• Journal of the Korean Chemical Society
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• v.39 no.1
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• pp.47-56
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• 1995

Tridentate Schiff base molybdenum(V) complexes such as [Mo(Ⅴ)2O(SOHB)4], [Mo(Ⅴ)2O3(SOIP)2(NCS)2] and [Mo(Ⅴ)2O3(SOTB)2(H20)2](SOHB: Salicylidene-o-imino hydroxybenzene, SOIP; Salicylidene-o-imino pyridine, SOTB; Salicylidene-o-imino thiolbenzene) were synthesized and identified by elemental analysis, spectroscopy, and thermogravimetric analysis (TGA). It was found that the mole ratio of Schiff base ligand to the metal in these complexes is 1 : 1 or 1 : 2. The redox processes of the complexes were investigated by cyclic voltammetric and differential pulse polarographic techniques in nonaquous solvent containing 0.1 M tetraethylammonium perchlorate (TEAP) as supporting electrolyte at glassy carbon electrode. It was found that diffusion controlled reduction processes with one electron were Mo(Ⅴ)Mo(Ⅴ)e-→ Mo(Ⅴ)Mo(Ⅳ)e-→Mo(Ⅳ)Mo(Ⅳ)e-→Mo(Ⅳ)Mo(Ⅲ).

• Journal of the Korean Chemical Society
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• v.38 no.2
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• pp.160-168
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• 1994

Pentadentate Schiff base molybdenum(Ⅴ) complexes such as [Mo(Ⅴ)O(Sal-DET)(NCS)] and [Mo(Ⅴ)O(Sal-DPT)(NCS)] were synthesized by Sabat method. The structure of these complexes were identified by elemental analysis, spectroscopy, and thermogravimetric analysis(T.G.A.). It was found that the mole ratio of Schiff base ligand to the complexes was found to be 1 : 1. The redox processes of the complexes were investigated by cyclic voltammetric and differential pulse polarographic technique in nonaqueous solvent containing 0. 1 M tetraethyl ammonium perchlorate(TEAP) as supporting electrolyte at glassy carbon electrode. It was found that diffusion controlled reduction processes of four steps with one electron were 2Mo(Ⅴ)$\rightleftarrow^{e-}$ Mo(Ⅴ)Mo(Ⅳ) $\longrightarrow^{e-}$ 2Mo(Ⅳ), Mo(Ⅳ) $\longrightarrow^{e-}$ Mo(Ⅲ) $\longrightarrow^{e-}$ Mo(Ⅱ)

• Bulletin of the Korean Chemical Society
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• v.11 no.6
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• pp.521-527
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• 1990

The binding characteristics and analytical applications of anilinium ion complexes with 18-crown-6 were studied by polarography and NMR. First, the electrochemical reduction of the 10 species of mono and dimethylsubstituted anilinium ion complexes with 18-crown-6 as host in methanol are examined. The addition of 18-crown-6 to anilinium guest solution the polarographic waves remain well defined but shifted toward more negative potentials, indicating the complex formation. The values of formation constants, log Κ for 10 species of methylsubstituted anilinium ion complexes with 18-crown-6 varies from 2.7 to 4.8 in methanol at $25^{\circ}C$. The stability order of complexes for 18-crown-6 is anilinilum > 4-methyl > 3,4-dimethyl > 3-methyl > 3,5-dimethyl > 2,4-dimethyl > 2,5-dimethyl > 2,3-dimethyl > 2-methyl > 2,6-dimethylanilinium ion. The steric hindrance shows significant effect. Second, Proton NMR was used to elucidate their interaction characteristics. From the results of so called NMR titration techniques, the behaviors of binding sites on complexation, and the stoichiometry and stability order of complex were obtained. And the later results show the satisfactory agreement with the quantitative values obtained by polarography. Finally, the individual determinations of anilinium ion mixtures were also accomplished by addition of 18-crown-6. In some mixtures of methyl or dimethylanilinium ions the reduction peaks of differential pulse method appeared into one unresolved wave attributed to the small difference of half-wave potential, ${\Delta}E_{1/2}$. In the presence of 18-crown-6, the polarographic waves were resolved into individual maxima because of the shift toward more negative direction by the difference of selectivity of anilinium ions with 18-crown-6. It may be concluded that quantitative analysis of methylanilinium ion mixture make possible because the half-wave potential shift by the selectivity difference due to the steric hindrance between methyl group and 18-crown-6 on complexation.

