• Title/Summary/Keyword: Intermediate complex

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Comparative Studies between Chungju and Seosan Groups (충주층군(忠州層群)과 서산층군(瑞山層群)의 비교연구(比較硏究))

  • Na, Ki Chang;Kim, Hyung Shik;Lee, Dong Jin;Lee, Sang Hun
    • Economic and Environmental Geology
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    • v.15 no.4
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    • pp.177-188
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    • 1982
  • The Chungju and Seosan Groups have been known usually as Precambrian formations in Korea. But their relative and absolute ages have been controvericial problem in relation with other geologic system such as so-called Ogcheon and Yeoncheon Systems in Korea. This study has mainly focused on the corelation of the Chungju Group with the Seosan Group in their stratigraphy, structure, metamorphism, and iron ore deposits. In the process of study, the auther surveyed and reclassified the Chungju and Seosan Groups and corelated with Gyeonggi and Ogch cheon metamorphic belts and got some new data. The Chungju iron-bearing formations showing transtitional relation with the Gyeonggi Gneiss Complex and the Jangamri Formation consisting mainly of pebble bearing calcarious phyllite, should be seperated from the Gyemyeongsan formation which is mainly composed of metavolcanic rocks. The Jangamri Formation and the coaly phyllite, which can be corelated respectively with the Hwaggangri Formation and Changri Formation in Ogcheon Group, are repeated in the Gyemyeonsan and Munjuri Formations with the overturned anticlinal folding(F1). So the Chungju Group which was defined as an indipendant geologic unit from the Ogcheon Group should be limited only on the Chungju iron Formation. The Seosan Group can be classified stratigraphically such as Seosan Formation consisting of iron-bearing quartzite and mica schist, Daesan Formation overlying unconformably on the Seosan Formation and Gyeonggi Gneiss Complex. Taean Formation overlying unconformably on the Daesan Formation should be seperated from Seosan Group. There are many similarity in the stratigrphy, structure, and metamorphic facies between Chungju and Seosan Groups exept the metavolcanic rocks in the Gyemyeongsan and Munjuri Formations and the pebble bearing calcareous phyllite in the Jangamri Formation. The two Groups were deformed with two kinds of differant stages, the first shows $N30^{\circ}-40^{\circ}E$ trend of fold axis, the second $N70^{\circ}-80^{\circ}W$ respectively. The Seosan Formation, which is the lowest formation in Seosan Group and bearing the iron formation, was metamorphosed at 2500 m. y. before. These age is similar with the metamorphic age of Gyeonggi metamorphic belt and with the age of Algoman and Kenoran Orogenies which devide the Precambrian into Archean and Proterozoic Era. So the Seosan Formation, which is included in some migmatitic rocks of Gyeonggi Gneiss Complex, is the oldest formation in Korea and can be corelated with the Anshan Group which bears the oldest iron formation in China. The metamorphic facies of the Precambrian metamorphism in Seosan area is simillar with that of Chungju area, showing high temperature-low pressure amphibolite facies which is corelated with the Gyeonggi metamorphic belt, the oldest metamorphic belt in Korea ($650^{\circ}-680^{\circ}C$, 3.2-4.4 Kb). The high temperature intermediate pressure amphibolite facies in Seosan area with the low temperature-intermediate presure greenschist facies of Taean formation is corelated with that of Ogcheon Group ($590^{\circ}-640^{\circ}$ C, 5.2-6.3 Kb). The Chungju and Seosan iron formations were deposited in Archean, showing geochemical composition of Precambrian iron formations. The Chungju iron formation was mainly formed by the chemical precipitation, on the other hand, the Seosan iron formation was formed by alternated action of chemical and detrital depositions.

