• Bulletin of the Korean Chemical Society
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• v.27 no.9
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• pp.1405-1417
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• 2006

The geometrical structures, potential energy surfaces, and energetics for the ligand exchange reactions of tetracoordinated platinum $(PtY_2L_2\;:\;Y,\;L=Cl^-,\;OH^-,\;OH_2,\;NH_3)$ complexes in the ligand-solvent interaction systems were investigated using the ab initio Hartree-Fock (HF) and Density Functional Theory (DFT) methods. The potential energy surfaces for the ligand exchange reactions used for the conversions of $(PtCl_4\;+\;H_2O)^{^\ast_\ast}\;to\;[PtCl_3(H_2O)\;+\;Cl^-]$ and $[Pt(NH_3)_2Cl_2\;+\;H_2O]$$[Pt(NH_3)_2Cl_2\;+\;H_2O]$ to $[Pt(NH_3)_2Cl(H_2O)\;+\;Cl^-] $ were investigated in detail. For these two exchange reactions, the transition states $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime])^{^\ast_\ast} $ correspond to complexes such as $(PtCl_4{\cdot}{\cdot}{\cdot}H_2O)^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$, respectively. In the transition state, $([PtCl_4{\cdot}{\cdot}{\cdot}H_2O]^{^\ast_\ast}$ and $[Pt(NH_3)_2Cl_2{\cdot}{\cdot}{\cdot}H_2O]]^{^\ast_\ast})$ have a kind of 6-membered $(Pt-Cl{\cdot}{\cdot}{\cdot}HOH{\cdot}{\cdot}{\cdot}Cl)$ and $(Pt-OH{\cdot}{\cdot}{\cdot}Cl{\cdot}{\cdot}{\cdot}HN)$ interactions, respectively, wherein a central Pt(II) metal directly combines with a leaving $Cl^-$ and an entering $H_2O$. Simultaneously, the entering $H_2O$ interacts with a leaving $Cl^-$. No vertical one metal-ligand interactions $([PtY_2L_2{\cdot}{\cdot}{\cdot}L^\prime]) $ are found at the axial positions of the square planar $(PtY_2L_2)$ complexes, which were formed via a vertically associative mechanism leading to $D_{3h}$ or $C_{2v}$-transition state symmetry. The geometrical structure variations, molecular orbital variations (HOMO and LUMO), and relative stabilities for the ligand exchange processes are also examined quantitatively. Schematic diagrams for the dissociation reactions of {PtCl4(H2O)n(n=2,4)} into {$PtCl_3(H_2O)_{(n-2)}\;+\;Cl^-(H_2O)_2$} and the binding energies {$PtCl_4(H_2O)_n$(n = 1-5)} of $PtCl_4$ with water molecules are drawn.

• Bulletin of the Korean Chemical Society
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• v.34 no.6
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• pp.1684-1688
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• 2013

A rapid and sensitive method for determining usnic acid of Lethariella cladonioides in rat was established using high performance liquid chromatography (HPLC) quadrupole time-of-flight (QTOF) tandem mass (MS/MS). Rat plasma was pretreated by mixture of acetonitrile and chloroform to precipitate plasma proteins. Chromatographic separation was achieved on a column ($50{\times}2.1$ mm, $5{\mu}m$) with a mobile phase consisting of water (containing $5{\times}10^{-3}$ M ammonium formate, pH was adjusted to 3.0 with formic acid) and acetonitrile (20:80, v/v) at a flow rate of 0.3 mL/min. A tandem mass spectrometric detection with an electrospray ionization (ESI) interface was conducted via collision induced dissociation (CID) under negative ionization mode. The MS/MS transitions monitored were m/z 343.0448 ${\rightarrow}$ m/z 313.2017 for usnic acid and m/z 153.1024 ${\rightarrow}$ m/z 136.2136 for protocatechuic acid (internal standard). The linear range was calculated to be 2.0-160.0 ng/mL with a detection limit of 3.0 pg/mL. The inter- and intra-day accuracy and precision were within ${\pm}7.0%$. Pharmacokinetic study showed that the apartment of usnic acid in vivo confirmed to be a two compartment open model. The method was fully valid and will probably be an alternative for pharmacokinetic study of usnic acid.

