• Journal of the Korean Chemical Society
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• v.32 no.5
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• pp.443-451
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• 1988

New crown ether dye-Ⅰ and dye-Ⅱ having an azo group(-N=N-) were synthesized from monobenzo-15-crown-5 and dibenzo-18-crown-6. These dyes showed ${\lambda}_{max}$ of 377 and 383nm respectively. The complexes of alkali metal ions ($Na^+$, $K^+$, $Cs^+$) with dye ligands showed band shift (390~400nm) and intensity increased. For a given anion, the extraction constants are in the order of $K^+$ < $Cs^+$ < $Na^+$ for dye-Ⅰ and $Cs^+$ < $Na^+$ < $K^+$ for dye-Ⅱ. These results show that the selectivity of crown ethers toward the alkali metal ions is dependant on the charge density of cation and the size of crown ether cavity. For a given cation, the order of the extraction constant is $Cl^-$ < $Br^-$ < $I^-$ < picrate. This order coincides with the degree of anion solvation effect.

• Analytical Science and Technology
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• v.19 no.2
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• pp.131-141
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• 2006

Hydrobromic acid salt of a $N_2O_2$ tetradentate ligand, N,N'-bis(2-hydroxybenzyl)-ethylene-diamine ($H-BHE{\cdot}2HBr$) was synthesized. $Br-BHE{\cdot}2HBr$, $Cl-BHE{\cdot}2HBr$, $CH_3-BHE{\cdot}2HBr$ and $CH_3O-BHE{\cdot}2HBr$ having Br, Cl, $CH_3$ and $CH_3O$ substituents at 5-position of the phenol group of $H-BHE{\cdot}2HBr$ were also synthesized. $Nap-BHE{\cdot}2HBr$ having naphthalen-2-ol instead of the phenol group was also synthesized. The potentiometry study in aqueous solution revealed that the proton dissociations of the synthesized ligands occurred in four steps and the order of the calculated overall proton dissociation constants (${\log}{\beta}_p$) of each ligand was Br-BHE < Cl-BHE < H-BHE < Nap-BHE < $CH_3$-BHE < $CH_3O$-BHE. The order showed a similar trend to that of Hammett substituent constants(${\sigma}_P$). The order of the stability constants (${\log}K_{ML}$) was CO(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II). The order in their stability constants (${\log}K_{ML}$) of each transition metal complex agreed well with that of the overall proton dissociation constants (${\log}{\beta}_p$).

• Journal of Adhesion and Interface
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• v.24 no.4
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• pp.136-142
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• 2023

In this study, TEOS was used as a silica source, and a triblock copolymer (P123) was used as a template to produce mesoporous silica with a well-ordered hexagonal mesopore array through a self-assembly method and hydrothermal process under acidic condition. (Surfactant-extracted SBA-15). Surfactant-extracted SBA-15 showed the particle shape of a short rod with a size of approximately 980 nm. The surface area and pore diameter were 730 m²g^-1 and 70.8 Å, respectively. Meanwhile, aminosilane (3-aminopropyltriethoxysilane, APTES) was grafted into the mesopores using a post-synthesis method. Mesoporous silica (APTES-SBA-15) modified with aminosilane had a well-ordered pore structure (p6mm) and well-maintained the particle shape of short rods. The surface area and pore diameter of APTES-SBA-15 decreased to 350 m²g^-1 and 60.7 Å, respectively. APTES-modified mesoporous silica was treated with a solution of rare earth metal ions (Eu³⁺, Tb³⁺) to synthesize a mesoporous silica material in which rare earth metal complexes were introduced into the mesopores. (Eu/APTES-SBA-15, Tb/APTES-SBA-15) These materials exhibited characteristic photoluminescence spectra by λ_ex=250 nm. (⁵D₄→⁷F₅ (543.5 nm), ⁵D₄→⁷F₄ (583.5 nm), ⁵D₄→⁷F₃ (620.2 nm) transitions for Tb/APTES-SBA-15; ⁵D₀→⁷F₀ (577.7 nm), ⁵D₀→⁷F₁ (592.0 nm), ⁵D₀→⁷F₂ (614.9 nm), ⁵D₀→⁷F₃ (650.3 nm) and ⁵D₀→⁷F₄ (698.5 nm) transitions for Eu/APTES-SBA-15)

• Journal of the Korean Chemical Society
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• v.54 no.5
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• pp.541-550
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• 2010

A new $N_4O_3$ heptadentate ligand, N,N'-Bis(2-hydroxybenzyl)-1,3-bis[(2-aminoethyl)amino]-2-propanol(H-BAP 4HCl)was synthesized. The hydrochloric acid salts of Br-BAP 4HCl, Cl-BAP 4HCl, $CH_3O$-BAP 4HCl and $CH_3$-BAP 4HCl containing Br-, Cl-, H-, $CH_3O-$ and $CH_{3^-}$ groups at the para-site of the phenol group of the H-BAP were synthesized. The structures of the ligands were confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible and mass spectra. The elemental stepwise protonation constants(${logK_n}^H$) of the synthesized $N_4O_3$ ligands showed six steps of the proton dissociation. The orders of the overall dissociation constants($log{\beta}_p$) of the ligands were Br-BAP < Cl-BAP < H-BAP < $CH_3O$-BAP < $CH_3$-BAP. The orders agreed well with that of Hammett substituent constants($\sigma_p$). The calculated stability constants($logK_{ML}$) between the ligands and transition metal ions agreed well with the order of the overall proton dissociation constants of the ligands but they showed a reverse order in Hammestt substituent constants($\sigma_p$). The order of the stability constants between the transition metal ions with the ligands were Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II).

