• Bulletin of the Korean Chemical Society
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• v.17 no.5
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• pp.428-432
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• 1996

Amino acid cobalt(Ⅲ) complexes of 1,3-diminopropane-N,N'-di-α-(β-methyl)-pentanoic acid (H2dpdmp), uns-cis-[Co(dpdmp)(aa)] (aa=glycine, S-alanine, R-aspartic acid, sarcosine) have been prepared from the reaction between the uns-cis-[Co(dpdmp)Cl2]- complex and the corresponding amino acid. In the reaction with the uns-cis-[Co(dpdmp)Cl2]- complex, glycine and S-alanine have yielded both merridional and facial isomers, while R-aspartic acid and sarcosine, only merridional isomers. The stereospecific substitution reaction of R-aspartic acid to racemic uns-cis-[Co(dpdmp)Cl2]- complex has yielded two merridional diastereomers; ΛR-uns-cis- and ΛR-uns-cis-[Co(dpdmp)(R-asp)]. It is of interest to note that this is one of the few CoⅢ(ONNO)(aa) type complex preparations, which gives only one isomer with stereospecificity. On the other hand, two merridional products obtained from the reaction of sarcosine with racemic uns-cis-[Co(dpdmp)Cl2]- are turned out to be mixtures of optical isomers.

• Bulletin of the Korean Chemical Society
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• v.7 no.5
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• pp.338-341
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• 1986

Hydrocarbon solution of $Ir(PPh_3)_2(CO)OClO_3$ reacts with $Ph_2PC_6H_4$-o-CHO and 3-methyl-2-aminopyridinyl aldimine to yield ${\bar{Ir(Ph_2PC_6H_4-o-CO)}}\;(PPh_3)_2(CO)(H)ClO_4$(1) and ${\bar{Ir(NC_6H_6NC}}C_6H_5)(PPh_3)_2(CO)(H)ClO_4$(2), respectively. The compound $Ir(PPh_3)_2N_2Cl$ also reacts with $Ph_2PC_6H_4$-o-CHO and 3-methyl-2-aminopyridinyl aldimine to give ${\bar{Ir(Ph_2PC_6H_4-o-C}}O)(PPh_3)_2(H)Cl(3)$ and $Ir(NC_6H_5NCC_6H_5(PPh_3)_2(H)Cl(4)$, respectively. Compounds 1, 2, 3, and 4 were characterized by infrared, $^1H$ NMR, $^{31}p$ NMR, UV spectra, and conductivity measurements.

• Journal of the Korean Chemical Society
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• v.24 no.2
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• pp.139-145
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• 1980

High spin iron(II) complexes of 1,4,8,11-tetraazacyclotetradecane (cyclam), a macrocyclic ligand, and 1,5,8,12-tetraazadodecane (3,2,3-tet), a noncyclic ligand, have been prepared. The reaction of low spin $[Fe(cyclam)(CH_3CN)_2](ClO_4)_2$ with chloride ion in methanol produces high-spin $[Fe(cyclam)Cl]ClO_4$. Although $[Fe(cyclam)(CH_3CN)_2](ClO_4)_2$ is low spin, $[Fe(3,2,3-tet)(CH_3CN)_2](ClO_4)_2$ isolated in the present study is high spin. This difference is explained in terms of the smaller constrictive effect exerted by the noncyclic ligand than the cyclic ligand. The isolation of $[Fe(cyclam)Cl]ClO_4$ provides evidences against the current view that the presence of either unsaturation or substituents on the macrocyclic ligands is necessary for the successful preparation of high spin five-coordinate iron (II) complexes. Reactions of $[Fe(cyclam)Cl]ClO_4\;and\;[Fe(3,2,3-tet)(CH_3CN)_2](ClO_4)_2$ with carbon monoxide yield low spin six-coordinate $[Fe(cyclam)Cl(CO)]ClO_4\;and\;[Fe(3.2,3-tet)(CH_3CN)(CO)](ClO_4)_2$, respectively.