• Korean Journal of Biological Psychiatry
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• v.3 no.2
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• pp.240-244
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• 1996

The effects of chronic treatment with haloperidol on the binding capacities of dopamine(DA) $D_2$-like receptor were investigated in rat striatum and olfactory tubercle. The authors tried to confirm the dose-response effects with usual dose and low dose haloperidol. Rats were treated with haloperidol(0.05, 0.15, 0.5, 1.5mg/kg/day in drinking water) for four weeks. Saturation analysis of the binding of [$^3H$]spiperone to striatal membranes showed that the haloperidol treatment(0.05, 0.5, 1.5mg/kg) induced significant proliferation. The changes of dissociation constant(Kd) were not significant in striatum. The maximal binding density(Bmax) and Kd increased remarkably following the treatment with usual dose haloperidol (1.5mg/kg) in olfactory tubercle. Although there was increasing trend other the treatment with low dose haloperidol, the change of Bmax was not significant statistically. The present findings indicate that low dose haloperidol induces the proliferation of DA $D_2$-like receptor in striatum and interact with the dopaminergic transmission which might underlie the antipsychotic effect. This finding may support the recent clinical suggestion on the low dose strategy in the treatment of schizophrenia.

• Korean Journal of Food Science and Technology
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• v.46 no.4
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• pp.404-409
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• 2014

In this study, the effects of high-pressure homogenizer treatment on the physicochemical properties of wheat bran from different areas were evaluated. The results showed that the high-pressure homogenizer process could effectively decrease particle size and loosen the microstructure of the wheat bran matrix. As the particle size decreased, the bulk density of wheat bran was significantly decreased (p<0.05) and the water-holding capacity, swelling capacity, oil-holding capacity, and cation-exchange capacity were substantially increased. In addition, microscopic analysis revealed the gradual disintegration of the original cell wall structure and the dissociation of bran tissues over the course of high-pressure homogenization treatment. Scanning electron micrographs showed that the process could also effectively separate out the structural components of wheat bran. These results suggest that the high-pressure homogenizer process is an effective method to modify the physicochemical properties of wheat bran and likely other cereal brans, which might provide potential fiber-rich ingredients for use in functional foods.

• Journal of Soil and Groundwater Environment
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• v.20 no.4
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• pp.1-7
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• 2015

The degradation of off-flavors which is 2-Methylisoborneol (2-MIB) and geosmin by means of ultrasound (US) and pulsed ultraviolet (PUV) irradiation and its combination with catalyst (wire mesh, wire mesh coated TiO₂, and TiO₂) and additive (H₂O₂) were investigated via water system. A combination treatment of TiO₂ and H₂O₂ heterogeneity with US (24 kHz) and PUV (6000 W) has shown improved results in destroying 2-MIB and geosmin, which may be attributed to chain reactions by the enhanced formation of hydroxyl radicals (·OH) through H₂O₂ dissociation and reactive oxide ions of TiO₂ addition. Rapid degradation of off-flavors occurred within 2 min under PUV process with H₂O₂ 100 mg/L (81.5% for 2- MIB; 79.3% for geosmin) and TiO₂ 100 mg/L (83.7% for 2-MIB; 79.8% for geosmin), while compared with H2O2 100 mg/L (58.4% for 2-MIB; 58.0% for geosmin) and TiO₂ 100 mg/L (59.2% for 2-MIB; 38.5% for geosmin) within 5 min under US process. Surprisingly, the emphasis was given on the comparison with the same injected energies between PUV and US on degradation efficiency. Based on the injected energy comparison, the US provided better degradation performance under equal input power of 200 kJ with H₂O₂ 100 mg/L, while compared with H₂O₂ 100 mg/L under PUV process. Our findings suggest that US can be more effective compared to PUV for the degradation of off-flavors in aspect of energy consumptions.

• Analytical Science and Technology
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• v.16 no.6
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• pp.443-449
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• 2003

Thermal neutron irradiation experiment of boric acid solution was carried out using HANARO in following three conditions: (A) $^{10}B$ concentration = $203.0{\mu}g/mL$, irradiation time = 1 hr; (B) $^{10}B$ concentration = $381.4{\mu}g/mL$, irradiation time = 1 hr; (C) $^{10}B$ concentration = $381.4{\mu}g/mL$, irradiation time = 0.5 hr. The amount of lithium produced from $^{10}B(n{\cdot}{\alpha})^7Li$ reaction which was generated on neutron irradiation, was measured by flameless atomic absorption spectroscopy. The concentration of $^7Li$ measured in the three experiments was $0.18{\mu}g/mL$ (78.3% of theoretical value, $0.23{\mu}g/mL$) in (A), $0.31{\mu}g/mL$ (70.5% of theoretical value, $0.44{\mu}g/mL$) in (B) and $0.16{\mu}g/mL$ (71.6% of theoretical value, $0.22{\mu}g/mL$) in (C). The pH value of irradiated boric acid was shifted to considerably low. It is estimated that boric acid would be transformed into the polyborate fonn, by radiolysis products of water, which has high dissociation constant.