• Analytical Science and Technology
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• v.14 no.2
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• pp.159-166
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• 2001

A humic acid(HA, Aldrich Co) sample was subjected to ultrafiltration for molecular size fractionation and three fractions of different nominal size($F_1$: 1,000-10,000 daltons; $F_2$: 10,000-50,000 daltons; $F_3$: 100,000-300,000 daltons) were obtained. The structural characteristics of the size-fractionated HA were analyzed using their IR and solid state C-13 NMR spectral data, and the carboxylate group contents of the humic acids were determined using their pH titration data. The $^7F_0-{^5}D_0$ excitation spectra of Eu(III) complexes of the size-fractionated mgHA in aqueous solution were acquired($[Eu(III)]=1.0{\times}10^{-4}mol\;L^{-1}$, $(HA)=470-970mg\;L^{-1}$) at pH 5.0 using a pulsed tunable laser system, in which metal binding properties of the size-fractionated HA were elucidated and compared on another. Characterization of the IR and C-13 NMR spectral data indicated that the fraction($F_3$) with molecules of larger size were primarily aliphatic, while the fractions($F_1$, $F_2$) with smaller molecules of less than 50,000 daltons were predominantly aromatic. Titration data were consistent with an increase in the number of carboxylate groups per unit mass as molecular size became smaller. The $^7F_0-{^5}D_0$ excitation spectral data of Eu(III)-humate complexes showed that the peak maxima on these spectra were shifted toward lower energies with increasing molecular size of HA, indicating the higher degree of bindings of the Eu in the molecules of larger size. We also discussed the relationship of the lower energy shifts of the maximum peaks with increasing the molecular size of HA with the structural differences of the size-fractionated HA.

• Economic and Environmental Geology
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• v.56 no.6
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• pp.847-870
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• 2023

The safe disposal of high-level radioactive waste requires accurate predictions of the long-term geochemical behavior of radionuclides. To achieve this, the present study was conducted to model geochemical behaviors of uranium (U), plutonium (Pu), and palladium (Pd) under different hydrogeochemical conditions that represent deep groundwater in Korea. Geochemical modeling was performed for five types of South Korean deep groundwater environment: high-TDS saline groundwater (G1), low-pH CO₂-rich groundwater (G2), high-pH alkaline groundwater (G3), sulfate-rich groundwater (G4), and dilute (fresh) groundwater (G5). Under the pH and Eh (redox potential) ranges of 3 to 12 and ±0.2 V, respectively, the solubility and speciation of U, Pu, and Pd in deep groundwater were predicted. The result reveals that U(IV) exhibits high solubility within the neutral to alkaline pH range, even in reducing environment with Eh down to -0.2 V. Such high solubility of U is primarily attributed to the formation of Ca-U-CO₃ complexes, which is important in both G2 located along fault zones and G3 occurring in granitic bedrocks. On the other hand, the solubility of Pu is found to be highly dependent on pH, with the lowest solubility in neutral to alkaline conditions. The predominant species are Pu(IV) and Pu(III) and their removal is predicted to occur by sorption. Considering the migration by colloids, however, the role of colloid formation and migration are expected to promote the Pu mobility, especially in deep groundwater of G3 and G5 which have low ionic strengths. Palladium (Pd) exhibits the low solubility due to the precipitation as sulfides in reducing conditions. In oxidizing condition, anionic complexes such as Pd(OH)₃^-, PdCl₃(OH)₂^-, PdCl₄^2-, and Pd(CO₃)₂^2- would be removed by sorption onto metal (hydro)oxides. This study will improve the understanding of the fate and transport of radionuclides in deep groundwater conditions of South Korea and therefore contributes to develop strategies for safe high-level radioactive waste disposal.

• Journal of Soil and Groundwater Environment
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• v.12 no.4
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• pp.16-24
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• 2007

An investigation on the polluted sediments in the Lake Sihwa and the benthos that inhabited on the sediments was conducted. Cost effective remediation alternatives were derived form the results of the investigation. The sediment samples taken from four sampling points out of thirteen showed relatively high heavy metal (particularly copper) concentrations which exceeded the Effects Range Low (ERL) of the National Oceanic and Atmospheric Administration, USA. The four sampling points were located in front of industrial complexes. Although the heavy metals appeared to have affected the growth of the benthos, the concentration of it did not exceed the criteria of dredging that were developed by Netherlands or the State of Washington, USA. However, contamination by organic matters and sulfur compounds was severe, which exceeded the criteria of dredging that were established in Japan. The sediments taken from the four sampling points which were contaminated with heavy metals showed higher organic matter content in general. The organic matters in the sediments depleted oxygen in summer, which appeared to be fatal to the benthos. A comprehensive analysis on the sediments, benthos, and other environmental impact from the contaminated sediments drew a conclusion that the benthonic environment of the Lake Sihwa needed a stepwise remediation, giving a particular emphasis on the clean up of the sediments upstram of the Lake which could cause odor problems to the nearby residential area.