• Analytical Science and Technology
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• v.10 no.3
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• pp.187-195
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• 1997

Chemically modified electrodes(CMEs) for Ag(I) were constructed by incoporating 1,5,9,13-tetrathiacyclohexadecane([16]-ane-$S_4$) with a conventional carbon-paste mixture composed of graphite powder and nujol oil. Ag(I) ion was chemically deposited onto the surface of the modified electrode with [16]-ane-$S_4$ by immersion of the electrode in the acetate buffer solution(pH=4.5) containing $5.0{\times}10^{-4}M$ Ag(I) ion. And then the electrode deposited with Ag(I) was reduced at -0.3V vs. S.C.E. Well-defined stripping voltammetric peaks could be obtained by scanning the potential to the positive direction. The CME surface was regenerated with exposure to 0.1M $HNO_3$ solution and was reused for the determination of Ag(I) ion. When deposition/measurement/regeneration cycles were 10 times, the response could be reproduced with relative standard deviation of 6.08%. In case of differential pulse stripping voltammetry, the calibration curve for Ag(I) was linear over the range of $5.0{\times}10^{-7}{\sim}1.5{\times}10^{-6}M$. And the detection limit was $2.0{\times}10^{-7}M$. Various ions such as Cd(II), Ni(II), Pb(II), Zn(II), Mn(II), Mg(II), EDTA, and oxalate(II) did not influence the determination of Ag(I) ion, except Cu(II) ion.

• Journal of the Korean Chemical Society
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• v.36 no.5
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• pp.709-719
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• 1992

We synthesized the binuclear tetradentate Schiff base cobalt(II), nickel(II) and copper(II) complexes such as [Co(II)_2(TSBP)(L)_4], [Ni(II)_2(TSBP)(II)_4] and [Cu(II)_2(TSBP)] (TSBP: 3,3',4,4'-tetra(salicylideneimino)-1,1'-biphenyl, L: Py, DMSO and DMF). We identified the binucleated structure of these complexes by elemental analysis, IR-spectrum, UV-visible spectrum, T.G.A. and D.S.C. According to the results for cyclic voltammogram and differential pulse polarogram of 1 mM complexes in nonaqueous solvents included 0.1M TEAP-L (L; Py, DMSO and DMF) as supporting electrolyte, it was found that diffusionally controlled redox processes of four steps through with one electron for binucleated Schiff base Cobalt(II) complex was Co(III)_2 {^\longrightarrow \\_\longleftarrow^e^-}Co(III)Co(II)_2{^\longrightarrow \\_\longleftarrow^e^-}Co(II){^\longrightarrow \\_\longleftarrow^e^-}Co(I){^\longrightarrow \\_\longleftarrow^e^-}Co(I)_2 and two steps with one electron for Nickel(II) and Copper(II) complexes were M(II)_2 {^\longrightarrow \\_\longleftarrow^e^-}M(I)M(I){^\longrightarrow \\_\longleftarrow^e^-}M(I)_2 (M; Ni and Cu) in nonaqueous solvents.

• Journal of Conservation Science
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• v.30 no.1
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• pp.95-101
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• 2014

Silver objects tarnish with black from reaction with sulfurous acid or hydrogen sulfide of atmospheric. Blackening of silver objects results from formation of silver sulfide($Ag_2O$) on the surface. Silver sulfide usually is usually removed by conservation treatment. There are several cleaning methods such as chemical, electrochemical and micro-abrasion cleaning, but all of them consume silver. This study investigated the safe and effective parameter of laser cleaning by test on silver coupons. Laser cleaning is a selective process for the removal of specific substances. At first, laser cleaning applied to plain silver coupons, which were not corroded, to find out the safe range of laser energy density. From results, plain silver coupons were not changed at 1064nm below $4.00J/cm^2$ and at 532nm below $2.39J/cm^2$. The corrosion layer(silver sulfide) of artifical corroded silver coupons was removed at 1064nm with $2.39J/cm^2$ by 5~10 pulses and at 532nm with $1.19J/cm^2$ by 5~10 pulses. The removal thickness of corrosion layer was about 13-25nm per a laser pulse using AES analysis. In addition, laser cleaning tested the tarnish silver rings based on the results of silver coupons. As a result of test, the black surface were clean successfully and gave luster of silver, which showed the application possibility of laser cleaning for silver objects.

• Analytical Science and Technology
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• v.5 no.3
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• pp.239-247
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• 1992

The complexations and selectivities of the 10 species of mono- and dimethylsubstituted anilinium ions with 18-crown-6 in methanol are examined at dropping mercury electrode. The stability constants of these complexes varies drastically due to the steric hindrance by the positions and numbers of methyl groups. And the analyses of the isomeric mixtures of methylanilinium, which are impossible to detect due to the overlapped peaks in normal conditions, were also accomplished by the additions of 18-crown-6 as the supporting complexing agent using the selective complexations by the steric hindrance effects. As results in case of the difference of stability, ${\Delta}log\;K$ were about 0.7~1.3, it was possible to confirm the existence of two species qualitatively. Otherwise when ${\Delta}log\;K$ were large than 1.6, the quantitative determinations of each species could be accomplished sucessfully. From these results it is deduced that the selective recongnition of the positions and numbers of methyl groups as the steric hindrance in anililniums by 18-crown-6 cause the large variation of the magnitudes of negative shift of reduction waves for guest ions in mixtures.