• Korean Chemical Engineering Research
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• v.46 no.6
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• pp.1095-1099
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• 2008

In this study, we investigated that hydrate formation and phase behavior of the $THF+H_2$ binary clathrate hydrates. In order to confirm the binary clathrate hydrate formation we employed the Raman and NMR spectroscopies that are known to be quite powerful tools, particularly for examining the cage occupancy pattern of guest molecules. In addition, we traced the P-T profiles from clathrate hydrate formation and dissociation process, which made it possible for the resulting phase equilibrium boundary to be clearly established. In the binary clathrate hydrate matrix we further identified that the relatively large THF molecules can only occupy the large $5^{12}6^4$ cavities, while the small $H_2$ molecules are entrapped in the empty $5^{12}$ cavities in structure-II, making the hydrate to be stable above 273 K even at relatively low pressure condition. Considering that pure $H_2$ hydrate can be produced at the extreme pressures higher that 1,000 bar, we can conclude that the water-soluble second guest inclusion induces $H_2$ storage and transportation to be readily achievable under much milder conditions.

• The Korean Journal of Petroleum Geology
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• v.10 no.1_2 s.11
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• pp.18-22
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• 2004

To identify and interpret the distribution and the characteristics of the gas hydrate layers in the Ulleung Basin, we have surveyed and gathered the multi-channel seismic data, Chirp sub-bottom profiler, SeaBeam and 12 m piston core samples since 1996. In previous works, high-resolution seismic profiles showed acoustic anomalies such as acoustic void, acoustic turbidity and pock mark which indicate the presence of gas-charged sediments. The patterns of horizontal degassing cracks originated from free methane expansion is the strong indicator of shallow gas-charged sediments in the core samples. The observation of submarine slides and slumps from destabilizing the sediments in the southern part of the Ulleung Basin may also point out that the gas had been released from gas hydrate dissociation during lowstand of sea level. The multi-channel seismic data show BSR, blanking and phase reversal. The gas hydrate layers above which large-scale shallow gases are distributed exist at the depth of about 200 m from the sea-floor with water depth of 2,100 m. From the interpretation of seismic sections in the southern Ulleung Basin, gas hydrate layers occur in the Pleistocene-Holocene sediments. These gas-charged sediments, acoustic anomalies and BSR may be all related to the existence of gas hydrate layers in the study area.

• Journal of Korean Society of Environmental Engineers
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• v.39 no.11
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• pp.613-625
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• 2017

For two agricultural reservoirs that are rented for fishing spots, benthic nutrient fluxes experiment were performed two times with two sediments from fishing-effective zone and one sediment from fishing-ineffective zone using laboratory core incubation in oxic and anoxic conditions. During benthic nutrient fluxes experiment, the changes in DO, EC, pH, and ORP in the supernatant were not significantly different between fishing-effective zone and fishing-ineffective zone, and were similar to the sediment-hypolimnetic diffused boundary layer in agricultural reservoir. Except for $NO_3{^-}-N$, more benthic nutrient fluxes of $NH_4{^+}-N$, T-P, and $PO{_4}^{3-}-P$ from sediment to hypolimnetic was measured in anoxic than in oxic conditions (p<0.05). As the DO concentration in hypolimnetic decreases, the microorganism-mediated ammonification is promoted, the nitrification is suppressed, and finally the $NH_4{^+}-N$ diffuses out from sediment to hypolimnetic. Also, the diffusion of T-P and $PO{_4}^{3-}-P$ from sediments to hypolimnetic is accelerated through the dissociation of the phosphorus bound to both organic matters and metal hydroxides. The difference in the benthic nutrient diffusive fluxes between fishing-effective zone and fishing-ineffective zone was not statistically significant (p>0.05). Therefore, it was found that fishing activities did not increase the benthic nutrient diffusive fluxes to a statistically significant level. Due to the short fishing activities of 10 years and the rate-limited diffusion of the laboratory core incubation, the contribution of fishing activities on sediment pollution is estimated to be low. No significant correlation was found between the total amount of nutrients in sediment and the benthic nutrient diffusive fluxes in both aerobic and anaerobic conditions. Therefore, nutrients input from various nonpoint sources of watersheds are considered to be a more dominant factor rather than fishing activities in water quality deterioration, and both aeration and water circulation in hypolimnetic were required to suppress the anoxic environment in agricultural reservoirs.