• Journal of the Korean Chemical Society
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• v.38 no.12
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• pp.898-907
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• 1994

The solvent extraction of an inorganic trace mercury in sea water samples was studied using zinc diethyldithiocabamate $Zn(DDC)_2$ as chelating agent. The $Zn(DDC)_2$ which maintained the stability of DDC- in the acidic aqueous solution in the course of extraction was synthesized from NaDDC and $ZnSO_4$ in this laboratory. The trace of mercury(Ⅱ) was extracted at pH 3.0 from 100 ml of sea water into 10ml of chloroform containing 0.05 M $Zn(DDC)_2$ by shaking for 5 minutes. And from the organic phase, the $Hg(DDC)_2$ was back-extracted into 10ml of 1 to 1 mixed acid of each 3% (v/v) nitric acid and hydrochloric acid by shaking for 25 minutes. The mercury back-extracted was determined by a cold vapor atomic absorption spectrophotometry. The trace mercury(Ⅱ) was so successfully extracted that this procedure could be applied to its determination in the sea water. That is, the recoveries of mercury in two kinds of samples into which as given amount of Hg(Ⅱ) was spiked were 90.0% and 93.3%, respectively.

• Investigative Magnetic Resonance Imaging
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• v.3 no.2
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• pp.159-166
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• 1999

Purpose : To evaluate the effect of rotational correlation time (${\tau}_R$) and the possible related changes of other parameters, ${\tau}_M,{\;}{\tau}_S,{\;}and{\;}(\tau}_V$ of gadolinium (Gd) chelate on T1 relaxation enhancement in two pool model. Materials and Methods : The NMRD (Nuclear Magnetic Relaxation Dispersion) profiles were simulated from 0.02 MHz to 800 MHz proton Larmor frequency for different values of rotational correlation times based on Solomon-Bloembergen equation for inner-sphere relaxation enhancement. To include both unbound pool (pool A) and bound pool (pool B), the relaxivity was divided by contribution from unbound pool and bound pool. The rotational correlation time for pool A was fixed at the value of 0.1 ns, which is a typical value for low molecular weight complexes such as Gd-DTPA in solution and ${\tau}_R$ for pool B was changed from 0.1 ns to 20 ns to allow the slower rotation by binding to macromolecule. The fractional factor of was also adjusted from 0 to 1.0 to simulate different binding ratios to macromolecule. Since the binding of Gd-chelate to macromolecule cab alter the electronic environment of Gd ion and also the degree of bulk water access to hydration site of Gd-chelate, the effects of these parameters were also included. Results : The result shows that low field profiles, ranged from 0.02 to 40 MHz, and dominated by contribution from bound pool, which is bound to macromolecule regardless of binding ratios. In addition, as more Gd-chelate bound to macromolecule, sharp increase of relaxivity at higher field occurs. The NMRD profiles for different values of ${\tau}_S$ show the enormous increase of low field profile whereas relaxivity at high field is not affected by ${\tau}_S$. On the other hand, the change in ${\tau}$V does not affect low field profile but strongly in fluences on both inflection fie이 and the maximum relaxivity value. The results shows a fluences on both inflection field and the maximum relaxivity value. The results shows a parabolic dependence of relaxivity on ${\tau}_M$. Conclusion : Binding of Gd-chelate to a macromolecule causes slower rotational tumbling of Gd-chelate and would result in relaxation enhancement, especially in clinical imaging field. However, binding to macromolecule can change water enchange rate (${\tau}_M$) and electronic relaxation ($T_le$) vis structural deformation of electron environment and the access of bulk water to hydration site of metal-chelate. The clinical utilities of Gd-chelate bound to macromolecule are the less dose requirement, the tissue specificity, and the better perfusion and intravascular agents.

• The Korean Journal of Pesticide Science
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• v.4 no.1
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• pp.32-37
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• 2000

A series of transition metal complexes of 3,6-bis(6'-methyl-2'-pyridyl)pyridazine ($L^{1}$) and 3,6-bis(2'-pyridyl)pyridazine ($L^{2}$) as artificial nuclease, $1{\sim}8$ were synthesized. After determining of X-ray crystal structure, hydrolysis rate constants of phosphates, as DNA model compound and biological activities were confirmed. $L^{2}$-Zn(II) complex, 8 was shown the best hydrolysis rate constant. The $L^{2}$-Ni(II) complex, 5 and $L^{2}$-Co(II) complex, 6 showed the highest herbicidal activity against SCP (Scriptus Juncoids) with excellent tolerance to rice, ORY (Oryzae sativa L.). And the $L^{1}$-Co(II) complex, 2, $L^{1}$-Zn(II) complex, 4 and ligand ($L^{1}$ amp; $L^{2}$) displayed above 90% fungicidal activity against MAG (Magnaporthe grisea).