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Dynamic lipopolysaccharide transfer cascade to TLR4/MD2 complex via LBP and CD14

  • Kim, Soo Jin;Kim, Ho Min
    • BMB Reports
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    • v.50 no.2
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    • pp.55-57
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    • 2017
  • Toll-like receptor 4 (TLR4) together with MD2, one of the key pattern recognition receptors for a pathogen-associated molecular pattern, activates innate immunity by recognizing lipopolysaccharide (LPS) of Gram-negative bacteria. Although LBP and CD14 catalyze LPS transfer to the TLR4/MD2 complex, the detail mechanisms underlying this dynamic LPS transfer remain elusive. Using negative-stain electron microscopy, we visualized the dynamic intermediate complexes during LPS transfer-LBP/LPS micelles and ternary CD14/LBP/LPS micelle complexes. We also reconstituted the entire cascade of LPS transfer to TLR4/MD2 in a total internal reflection fluorescence (TIRF) microscope for a single molecule fluorescence analysis. These analyses reveal longitudinal LBP binding to the surface of LPS micelles and multi-round binding/unbinding of CD14 to single LBP/LPS micelles via key charged residues on LBP and CD14. Finally, we reveal that a single LPS molecule bound to CD14 is transferred to TLR4/MD2 in a TLR4-dependent manner. These discoveries, which clarify the molecular mechanism of dynamic LPS transfer to TLR4/MD2 via LBP and CD14, provide novel insights into the initiation of innate immune responses.

Accurate Closed-Form Green′s Function for the Analysis of coplanar Waveguides (코플래너 도파로 해석을 위한 정확한 Closed-Form 그린함수)

  • Gang, Yeon-Deok;Lee, Taek-Gyeong
    • Journal of the Institute of Electronics Engineers of Korea TC
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    • v.37 no.11
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    • pp.23-31
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    • 2000
  • In the layered medium, infinite Sommerfeld integral must be evaluated to calculate a space domain Green's function. The complex image method and the two-level method provide rapid calculation and accurate solutions in the near-field region. However, in the intermediate and far-field region, the solutions are inaccurate due to the deformation of the sampling contour. In this paper, we propose a method to calculate an accurate closed-form Green's function for coplanar structure by sampling data on the real axis.

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Pervaporation of Pyridine-Water Mixture throuoh Poly(acrylonitrile-co-vinyl phosphonic acid) membrane (폴리(아크릴로니트릴-비닐포스포닉산) 공중합체 막을 이용한 피리딘-물 혼합물의 투과증발분리)

  • Park, C.H.;Nam, S.Y.;Kim, Y.;Lee, Y.M.;Kujawski, Wojciech
    • Proceedings of the Membrane Society of Korea Conference
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    • 1998.04a
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    • pp.89-92
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    • 1998
  • 1. Introduction : Among many azeotropic compounds, pyridine which forms an azeotropic mixture with three moles of water boiling at 92-93$\circ$C is very useful synthetic intermediate in laboratory and industry. With conventional separation method, the dehydration of pyridine aqueous solution is difficult and requires strong drying chemicals. To overcome these difficulties, several researchers have investigated on the separation of pyridine from aqueous solution through polymer membranes. Kujawski reported several ion-exchang membranes containing carboxylic and sulfonic fuctional group for dehydration of aqueous pyridine solution [1]. We have applied the idea of activation of water tranport through ion-dipole interactions between polymer membrane and aclueous feed. Our previous studies reported on the in-situ complex membrane to separate water from aqueous pyridine solution based on simple acid'-base theory [2, 3]. Water transport was enhanced through in-situ complex formation between the , acid moiety in the membrane and the incoming pyridine moiety in the feed.

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Influences of seepage force and out-of-plane stress on cavity contracting and tunnel opening

  • Zou, Jin-Feng;Chen, Kai-Fu;Pan, Qiu-Jing
    • Geomechanics and Engineering
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    • v.13 no.6
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    • pp.907-928
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    • 2017
  • The effects of seepage force and out-of-plane stress on cavity contracting and tunnel opening was investigated in this study. The generalized Hoek-Brown (H-B) failure criterion and non-associated flow rule were adopted. Because of the complex solution of pore pressure in an arbitrary direction, only the pore pressure through the radial direction was assumed in this paper. In order to investigate the effect of out-of-plane stress and seepage force on the cavity contraction and circular tunnel opening, three cases of the out-of-plane stress being the minor, intermediate, or major principal stress are assumed separately. A method of plane strain problem is adopted to obtain the stress and strain for cavity contracting and circular tunnel opening for three cases, respectively, that incorporated the effects of seepage force. The proposed solutions were validated by the published results and the correction is verified. Several cases were analyzed, and parameter studies were conducted to highlight the effects of seepage force, H-B constants, and out-of-plane stress on stress, displacement, and plastic radius with the numerical method. The proposed method may be used to address the complex problems of cavity contraction and tunnel opening in rock mass.