• Proceedings of the Korea Environmental Mutagen Society Conference
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• 2003.10a
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• pp.34-63
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• 2003

Occupational and environmental exposure to manganese continue to represent a realistic public health problem in both developed and developing countries. Increased utility of MMT as a replacement for lead in gasoline creates a new source of environmental exposure to manganese. It is, therefore, imperative that further attention be directed at molecular neurotoxicology of manganese. A Need for a more complete understanding of manganese functions both in health and disease, and for a better defined role of manganese in iron metabolism is well substantiated. The in-depth studies in this area should provide novel information on the potential public health risk associated with manganese exposure. It will also explore novel mechanism(s) of manganese-induced neurotoxicity from the angle of Mn-Fe interaction at both systemic and cellular levels. More importantly, the result of these studies will offer clues to the etiology of IPD and its associated abnormal iron and energy metabolism. To achieve these goals, however, a number of outstanding questions remain to be resolved. First, one must understand what species of manganese in the biological matrices plays critical role in the induction of neurotoxicity, Mn(II) or Mn(III)? In our own studies with aconitase, Cpx-I, and Cpx-II, manganese was added to the buffers as the divalent salt, i.e., $MnCl_2$. While it is quite reasonable to suggest that the effect on aconitase and/or Cpx-I activites was associated with the divalent species of manganese, the experimental design does not preclude the possibility that a manganese species of higher oxidation state, such as Mn(III), is required for the induction of these effects. The ionic radius of Mn(III) is 65 ppm, which is similar to the ionic size to Fe(III) (65 ppm at the high spin state) in aconitase (Nieboer and Fletcher, 1996; Sneed et al., 1953). Thus it is plausible that the higher oxidation state of manganese optimally fits into the geometric space of aconitase, serving as the active species in this enzymatic reaction. In the current literature, most of the studies on manganese toxicity have used Mn(II) as $MnCl_2$ rather than Mn(III). The obvious advantage of Mn(II) is its good water solubility, which allows effortless preparation in either in vivo or in vitro investigation, whereas almost all of the Mn(III) salt products on the comparison between two valent manganese species nearly infeasible. Thus a more intimate collaboration with physiochemists to develop a better way to study Mn(III) species in biological matrices is pressingly needed. Second, In spite of the special affinity of manganese for mitochondria and its similar chemical properties to iron, there is a sound reason to postulate that manganese may act as an iron surrogate in certain iron-requiring enzymes. It is, therefore, imperative to design the physiochemical studies to determine whether manganese can indeed exchange with iron in proteins, and to understand how manganese interacts with tertiary structure of proteins. The studies on binding properties (such as affinity constant, dissociation parameter, etc.) of manganese and iron to key enzymes associated with iron and energy regulation would add additional information to our knowledge of Mn-Fe neurotoxicity. Third, manganese exposure, either in vivo or in vitro, promotes cellular overload of iron. It is still unclear, however, how exactly manganese interacts with cellular iron regulatory processes and what is the mechanism underlying this cellular iron overload. As discussed above, the binding of IRP-I to TfR mRNA leads to the expression of TfR, thereby increasing cellular iron uptake. The sequence encoding TfR mRNA, in particular IRE fragments, has been well-documented in literature. It is therefore possible to use molecular technique to elaborate whether manganese cytotoxicity influences the mRNA expression of iron regulatory proteins and how manganese exposure alters the binding activity of IPRs to TfR mRNA. Finally, the current manganese investigation has largely focused on the issues ranging from disposition/toxicity study to the characterization of clinical symptoms. Much less has been done regarding the risk assessment of environmenta/occupational exposure. One of the unsolved, pressing puzzles is the lack of reliable biomarker(s) for manganese-induced neurologic lesions in long-term, low-level exposure situation. Lack of such a diagnostic means renders it impossible to assess the human health risk and long-term social impact associated with potentially elevated manganese in environment. The biochemical interaction between manganese and iron, particularly the ensuing subtle changes of certain relevant proteins, provides the opportunity to identify and develop such a specific biomarker for manganese-induced neuronal damage. By learning the molecular mechanism of cytotoxicity, one will be able to find a better way for prediction and treatment of manganese-initiated neurodegenerative diseases.