzing of NIST SRM 955a series(lead in blood).

• Bulletin of the Korean Chemical Society
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• v.18 no.9
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• pp.1017-1021
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• 1997

Solvolyses of p-methoxyphenyl chloroformate in water, D2O, CH3OD, 50% D2O-CH3OD, and in aqueous binary mixtures of acetone, ethanol and methanol are investigated at 25.0 ℃. Product selectivities are reported at 25 ℃ for a wide range of ethanol-water and methanol-water solvent compositions. The Grunwald-Winstein plots of first-order rate constants for p-methoxyphenyl chloroformate with YCl (based on 1-adamantyl chloride) show marked dispersions into three separate curves for the three aqueous mixtures with a small m value and a rate maximum for aqueous alcohol solvents. Third-order rate constants, kww, kaw, kwa and kaa were calculated from the observed kww and kaa values together with kaw and kwa calculated from the intercept and slope of the plot of 1/S vs. [alcohol]/[water]. The calculated rate constants, kcalc and mol % of ester agree satisfactorily with those of the observed rate constants, kobs and mol % of ester, supporting the stoichiometric solvation effect analysis. The kinetic solvent isotope effects determined in water and methanol are consistent with the proposed mechanism of the general base catalyzed carbonyl addition-elimination.

• Bulletin of the Korean Chemical Society
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• v.20 no.12
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• pp.1451-1456
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• 1999

Solvolyses of α-methoxy-α-(trifluoromethyl)phenylacetyl chloride in H₂O, D₂O, CH₃OD, 50% D₂O-CH₃OD, and in aqueous binary mixtures of acetone, dioxane, ethanol and methanol are investigated at 25.0℃. The Grunwald-Winstein plots of first-order rate constants for α-methoxy- α-(trifluoromethyl)phenylacetyl chloride with $Y_{Cl}$ show a dispersion phenomenon. Solvent nucleophilicity N has been shown to give considerable im-provement when it is added as an 1N term to the original Grunwald-Winstein for the solvolyses of α-methoxy- α-(trifluoromethyl)phenylacetyl chloride. The dispersions in the Grunwald-Winstein correlations in the present studies are caused by solvent nucleophilicity. The magnitude of l and m values associated with a change of solvent composition predicts the associative $S_N2$ transition state. The kinetic solvent isotope effects determined in deuterated water and methanol are consistent with the proposed mechanism of the general base catalyzed associative $S_N2$ or $S_AN$ mechanism for the of α-methoxy- α-(trifluoromethyl)phenylacetyl chloride.

• The Sea:JOURNAL OF THE KOREAN SOCIETY OF OCEANOGRAPHY
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• v.14 no.2
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• pp.80-89
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• 2009

The rates of sediment oxygen demand(SOD) and denitrification(DNF) were measured using $^{15}N$ isotope pairing technique in intact sediment cores in the shelf of Dok Island. The SOD and DNF in the continental shelf of Dok Island were ranged from 1.04 to $9.08\;mmol\;m^{-2}\;d^{-1}$ and from 7.06 to $37.67\;{\mu}mol\;m^{-2}\;d^{-1}$, respectively. The SOD and DNF values in this study are higher than typical deep sea sediment. The SOD and DNF in this study were high in the high organic matter content sediment and high organic matter content was promotive of coupled nitrification-denitrification. Organic carbon contents in surface sediment ranged from 1.8 to 2.4%, which is higher than typical deep sea sediments. Therefore we conclude that the organic matter content in surface sediment is determined by the nature of the export production not the water depth in East sea sediment and the nature of the export production also determines remineralization processes such as SOD and DNF in East sea/Ulleung Basin sediment.

• Bulletin of the Korean Chemical Society
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• v.30 no.10
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• pp.2413-2418
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• 2009

