• Journal of the Korean Chemical Society
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• v.33 no.6
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• pp.662-668
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• 1989

The decomposition reaction of hydrogen peroxide was carried out by using metal-4,4',4",4"'-tetraaminophthalocyanine [Mt-$PcNH_2$, Mt = Fe(III), Co(II)] supported on poly (styrene-co-methacrylic acid), in heterogeneous aqueous system. These catalysts showed a catalse-like activity and Fe(III)-$PcNH_2$ supported on the copolymer was particularly effective for the decomposition of hydrogen peroxide. It was found that the rate of decomposition increased smoothly in the higher pH region and catalytic reaction was interfered by adding $CN^-,\;CNS^-,\;{C_2O_4}^{-2},\;I^-$ ions. The kinetics of the catalytic reaction was also investigated and the reaction proceeds according to the Michaelis-Menten type mechanism.

• KSBB Journal
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• v.9 no.3
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• pp.279-286
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• 1994

A mathematical model has been derived and used to describe phosphoprotein partitioning in Fe(III) IDA-PEG/dextran two-phase systems. This model includes the inhibitory effects of hydrogen and hydroxyl ion concentrations on protein partitioning. For aqueous two-phase partitioning experiments, the Al and A2 subcomponents of ovalbumin carrying two and one surface phosphoryl group(s) were purified using an immobilized metal ion affinity chromatography (IMAC). The ratio of partition coefficients in the presence and absence of Fe(III)IDA-PEG, K/Ko, increased in the pH range of 3.0 to 5.0 due to deprotonation of the second oxygen of the phosphoryl group, and above pH 5.0 declined steeply by the inhibitory binding of hydroxyl ions to the metal ion. This partitioning behavior was well described by the mathematical model. The binding constants for formation of the complex between the phosphoryl group and the Fe(III)IDA-PEG were found to be $6.1{\times}10^3M^{-1} and 2.3{\times}10^4M^{-1}$ in the top and bottom phases, respectively. These values are 3-5 times those for interaction of Cu(II)IDA-PEG with a single surface-accessible histidine.

• Bulletin of the Korean Chemical Society
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• v.30 no.7
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• pp.1516-1520
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• 2009

A sensitive technique for the determination of trace Co(II) in various samples after column preconcentration by adsorbing onto silica gel loaded with 1-nitroso-2-naphthol was developed. Several experimental conditions, such as pH of sample solution, the amount of silica gel loaded with 1-nitroso-2-naphthol, the flow rate for adsorption and so forth, were optimized. The interfering effects of diverse concomitant ions were investigated. Fe(III) interfered with more than any other ions, but the interference by Fe(III) was completely eliminated by adjusting the amount of silica gel loaded with 1-nitroso-2-naphthol to 0.30 g. The dynamic range, the correlation coefficient ($R^2$), and the detection limit obtained by the proposed technique were 3.0-140.0 ng m$L^{-1}$, 0.9942, and 1.81 ng m$L^{-1}$, respectively. For validating the technique, the aqueous samples (tap water, reservoir water, stream water, and wastewater) and the plastic samples were used as real samples. Recovery yields of 93.0-107.0% were obtained. These measured data were not different from ICP-MS data at the 95% confidence level by F test. Based on the results of the experiment, it has been found that the proposed technique can be applied to the determination of Co(II) in various real samples.

• Journal of Korean Society of Environmental Engineers
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• v.29 no.7
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• pp.778-782
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• 2007

This study investigated the dechlorination mechanisms of TCE by Fe(II) associated with cement. Batch slurry experiments were peformed to investigate the behaviors of selected ions; Fe(II), Fe(III), $Ca^{2+}$, $SO_4^{2-}$ in cement/Fe(II) system. The kinetic experiments of TCE in cement/Fe(II) systems showed that injected Fe(II) was mostly sorbed on cement within 0.5 day and 90% of injected 200 mM sulfate was sorbed on cement within 0.5 day when $[TCE]_0$ = 0.25 mM and $[Fe(II)]_0$ = 200 mM. The kinetic experiments of TCE in hematite/CaO/Fe((II) systems were conducted for simulation of cement/Fe(II) system. Calcium oxide that is one of the major components in cement hydration reactions or has a reactivity in limited conditions. Hematite assumed the ferric iron oxide component of cement. The reactivities observed in hematite/CaO/Fe(II) system were comparable to those reported for cement/Fe(II) systems containing similar molar amounts of Fe(II). The behavior of Fe(II) and $SO_4^{2-}$ sorbed on solid phase at an early stage of reaction in hematite/CaO/Fe(II) system was similar to that of cement/Fe(II) system. Ferric ion was released from hematite at an early period of reaction at low pH. The experimental evidence of kinetic test using hematite/CaO/Fe(II) system implies that the reactive reductant is a mixed-valent Fe(II)-Fe(III) mineral, which may be similar to green rust. Fe(II) sorbed on cement can be converted to new mineral phase having a reactivity such as Fe(II)-Fe(III) (hydr)oxides in cement/Fe(II) systems.

