• Journal of the Korean Chemical Society
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• v.28 no.6
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• pp.384-392
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• 1984

Reaction of the Fe(II) complex of a fully saturated tetradentate macrocyclic ligand [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$, where [14]ane$N_4$ represents 1,4,8,11-tetraazacyclotetradecane, with $O_2$ has been investigated in acetonitrile solutions. [Fe([14]aneN$_4)(CH_3CN)_2]^{2+}$ reacts with oxygen to yield low spin Fe(III) species, [Fe([14]aneN$_4)(CH_3CN)_2]^{3+}$, which undergoes metal ion assisted oxidative dehydrogenation of the macrocyclic ligand to produce low spin Fe(II) complex, [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$. The macrocyclic ligand in [Fe([14]tetraeneN$_4)(CH_3CN)_2]^{2+}$ is highly unsaturated and its double bonds are conjugated. [Fe([14]dieneN$_4)(CH_3CN)_2]^{2+}$ and [Fe([14]dieneN$_4)(CH_3CN)_2]^{3+}$ are isolated as the intermediates of the reaction. The Fe(II) complexes involved in this oxidative dehydrogenation reaction react with carbon monoxide to give respective carbon monoxide derivatives, [FeL$(CH_3CN)(CO)]^{2+}$ (where L = macrocyclic ligand). The values of $v_{CO}$ of [FeL$(CH_3CN)(CO)]^{2+}$, and the electrochemical oxidation potentials of Fe(II) ${\to}$ Fe(III) and the qualitative stability toward air-oxidation for [FeL(CH$_3CN_2)^{2+}$ increase as the degree of unsaturation of the macrocyclic ligands increase.

• Bulletin of the Korean Chemical Society
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• v.16 no.11
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• pp.1060-1064
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• 1995

The reactivity of superoxide ion (O2-.) with halogenated substrates is investigated by cyclic voltammetry and rotated ring-disk electrode method in aprotic solvents. The more positive the reduction potential of the substituted nitrile, the more facile is nucleophilic displacement by O2-.. The reaction rates of halogenonitriles with O2-. vary according to the leaving-group propensity of halide (Br > Cl > F). The relative reaction rates of other substituted nitriles are in the order of electron-withdrawing propensity of the substituent group (CN > C(O)NH2 > Ph ≒ CH2CN). The reaction of O2-. with dihalocarbons indicates that five-membered rings can be rapidly formed by the cyclization of substrate and O2-., and the relative rates of cyclization depend on the number of methylenic carbons {Br(CH2)nBr, [n=1 < 2 < 3 > 4 > 5]}. Mechanisms are proposed for the reaction of O2-. with halogenated substrates.

• Journal of the Korean Chemical Society
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• v.68 no.3
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• pp.139-145
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• 2024

This study aims to elucidate the mechanism involved in the hydrolysis of the hexacyanoferrate(III) complex ion (Fe(CN)₆^3-) and the mechanism leading to the formation of Prussian blue (Fe^III₄[Fe_II(CN)₆]₃·xH₂O, PB) in acidic aqueous solutions at moderately elevated temperatures. Hydrolysis constitutes a crucial step in generating PB through the widely used single-source or precursor method. Recent PB syntheses predominantly rely on the single-source method, where hexacyanoferrate(II/III) is the exclusive reactant, as opposed to the co-precipitation method employing bare metal ions and hexacyanometalate ions. Despite the widespread adoption of the single-source method, mechanistic exploration remains largely unexplored and speculative. Utilizing UV-vis spectrophotometry, negative-ion mode liquid chromatography-electrospray ionization-mass spectrometry (LC-ESI-MS), and a devised reaction, this study identifies crucial intermediates, including aqueous Fe^2+/3+ ions and hydrocyanic acid (HCN) in the solution. These two intermediates eventually combine to form thermodynamically stable PB. The findings presented in this research significantly contribute to understanding the fundamental mechanism underlying the acid-catalyzed hydrolysis of the hexacyanoferrate(III) complex ion and the subsequent formation of PB, as proposed in the sequential mechanism introduced herein. This finding might contribute to the cost-effective synthesis of PB by incorporating diverse metal ions and potassium cyanide.