Dehydrogenation of Ethylalcohol Catalyzed by Alcoholdehydrogenase Under High Pressure

  • Jee Jong-Gi;Shin Jin-Young;Hwang Jung-Ui
    • Bulletin of the Korean Chemical Society
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    • v.10 no.1
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    • pp.50-57
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    • 1989
  • A pressure effect of the dehydrogenation of ethylalcohol catalyzed by alcoholdehydrogenase was observed in Tris-HCl buffer, pH 8.8 from $25^{\circ}C$ to $35^{\circ}C$ under high pressure system by using our new theory. The theory makes it possible for us to obtain all rate and equilibrium constants for each step of all enzymatic reaction with a single intermediate. We had enthalpy and volume profiles of the dehydrogenation to suggest a detail and reasonable mechanism of the reaction. In these profiles, both enthalpy and entropy of the reaction are positive and their values decrease with enhancing pressure. It means that the first step is endothermic reaction, and its strength decrease with elevating pressure. At the same time, all activation entropies have large negative values, which prove that not only a ternary complex has a more ordered structure at transition state, but also water molecules make a iceberg close by the activated complex. In addition to this fact, the first and second step equilibrium states are controlled by enthalpy. The first step kinetic state is controlled by enthalpy but the second step kinetic state is controlled by entropy.

Electrochemical Behavior of Mordant Red 19 and its Complexes with Light Lanthanides

  • Sang Kwon Lee;Taek Dong Chung;Song-Ju Lee;Ki-Hyung Chjo;Young Gu Ha;Ki-Won Cha;Hasuck Kim
    • Bulletin of the Korean Chemical Society
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    • v.14 no.5
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    • pp.567-574
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    • 1993
  • Mordant Red 19(MR19) is reduced at mercury electrode at -0.67 V vs. Ag/AgCl with two electrons per molecule in pH 9.2 buffer by differential pulse polarography and linear sweep voltammetry. The peak potential is dependent on the pH of solution. The exhaustive electrolysis, however, gives 4 electrons per molecule because of the disproportionation of the unstable hydrazo intermediate. The electrochemical reduction of lanthanide-MR19 complexes is observed at more cathodic potential than that of free ligand. The difference in peak potentials between complex and free ligand varies from 75 mV for $La^{3+}$ to 165 mV for $Tb^{3+}$ and increases with increasing the atomic number of lanthanide. The electrochemical reduction of lanthanide complexes with MR19 is due to the reduction of ligand itself, and it can be potentially useful as an indirect method for the determination of lanthanides. The shape of i-E curves and the scan rate dependence indicates the presence of adsorption and the adsorption was confirmed by potential double-step chronocoulometry and the effect of standing time. Also the surface excess of the adsorbed species and diffusion coefficients are determined. The composition of the complex is determined to be 1 : 2 by spectrophotometric and electrochemical methods.

Integrated Thermochemical Approach to Collision-Induced Dissociation Process of Peptides

  • Shin, Seung Koo;Yoon, Hye-Joo
    • Mass Spectrometry Letters
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    • v.12 no.4
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    • pp.131-136
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    • 2021
  • Collision-induced dissociation of peptides involves a series of proton-transfer reactions in the activated peptide. To describe the kinetics of energy-variable dissociation, we considered the heat capacity of the peptide and the Marcus-theory-type proton-transfer rate. The peptide ion was activated to the high internal energy states by collision with a target gas in the collision cell. The mobile proton in the activated peptide then migrated from the most stable site to the amide oxygen and subsequently to the amide nitrogen (N-protonated) of the peptide bond to be broken. The N-protonated intermediate proceeded to the product-like complex that dissociated to products. Previous studies have suggested that the proton-transfer equilibria in the activated peptide affect the dissociation kinetics. To take the extent of collisional activation into account, we assumed a soft-sphere collision model, where the relative collision energy was fully available to the internal excitation of a collision complex. In addition, we employed a Marcus-theory-type rate equation to account for the proton-transfer equilibria. Herein, we present results from the integrated thermochemical approach using a tryptic peptide of ubiquitin.