• Bulletin of the Korean Chemical Society
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• v.28 no.10
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• pp.1683-1688
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• 2007

This paper presents a novel simple method for introducing gold nanoparticles in a poly(4-vinylpyridine) (PVP) polymer layer over a glassy carbon (GC) electrode with the aim of forming a tunable electrochemical interface against a cationic ruthenium complex. Initially, AuCl4 ? ions were spontaneously incorporated into a polymer layer containing positively charged pyridine rings in an acidic media by ion exchange. A negative potential was then applied to electrochemically reduce the incorporated AuCl4 ? ions to gold nanoparticles, which was confirmed by the FE-SEM images. The PVP layer with an appropriate thickness over the electrode blocked electron transfer between the electrode and the solution phase for the redox reactions of the cationic Ru(NH3)6 2+ ions. However, the introduction of gold nanoparticles into the polymer layer recovered the electron transfer. In addition, the electron transfer rate between the two phases could be tuned by controlling the number density of gold nanoparticles.

• Analytical Science and Technology
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• v.14 no.6
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• pp.530-534
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• 2001

Effect of stripping solutions on the Duolite GT-73 chelating resin for ten elements, Ag(I), Al(III), Ca(II), Cd(II), Cu(II), Fe(II), Hg(II), Mn(II), Pb(II), and Zn(II), was investigated. Relation between affinities of the metal ions and solubility products of metal sulfides was studied. The smaller the solubility product of metal sulfideis, the larger the affinitie with the ionsis. The ions which have the solubility products larger than $10^{-23}$ could be effectively desorbed with nitric acid. Complexation with chloride ion enhanced the desorption efficiencies of the ions having moderately strong affinity with the resin. The ions which have very strong affinity by the chelating resin can be desorbed by complextion with thiourea and hydrochloric acid.

• Bulletin of the Korean Chemical Society
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• v.15 no.6
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• pp.465-468
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• 1994

The charge transfer compounds $(TTF)_4FeCl_3{\cdot}CH_3OH,\;(TTF)_4SbCl_4\;and\;(TTF)_5(SbBr_4)_2{\cdot}CH_3COCH_3$ were prepared from reactions of the TTF (tetrathiafulvalene) and metal halides. The compounds were characterized by spectroscopic (UV,IR, EPR and XPS) methods, magnetic susceptibility and electrical conductivity measurements. The d.c electrical conductivities of the pressed pellets are in the order of $10^{-1}-10^{-3} Scm^{-1}$, which lies in the range of semiconductor region at room temperature. It means that the partially ionized TTF has stacked in low-dimensional chain in each compound. Spectroscopic properties also indicate that TTF molecules are partially ionized and charge transfer has occurred from (TTF)n to Fe(III) center in $(TTF)_4FeCl_3{\cdot}CH_3OH$ whereas to the $-SbX_4^-$ entity in $(TTF)_4SbCl_4\;and\;(TTF)_5(SbBr_4)_2{\cdot}CH_3COCH_3$. The EPR g values are consistent with TTF radical formation and EPR linewidths suggest the delocalization of unpaired electrons along TTF stacks. A signal arised from metal (Fe and Sb) ions were not detected in EPR spectra, indicating that metal ion is in the diamagnetic state in each compound. The diamagnetic state was also examined by the magnetic susceptibility measurement. The magnetic properties reveal the significant interaction between the $TTF^+$ radical cations in the stacks. The oxidation state of metal ions was also investigated by XPS spectra.

• Journal of the Korean Chemical Society
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• v.27 no.5
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• pp.353-360
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• 1983