Rates of solvolyses of 4-nitrophenyl phenyl thiophosphorochloridate (4-N$O_2$PhOP(S)(Cl)OPh, $\underline{1}$) in ethanol, methanol, and aqueous binary mixtures incorporating ethanol, methanol, acetone, and 2,2,2-trifluroethanol (TFE) are reported. Thermodynamic parameters were determined at several temperatures in three representative solvents. The extended Grunwald-Winstein equation was applied to 29 solvents and the correlation coefficient (R) showed 0.959. The sensitivities (l = 1.37 and m = 0.62) are similar to those obtained for diphenyl thiophosphorochloridate (($PhO)_2$PSCl, $\underline{2}$), diphenyl phosphorochloridate (($PhO)_2$POCl, $\underline{3}$), diphenyl phosphinic chloride ($Ph_2$POCl, $\underline{4}$), and diphenyl thiophosphinic chloride ($Ph_2$PSCl, $\underline{5}$). The solvolytic reaction mechanism of 4-nitrophenyl phenyl thiophosphorochloridate ($\underline{1}$) is suggested to be proceeded a $S_N$2 process as previously reported result. The activation enthalpies are shown as slightly low as ${\Delta}H^{\neq}\;=\;9.62\;to\;11.9\;kcal{\cdot}mol^{-1}$ and the activation entropies are shown as slightly high negative value as ${\Delta}S^{\neq}\;=\;-34.1\;to\;-44.9\;cal{\cdot}mol^{-1}{\cdot}K^{-1}$ compared to the expected $S_N$2 reaction mechanism. Kinetic solvent isotope effects are accord with a typical $S_N$2 mechanism as shown in the range of 2.41 in MeOH/ MeOD and 2.57 in $H_2O/D_2O$ solvent mixtures.

• Economic and Environmental Geology
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• v.36 no.6
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• pp.391-405
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• 2003

The Daebong gold-silver deposit consists of mesothermal massive quartz veins thar are filling the fractures along fault shear (NE, NW) Bones within banded or granitic gneiss of Precambrian Gyeonggi massif. Based on vein mineralogy, ore textures and paragenesis, ore mineralization of this deposits is composed of massive white quartz vein(stage I) which was formed in the same stage by multiple episodes of fracturing and healing, and transparent quartz vein(stage II) which is separated by a major faulting event. Stage I is divided into the 3 substages. Ore minerals of each substages are as follows: 1) early stage I=magnetite, pyrrhotite, arsenopyrite, pyrite, sphalerite, chalcopyrite, 2) middle stage I=pyrrhotite, arsenopyrite, pyrite, marcasite, sphalerite, chalcopyrite, galena, electrum and 3) late stage I=pyrite, sphalerite, chalcopyrite, galena, electrum, argentite, respectively. Ore minerals of the stage II are composed of pyrite, sphalerite, chalcopyrite, galena and electrum. Systematic studies (petrography and microthermometry) of fluid inclusions in stage I and II quartz veins show fluids from contrasting physical-chemical conditions: 1) $H_2O-CO_2-CH_4-NaCl{\pm}N-2$ fluid(early stage I=homogenization temperature: 203∼3$88^{\circ}C$, pressure: 1082∼2092 bar, salinity: 0.6∼13.4 wt.%, middle stage I=homogenization temperature: 215∼28$0^{\circ}C$, salinity: 0.2∼2.8 wt.%) related to the stage I sulfide deposition, 2) $H_2O-NaCl{\pm}CO_2$ fluid (late stage I=homogenization temperature: 205∼2$88^{\circ}C$, pressure: 670 bar, salinity: 4.5∼6.7 wt.%, stage II=homogenization temperature: 201-3$58^{\circ}C$, salinity: 0.4-4.2 wt.%) related to the late stage I and II sulfide deposition. $H_2O-CO_2-CH_4-NaCl{\pm}N_2$ fluid of early stage I is evolved to $H_2O-NaCl{\pm}CO_2$ fluid represented by the $CO_2$ unmixing due to decrease in fluid pressure and is diluted and cooled by the mixing of deep circulated meteoric waters ($H_2O$-NaCl fluid) possibly related to uplift and unloading of the mineralizing suites. $H_2O-NaCl{\pm}CO_2$ fluid of stage II was hotter than that of late stage I and occurred partly unmixing, mainly dilution and cooling for sulfide deposition. Calculated sulfur isotope compositions ({\gamma}^{34}S_{H2S}$) of hydrothermal fluids (3.5∼7.9%o) indicate that ore sulfur was derived from mainly an igneous source and partly sulfur of host rock. Measured and calculated oxygen and hydrogen isotope compositions ({\gamma}^{18}O_{H_2O}$, {\gamma}$D) of ore fluids (stage I: 1.1∼9.0$\textperthousand$, -92∼-86{\textperthansand}$, stage II: 0.3{\textperthansand}$, -93{\textperthansand}$) and ribbon-banded structure (graphitic lamination) indicate that mesothermal auriferous fluids of Daebong deposit were two different origin and their evolution. 1) Fluids of this deposit were likely mixtures of $H_2O$-rich, isotopically less evolved meteoric water and magmatic fluids and 2) were likely mixtures of $H_2O$-rich. isotopically heavier $\delta$D meteoric water and magmaticmetamorphic fluids.