Contribution of a Low-Barrier Hydrogen Bond to Catalysis Is Not Significant in Ketosteroid Isomerase

  • Jang, Do Soo;Choi, Gildon;Cha, Hyung Jin;Shin, Sejeong;Hong, Bee Hak;Lee, Hyeong Ju;Lee, Hee Cheon;Choi, Kwan Yong
    • Molecules and Cells
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    • v.38 no.5
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    • pp.409-415
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    • 2015
  • Low-barrier hydrogen bonds (LBHBs) have been proposed to have important influences on the enormous reaction rate increases achieved by many enzymes. ${\Delta}^5$-3-ketosteroi isomerase (KSI) catalyzes the allylic isomerization of ${\Delta}^5$-3-ketosteroid to its conjugated ${\Delta}^4$-isomers at a rate that approache the diffusion limit. Tyr14, a catalytic residue of KSI, has been hypothesized to form an LBHB with the oxyanion of a dienolate steroid intermediate generated during the catalysis. The unusual chemical shift of a proton at 16.8 ppm in the nuclear magnetic resonance spectrum has been attributed to an LBHB between Tyr14 $O{\eta}$ and C3-O of equilenin an intermediate analogue, in the active site of D38N KSI. This shift in the spectrum was not observed in Y30F/Y55F/D38N and Y30F/Y55F/Y115F/D38N mutant KSIs when each mutant was complexed with equilenin, suggesting that Tyr14 could not form LBHB with the intermediate analogue in these mutant KSIs. The crystal structure of Y30F/Y55F/Y115F/D38N-equilenin complex revealed that the distance between Tyr14 $O{\eta}$ and C3-O of the bound steroi was within a direct hydrogen bond. The conversion of LBHB to an ordinary hydrogen bond in the mutant KSI reduced the binding affinity for the steroid inhibitors by a factor of 8.1-11. In addition, the absence of LBHB reduced the catalytic activity by only a factor of 1.7-2. These results suggest that the amount of stabilization energy of the reaction intermediate provided by LBHB is small compared with that provided by an ordinary hydrogen bond in KSI.

Simultaneous determination of illegal galactagogue adulterants in supplement diets by LC-MS/MS

  • Lee, Ji Hyun;Cho, So-Hyun;Park, Han Na;Park, Hyoung Joon;Kim, Nam Sook;Park, Sung Kwan;Kang, Hoil
    • Analytical Science and Technology
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    • v.31 no.4
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    • pp.171-178
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    • 2018
  • Recently, for successful lactation, many breastfeeding mothers seek various products, including herbal medicine, dietary supplements, and prescribed medicines, to improve milk production. As demand for galactogogues grows, it is highly possible that pharmaceutical galactogogues may be adulterated with illegal products to maximize their efficacy. For continuous control and supervision of illegal products, we developed and validated a simple and sensitive LC-MS/MS method capable of simultaneously determining five galactogogues. Chromatographic separation was conducted using an Agilent Poroshell $120SB-C_{18}$ column with a mobile phase consisting of 20 mM ammonium formate (pH 5.4) and 100 % acetonitrile. The total run time was 13 min per analyte. The proposed method was performed according to the guidelines of the International Conference of Harmonization and it produced reliable results. This method showed high sensitivity and specificity, with a limit of detection (LOD) and limit of quantitation (LOQ) of 0.01-0.82 ng/mL and 0.02-2.45 ng/mL, respectively, for the solid- and liquid-type samples. Specificity was evaluated by analyzing matrix-blank samples spiked with the target compounds at LOQ levels, which provided a good separation of all peaks without interference. Additionally, the repeatability and intermediate precision were typically <15 %, whereas the recovery was 80-120 % of the values obtained using blank samples. Thus, we concluded that this method could be used for the identification and quantification of galactogogues in food or herbal products.