• Bulletin of the Korean Chemical Society
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• v.35 no.7
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• pp.2043-2048
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• 2014

Two isomers of a new tetraaza macrotricycle 2,2,4,9,9,11-hexaazamethyl-1,5,8,12-tetraazatricyclo[$10.2.2^{5.8}$]-octadecane ($L^2$) containing additional N-$CH_2CH_2$-N linkages, C-meso-$L^2$ and C-racemic-$L^2$, have been prepared by the reaction of 1-bromo-2-chloroethane with C-meso-$L^1$ or C-racemic-$L^1$ ($L^1$ = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane). Both C-meso-$L^2$ and C-racemic-$L^2$ react with copper(II) ion to form $[Cu(C-meso-L^2)]^{2+}$ or $[Cu(C-racemic-L^2)]^{2+}$ in dehydrated ethanol, but do not with nickel(II) ion under similar conditions. Crystal structure of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ shows that the complex has distorted square-pyramidal coordination geometry with an apically coordinated water molecule. Unexpectedly, the Cu-N distances [2.016(3)-2.030(3) ${\AA}$] of [Cu(C-racemic-$L^2$)($H_2O$)]$(ClO_4)_2$ are longer than those [1.992(3)-2.000(3) ${\AA}$] of [Cu(C-racemic-$L^1$)($H_2O$)]$(ClO_4)_2$. As a result, $[Cu(C-racemic-L^2)(H_2O)]^{2+}$ exhibits weaker ligand field strength than $[Cu(C-racemic-L^1)(H_2O)]^{2+}$. The copper(II) complexes readily react with CN- ion to yield the cyano-bridged dinuclear complex $[Cu_2(C-meso-L^2)_2CN]^{3+}$ or $[Cu_2(C-racemic-L^2)_2CN]^{3+}$. Spectra and chemical properties of $[Cu(C-meso-L^2)]^{2+}$ and $[Cu_2(C-meso-L^2)_2CN]^{3+}$ are not quite different from those of $[Cu(C-racemic-L^2)]^{2+}$ and $[Cu_2(C-racemic-L^2)_2CN]^{3+}$, respectively.

• Analytical Science and Technology
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• v.14 no.6
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• pp.540-544
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• 2001

Determination of cyanide ion has been studied by adsorptive stripping voltammetry using hanging mercury electrode. Cyanide ion complexed with copper ion is adsorpbed on the electrode and oxidised at the positive potential scan. Optimal conditions of CN determination were found to be ; supporting electrolyte solution ; 0.1 M NaCl of ammonium buffer at pH 10, accumulation potential; -800 mV vs Ag/AgCl, accumulation time ; 300 s, scan rate ; 50mV/s. The linear concentration of cyanide ion was observed in the range $1{\times}10^{-8}$, $1{\times}10^{-7}M$. The detection limit(n/s=3) was $0.13{\mu}g/L$($5{\times}10^{-9}M$) with 3.5% RSD.

• Journal of Biomedical Engineering Research
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• v.25 no.2
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• pp.157-163
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• 2004