• Journal of the Korean Chemical Society
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• v.36 no.4
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• pp.565-578
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• 1992

It has been suggested that Hg$^{2+}$-promoted reaction of a series of cis-[Co(en)$_2$(L)Cl]$^{2+}$ (en = 1,2-diaminoethane) with L = NH$_3$, NH$_2$CH$_3$, glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN proceeds by dissociative interchange(I$_d$) mechanism from kinetic data, circular dichroism spectra, analyses of products, and the values of m(Grunwald-Winstein plot) using Y (solvent ionizing power) in aqueous solution and in mixed aqueous-organic solvent. It has been found that chloride replacement by water (aquation) for the series with L = NH$_3$ and NH$_2$CH$_3$ and chelation of ligand L to Co(Ⅲ) for the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, and NH$_2$CH$_2$CN occurs, respectively. The rate constants on Hg$^{2+}$-induced reaction of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were increased with increasing the contents of ethanol in mixed water-ethanol solvents. In mixed water-30${\%}$ organic solvents, the rate constants of the series except cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ have also been measured in the order 30${\%}$ 2-propanol-water > 30${\%}$ ethanol-water > water. However, the rate constants of cis-[Co(en)$_2$(NH$_2$CH$_2$CN)Cl]$^{2+}$ were reversed. The rate constants of the series with L= NH$_3$ and NH$_2$CH$_3$ were related to ligand field parameter (${\Delta}$), but those of the series with L = glyOC$_2$H$_5$, glyOCH$_3$, dl-alaOC$_2$H$_5$, NH$_2$CH$_2$CONH$_2$, NH$_2$CH$_2$CN were not. The reaction between the series and Hg2+ in aqueous media containing NO$_3^-$ has been investigated. The results for the reaction do not alter the mechanism, but the rate only was altered.

• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.534-541
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• 1987

The study of reaction mechanism for the substitution of ethylenediamine (en) for Cl and Hedta from $[CoCl(Hedta)]^-$ in the presence of $Hg^{2+}$ ion was carried out by uv and CD spectra. From the kinetic data, we proposed that the first ethylenediamine be substituted through the associative reaction path by means of interaction of $Hg^{2+}$ ion with Co(III), and that the second and the third ethylenediamine be substituted stepwise. From the optical purities of $[Co(en)_3]^{3+}$ which was formed after reaction, we suggested the critical stereochemical step and new substitution reaction paths.

• Journal of Life Science
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• v.20 no.2
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• pp.281-291
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• 2010

We investigated the antioxidant effects of hederagenin 3-O-b-D-glucopyranosyl($1{\rightarrow}3$)-a-L-rhamnopyranosyl($1{\rightarrow}2$)-a-L-arabinopyranoside (HDL) isolated from root bark of Ulmus davidiana on the activity of enzymes related to reactive oxygen species (ROS) in human osteosarcoma U2OS cells. Cobalt chloride ($CoCl_2$), a transition metal, was used as an inducer of oxidative stress, generating hydrogen peroxide ($H_2O_2$) via increasing xanthine oxidase (XO) activity. The increased levels of $H_2O_2$, XO, ferritin, and ferritin iron by $CoCl_2$ were diminished effectively by co-treatment with HDL in U2OS cells. Furthermore, decreased levels of antioxidant enzymes such as superoxide dismutase (SOD), catalase (CAT) by $CoCl_2$ were highly increased by co-treatment with HDL in U2OS cells; however, the levels of glutathione peroxidase (GPx) did not change. The increased contents of TBARS related to lipid peroxidation were significantly reduced by HDL in U2OS cells. The concentration of GSH changed in a pattern that went against regulated TBARS by $CoCl_2$ and HDL. We examined the expression of p53, $p21^{CIP1/WAF1}$, and $p27^{KIP1}$ proteins related to oxidative stress and cell cycle regulation. As a result, the expression of $p27^{KIP1}$ modulated by $CoCl_2$ was not changed by HDL. However, the expression of p53 and $p21^{CIP1/WAF}$ increased by $CoCl_2$ was reduced by HDL in U2OS cells. Together with alteration of p53 and $p21^{CIP1/WAF1}$ proteins, the accumulated cells at G1 phase by $CoCl_2$ was decreased by HDL in U2OS cells. Our data suggests that HDL inhibits $CoCl_2$-generated ROS in U2OS cells, providing potentially new antioxidant compounds that are isolated from natural products.