The adsorption behavior of 8-hydroxyquinoline (8HQ) on Amberlite XAD-4 and-7 resins was investigated by measuring its distribution coefficients under various experimental conditions, such as shaking time, pH and concentration of methanol in the medium. The application of 8HQ-impregnated-XAD resins for the absorption and separation of metal ions was studied. The maximum adsorption of 8HQ on XAD resins was observed in the 30% methanol solution having pH range from 6.0 to 9.0. The impregnation capacities of XAD resins for 8HQ were 3.81${\times}$10-2mmol, 8HQ/g, XAD-4 resins and 2.60${\times}$10-2mmol, 8HQ/g, XAD-7 resin, respectively. The 8HQ-impregnated-XAD resins were stable in pH range from 6.0 to 10.0 and the amount of 8HQ leached from XAD-4 resin by eluting with hydrochloric acid(above 5M) was negligible. The optimum pH range for the adsorption of metal ions on 8HQ-impregnated XAD resin was also 6.0 to 10.0, and the adsorption mole ratio of metal ion to 8HQ were 1 : 2 for Cu(II), Cd(II) and Ni(II), and 1 : 3 for Fe(III) at the above pH range. It was found that the absorbed metal ions on 8HQ-impregnated-XAD resins were recovered quantitatively with 5M HCl and 8HQ-impregnated-XAD-4 resin could be reusable over 5 times without decrease in its impregnation capacity.

• Bulletin of the Korean Chemical Society
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• v.32 no.10
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• pp.3592-3596
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• 2011

A novel poly(vinylchloride)-based membrane sensor using $N^1$,$N^3$,$N^5$-tris(2-(2,3-dihydroxybenzylamino)-ethyl)cyclohexane-1,3,5-tricarboxamide (CYCOENCAT, L) as ionophore has been prepared and explored as $Fe^{3+}$ selective electrode. The membrane electrode composed of ionophore, poly(vinylchloride) and o-nitropheyloctyl ether in the optimum ratio 4:33:63 gave excellent potentiometric response characteristics, and displayed a linear log[$Fe^{3+}$] versus EMF response over a wide concentration range of $1.0{\times}10^{-5}-1.0{\times}10^{-1}$ M with super nernstian slope of 28.0 mV/decade and the detection limit of $8.0{\times}10^{-6}$ M. The proposed ion selective electrode showed fast response time (< 15 s), wide pH range (3.0-7.0), high non-aqueous tolerance (up to 20%) and adequate long life time (120 days). It also exhibited very good selectivity for $Fe^{3+}$ relative to a wide variety of alkali, alkaline earth, transition and heavy metal ions. Further, the analytical applicability of the sensor was tested as an indicator electrode in the potentiometric titration of $Fe^{3+}$ with EDTA.

• Bulletin of the Korean Chemical Society
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• v.14 no.4
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• pp.439-444
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• 1993

The aerobic oxidation of the Fe(II) complex of 1,4,8,11-tetraazacyclotetradecane, [Fe(cyclam)$(CH_3CN)_2](ClO_4)_2$, in MeCN in the presence of a few drops of $HClO_4$ leads to low spin Fe(III) species [Fe(cyclam)$(CH_3CN)_2](ClO_4)_3$. The Fe(III) cyclam complex is further oxidized in the air in the presence of a trace of water to produce the deep green binuclear bismacrocyclic Fe(II) complex $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$. The Fe(II) ions of the complex are six-coordinated and the bismacrocyclic ligand is extensively unsaturated. $[Fe_2(C_{20}H_{36}N_8)(CH_3CN)_4](ClO_4)_4{\cdot}2CH_3CN$ crystallizes in the monoclinic space group $P2_1/n$ with a= 13.099 (1) ${\AA}$, b= 10.930 (1) ${\AA}$, c= 17.859 (1) ${\AA}$, ${\beta}$= 95.315 $(7)^{\circ}$, and Z= 2. The structure was solved by heavy atom methods and refined anisotropically to R values of R= 0.0633 and $R_w$= 0.0702 for 1819 observed reflections with F > $4{\sigma}$ (F) measured with Mo K${\alpha}$ radiation on a CAD-4 diffractometer. The two macrocyclic units are coupled through the bridgehead carbons of ${\beta}$-diimitie moieties by a double bond. The double bonds in each macrocycle unit are localized. The average bond distances of $Fe(II)-N_{imine}$, $Fe(II)-N_{amine}$, and $Fe(II)-N_{MeCN}$ are 1.890 (5), 2.001 (5), and 1.925 (6) ${\AA}$, respectively. The complex is diamagnetic, containing two low spin Fe(II) ions in the molecule. The complex shows extremely intense charge transfer band in the near infrared at 868 nm with ${\varepsilon}$= 25,000 $M^{-1}cm^{-1}$. The complex shows a one-electron oxidation wave at +0.83 volts and two one-electron reduction waves at -0.43 and-0.72 volts vs. Ag/AgCl reference electrode. The complex reacts with carbon monoxide in $MeNO_2$ to form carbonyl adducts, whose $v_{CO}$ value (2010 $cm^{-1}$) indicates the ${\pi}$-accepting property of the present bismacrocyclic ligand.