Nitrogen ion implantation and ion plating techniques were applied for improvement of the wear resistance of metallic implant materials. In this work, the wear dissolution behaviour of a nitrogen ion implanted super stainless steel (S.S.S, 22Cr-20Ni-6Mo-0.25N) was compared with those of S.S.S, 316L SS and TiN coated 316L SS. The amounts of Cr and Ni ions worn-out from the specimens were Investigated using an electrothermal atomic absorption spectrometry. Furthermore, the Ti(Grade 2) disks were coated with TiN, ZrN and TiCN by use of low temperature arc vapor deposition and the wear resistance of the coating layers was compared with that of titanium. The chemical compositions of the nitrogen ion implanted and nitride coated layers were examined with a scanting auger electron spectroscopy. It wat observed that the metal ions released from the nitrogen ion implanted S.S.S surface were significantly reduced. From the results obtained, it was shown that the nitrogen ion implanted zone obtained with 100 KeV ion energy was easily removed within 200,000 revolutions from a wear dissolution testing under a similar load condition when applied to artificial hip joint. The remarkable improvement in wear resistance weir confirmed by the nitrides coated Ti materials and the wear properties differ greatly according to the chemical composition of the coating layers. for specimens with the same coating thickness of about 3$\mu\textrm{m}$, TiCN coated Ti showed the highest wear resistance. However, after removing the coating layers, the wear rates of all nitrides coated Ti reverted to their normal rates of below 10,000 revolutions from Ti-disk-on-disk wear testing under the same load condition. From the results obtained, it is suggested that the insufficient depth of the 100 Kel N$\^$＋/ ion implanted zone and of the nitrides coated layers of 3$\mu\textrm{m}$ are subject to restriction when used as frictional parts of load bearing implants.

• Journal of Environmental Health Sciences
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• v.14 no.2
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• pp.65-71
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• 1988

In this study, the method of adsorption by activated carbon in the removal of Hg(II) ion in waste water was treated. The influence of kinds of activated carbon and effect of temperature and the influence of coexistent salt on adsorption rates, the influence of pH in the adsorption, equilibrium and adsorption of mercury from activated carbon were investigated. From the adsorption on activated carbon of mercury(II) ion in the presence of cyanide or thiocyanate ion was found that mercury(II) was easily adsorved onto the activated carbon in the form of complex artion such as Hg(CN)$_4^{2-}$, Hg(SCN)$_4^{2-}$ respectively. ZnCl$_2$ activation method had a higher adsorptive ability than steam activation method in adsorption of Hg on activated carbon. Activated carbon adsorbed iodide ion is very effective on adsorption of Hg.

• 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 Society of Industry Convergence
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• v.19 no.4
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• pp.198-205
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• 2016

For the study on the ion exchange of nickel hexacyanoferrate(NiHCNFe) electrode with the several cations, the film of hexacyanoferrate was prepared on the bare nickel surface by the electrochemical and chemical methods in the solution composed with 5mM K3Fe(CN)6 and 100mM KNO3. To compare the capability of the ion exchange of NiHCNFe film electrode, the repeated cyclic voltammograms were measured in the 0.5M cation nitrate solutions at $25^{\circ}C$ and pH7. It was found that the capacity of the electrochemically derivatized NiHCNFe reduced in the rate of 0.5~0.7%/cycle and was nearly exhausted at the 150th potential cycle. Better result was obtained from that the capacity loss of the chemically assembled NiHCNFe was less than 0.02%/cycle for 5,000cycles. Furthermore, the residual capacity was more than 30% at the 5,000th cycle.

• Bulletin of the Korean Chemical Society
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• v.31 no.3
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• pp.689-693
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• 2010

Second-order rate constants ($k_{CN^-}$) have been measured for nucleophilic substitution reactions of Y-substituted phenyl benzoates (1a-r) with $CN^-$ ion in 80 mol % $H_2O$/20 mol % DMSO at $25.0{\pm}0.1^{\circ}C$. The Br${\o}$nsted-type plot is linear with ${\beta}_{1g}$ = -0.49, a typical ${\beta}_{1g}$ value for reactions reported to proceed through a concerted mechanism. Hammett plots correlated with ${\sigma}^{\circ}$ and ${\sigma}^-$ constants exhibit many scattered points. In contrast, the Yukawa-Tsuno plot for the same reaction exhibits excellent linearity with ${\rho}_Y$ = 1.37 and r = 0.34, indicating that a negative charge develops partially on the oxygen atom of the leaving aryloxide in the rate-determining step (RDS). Although two different mechanisms are plausible (i.e., a concerted mechanism and a stepwise pathway in which expulsion of the leaving group occurs at the RDS), the reaction has been concluded to proceed through a concerted mechanism on the basis of the magnitude of ${\beta}_{1g}$ and ${\rho}_Y$ values.