• Journal of the Korean Chemical Society
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• v.55 no.1
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• pp.57-62
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• 2011

Sometimes inhabitants in remote areas have inadequate or no access to modern medicines or medical services. They can get benefit in term of the treatment against malaria by cultivating selected breeding of A. annua and making teas or decoctions from the plant materials following the proper way of tea preparation. In order to have the maximum extraction efficiency for artemisinin, different ways of tea preparations of A. annua were investigated by applying the developed DPP method and described in this article. Tea was prepared by three different ways (cooking, without cooking with/without shaking and microwave oven) with different times. From the results, it has been found that higher concentration of artemisinin (84.7%) can be attained by following the approach for tea preparation without cooking with shaking for 15 minutes (R.S.D. 2.34%). The concentration of artemisinin decreases with cooking more than 1.5 min in microwave oven. The utmost extraction (88.9% of artemisinin) is possible to extract by shaking with boiled 5% ethanol in distilled water (R.S.D. 2.28%).

• Applied Chemistry for Engineering
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• v.9 no.5
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• pp.719-725
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• 1998

Tridentate Schiff base ligands were prepared by the reactions of salicylaldehyde and 2-hydroxy-1-naphthaldehyde with 2-aminophenol and 2-amino-p-cresol. And then Cu(II) complexes of those ligands were synthesized. The structures and properties of ligands and their complexes were studied by elemental analysis, $^1H$-NMR, IR, UV-visible spectra, and thermogravimetric analysis. The mole ratio of Schiff base to the metal of complexes was found to be 1:1. Cu(II) complexes were contemplated to be four-coordinated square planar configuration containing one water molecule. The redox process of ligands and complexes in DMSO solution containing 0.1 M TBAP as a supporting electrolyte was investigated by cyclic voltammetry and differential pulse voltammetry with glassy carbon electrode. The redox process of the tridentate Schiff base ligands was totally irreversible. The redox process of Cu(II) complexes was quasi-reversible and diffusion-controlled as one electron by one step process Cu(II)/Cu(I). The reduction potentials of the Cu(II) complexes shifted in the positive direction in the order of [Cu(II)(HNIPC)($H_2O$)]>[Cu(II)(HNIP)($H_2O$)]>[Cu(II)(SIP)($H_2O$)]>[Cu(II)(SIPC)($H_2O$)].

• Applied Chemistry for Engineering
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• v.34 no.3
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• pp.258-263
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• 2023

In this study, conductive polymers and the enzyme tyrosinase (Tyr) were deposited on the surface of a screen printed carbon electrode (SPCE), which can be fabricated as a disposable sensor chip, and applied to the detection of bisphenol F (BPF), an endocrine disruptor with proven links to male diseases and thyroid disorders, using electrochemical methods. On the surface of the SPCE working electrode, which was negatively charged by oxygen plasma treatment, a positively charged conductive polymer, poly(diallyldimethyl ammonium chloride) (PDDA), a negatively charged polymer compound, poly(sodium 4-styrenesulfonate) (PSS), and another layer of PDDA were layered by electrostatic attraction in the order of PDDA, PSS, and finally PDDA. Then, a layer of Tyr, which was negatively charged due to pH adjustment to 7.0, was added to create a PDDA-PSS-PDDA-Tyr sensor for BPF. When the electrode sensor is exposed to a BPF solution, which is the substrate and target analyte, 4,4'-methylenebis(cyclohexa-3,5-diene-1,2-dione) is generated by an oxidation reaction with the Tyr enzyme on the electrode surface. The reduction process of the product at 0.1 V (vs. Ag/AgCl) generating 4,4'-methylenebis(benzene-1,2-diol) was measured using cyclic and differential pulse voltammetries, resulting in a change in the peak current with respect to the concentration of BPF. In addition, we compared the detection performance of BPF using an ionic liquid electrolyte as an alternative to phosphate-buffered saline, which has been used in many previous sensing studies. Furthermore, the selectivity of bisphenol S, which acts as an interfering substance with a similar structure to BPF, was investigated. Finally, we demonstrated the practical applicability of the sensor by applying it to analyze the concentration of BPF in real samples prepared in the laboratory.