• Journal of the Korean Chemical Society
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• v.32 no.3
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• pp.227-232
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• 1988

A kinetic study was made to determine the mechanism of the aquation of $cis-[Co(en)_2(NH_3)Cl]^{2+}\;in\;Hg^{2+}$ aqueous solution. The progress of reaction was followed UV/vis-spectrophotometrically by a measurement of the absorbance at a specific wave length (530nm) of $cis-[Co(en)_2(NH_3)Cl]^{2+}$ as a function of time. The experimental results have shown that the reaction rate is dependent upon the concentration of $Hg^{2+}$ that act as a catalyst. And it was found that the overall reaction proceed with second order, first order with respect to Co(III) complex and $Hg^{2+}$. Activation parameters, ${\Delta}H^{\neq}\;and\;{\Delta}S^{\neq}$, were obtained as 12.9 kcal/mol and -19.3 e.u., respectively. We have proposed a plausible reaction mechanism which is consistent with the observed rate equation.

• Journal of the Korean Chemical Society
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• v.32 no.4
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• pp.342-350
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• 1988

An experimental investigation is made to determine the mechanism of the aquation of $[Co(en)_2Cl_2]^+$ in $Hg^{2+}$ aqueous solution. The progress of reaction is followed UV/vis-spectrophotometrically by a measurment of the absorbance at a specific wavelength of Co(III) complex as a function of time. The aquation of cis-$[Co(en)_2Cl_2]^+$ and trans-$[Co(en)_2Cl_2]^+$ has been found to be first order and second order with respect to the concentration of $Hg^{2+}$ catalyst, respectively. It has been found that the reaction rate for aquation of the trans-form is faster than that of cis-form, and that the product of either cis-form or trans-form is always in the mixture ratio of 97 % to 3 %. Plausible reaction mechanism is proposed for the reaction system on the basis of kinetic data and activation parameters. Theoretical rate equation derived from the proposed mechanism is consistent with the observed one.

• IMMUNE NETWORK
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• v.13 no.4
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• pp.141-147
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• 2013

Hypoxia has been shown to promote inflammation, including the release of proinflammatory cytokines, but it is poorly investigated how hypoxia directly affects inflammasome signaling pathways. To explore whether hypoxic stress modulates inflammasome activity, we examined the effect of cobalt chloride ($CoCl_2$)-induced hypoxia on caspase-1 activation in primary mixed glial cultures of the neonatal mouse brain. Unexpectedly, hypoxia induced by oxygen-glucose deprivation or $CoCl_2$ treatment failed to activate caspase-1 in microglial BV-2 cells and primary mixed glial cultures. Of particular interest, $CoCl_2$-induced hypoxic condition considerably inhibited NLRP3-dependent caspase-1 activation in mixed glial cells, but not in bone marrow-derived macrophages. $CoCl_2$-mediated inhibition of NLRP3 inflammasome activity was also observed in the isolated brain microglial cells, but $CoCl_2$ did not affect poly dA:dT-triggered AIM2 inflammasome activity in mixed glial cells. Our results collectively demonstrate that $CoCl_2$-induced hypoxia may negatively regulate NLRP3 inflammasome signaling in brain glial cells, but its physiological significance remains to be determined.

• Korean Chemical Engineering Research
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• v.43 no.1
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• pp.76-79
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• 2005

Dry etching of NiFe, NiFeCo, and Ta for magnetic random access memory (MRAM) by inductively coupled plasmas (ICPs) of $Cl_2/Ar$ has been carried out. NiFe and NiFeCo showed maximum etch rates at a particular ICP source power, but the etch rate of Ta increased with the ICP source power. The etch rates of the magnetic thin films increased with the RF chuck power, but decreased with the operating pressure and the $Cl_2$ concentration. To avoid a corrosion problem by chlorine, the etched samples were rinsed with de-ionized water for 5 minutes after etching. The etch profile showed a clean and smooth surface at 50% $Cl_2$ concentration.