• Economic and Environmental Geology
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• v.32 no.2
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• pp.129-139
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• 1999

Hydrothermal gold deposits of the Trabong district in Vietnam occur as single-stage quartz $\pm$ calcite veins (0.3-1.2 m thick) which fill fault fractures in graphite-bearing gneiss and schist of the Chulai Complex and Kham Duc Formation of the Proterozoic age. Ore grades are 1.3 to 92.4 g/ton Au. Ore mineralogy is very simple, consisting mainly of pyrite with minor amounts of base-metal sulfides and electrum. Gold grains occur in two assemblages as follows: (1) early, Fe-rich (7.2-10.4 mole % FeS) sphalerite + electrum (50.4-64.3 atom % Au) assemblage occurring as inclusions in pyrite; (2) late, Fe-poor «4.7 mole % FeS) sphalerite + galena + electrum (47.6-81.7 atom % Au) assemblage occurring along fractures of pyrites. Based on fluid inclusion data and thermochemical considerations of ore mineral assemblages, ore minerals were formed at high temperatures (about $230^{\circ}C$ to $420^{\circ}C$) from $H_{2}O-CO_{2}(-CH_{4})$-NaCI fluids with the sulfur fugacity of about $10^{-6}$ to $10^{-10}$ atm. Fluid inclusion data also indicate that ore mineralization occurred mainly as a result of fluid unmixing accompanying $CO_2$ effervescence. Calculated oxygen and measured hydrogen isotope compositions of mineralizing waters (${\delta}^{18}O_{V-SMOW}$ values = 5.3 to 8.6$\textperthousand$, ${\delta}D_{V-SMOW}$ values = - 60 to - 52$\textperthousand$), along with the sulfur isotope compositions of vein sulfides (${\delta}^{34}S_{CDR}$ values = - 1.2 to 2.8$\textperthousand$) and carbon isotope compositions of inclusion $CO_2$ (${\delta}^{13}C_{PDB}$ values = - 4.7 to - 2.0$\textperthousand$) indicate that the high temperature (mesohypothermal) gold mineralization formed from a magmatic fluid.

• Economic and Environmental Geology
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• v.35 no.4
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• pp.299-316
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• 2002

The Samkwang gold-silver deposits consist of gold-silver-bearing hydrothermal massive quartz veins which filled the fractures along fault shear (NE, NW) zones within Precambrian banded or granitic gneiss of Gyeonggi massif. Ore mineralization of this deposits occurred within a single stage of quartz vein which was formed by multiple episodes of fracturing and healing. Based on vein mineralogy and paragenesis, massive quartz veins are divided into two main paragenetic stages which are separated by a major faulting event. Main ore mineralization occurred at stage I. Wall-rock alteration from this deposits occur as mainly sericitization, chloritization, silicification and minor amounts of pyritization, carbonitization, propylitization and argillitization. Ore minerals are composed mainly of arsenopyrite (29.21-32.24 As atomic %), pyrite, sphalerite (6.45-13.82 FeS mole %), chalcopyrite, galena with minor amounts of pyrrhotite, marcasite, electmm (39.98-66.82 Au atomic %) and argentite. Systematic studies of fluid inclusions in early quartz veins and microcracks indicate two contrasting physical-chemical conditions: 1). temperature (215-345$^{\circ}$C) and pressure (1296-2022 bar) event with $H_{2}O-CO_{2}-CH_{4}-NaCl$fluids (0.8-6.3 wt. %) related to the early sulfide deposition, 2). temperature (203-441$^{\circ}$C) and pressure (320 bar) event with $H2_{O}$-NaCI $\pm$ $CO_{2}$ fluids (5.7-8.8 wt. %) related to the late sulfide and electrum assemblage. The H20-NaCI $\pm$ $CO_{2}$ fluids represent fluids evolved through fluid unmixing of an $H_{2}O-CO_{2}-CH_{4}-NaCl$fluids due to decreases in fluid pressure and influenced of deepcirculated meteoric waters possibly related to uplift and unloading of the mineralizing suites. Calculated sulfur isotope compositions (${\delta}^{34}S_{fluid}$) of hydrothermal fluids (1.8-4.9$\textperthousand$) indicate that ore sulfur was derived from an igneous source. Measured and calculated oxygen and hydrogen isotope compositions (${\delta}^{18}O_{I120}$, ${\delta}D$) of ore fluids (-5.9~10.9$\textperthousand$, -102~-87$\textperthousand$) indicate that mesothermal auriferous fluids at Samkwang gold-silver deposits were likely mixtures of $H_{2}O$-rich, isotopically less evolved meteoric water and magmatic fluids.