• Macromolecular Research
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• v.12 no.3
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• pp.322-324
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• 2004

Poly(1-dodecyl-2,5-pyrrylene vinylene) (PDPV) has an extended 1t-conjugated structure and exhibits characteristic spectroscopic features. The PDPV we prepared has an absorption maximum at 510nm and its long absorption tail at ca. 750nm in methylene chloride is due to the long 1t-conjugated system connected to vinyl group. The large red-shift of emission was 625nm upon excitation at 480nm, which suggests the existence of a low emissive state. The emission of PDPV in less-polar solvents decreased markedly relative to that in the more-polar solvents; this observation was ascribed possibly to quenching by a strong vibrational mode of the dodecyl groups of PDPV in less-polar solvents. Furthermore, the emission from the high-energy side had a single decay component (0.1㎱, 49.96%), while that from the low-energy side had two components (0.6㎱, 27.1 %; 2.7㎱, 22.87%). We characterized the redox properties of PDPV by cyclic voltammetry. Every redox peak showed irreversible behavior; the oxidation peaks appeared at 1.7,0.8, and 0.6V and the reduction peak at -0.5V.

• Journal of Microbiology and Biotechnology
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• v.22 no.10
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• pp.1446-1451
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• 2012

Levodopa or L-3,4-dihydroxyphenylalanine (L-DOPA) is the precursor of the neurotransmitter dopamine. L-DOPA is a famous treatment for Parkinson's disease symptoms. In this study, electroenzymatic synthesis of L-DOPA was performed in a three-electrode cell, comprising a Ag/AgCl reference electrode, a platinum wire auxiliary electrode, and a glassy carbon working electrode. L-DOPA had an oxidation peak at 376 mV and a reduction peak at -550 mV. The optimum conditions of pH, temperature, and amount of free tyrosinase enzyme were pH 7, $30^{\circ}C$, and 250 IU, respectively. The kinetic constant of the free tyrosinase enzyme was found for both cresolase and catacholase activity to be 0.25 and 0.4 mM, respectively. A cyclic voltammogram was used to investigate the electron transfer rate constant. The mean heterogeneous electron transfer rate ($k_e$) was $5.8{\times}10^{-4}$ cm/s. The results suggest that the electroenzymatic method could be an alternative way to produce L-DOPA without the use of a reducing agent such as ascorbic acid.

• Bulletin of the Korean Chemical Society
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• v.14 no.2
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• pp.195-200
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• 1993

The neutral, reduced, and oxidized 2,2-trans isomers of $Rh_2(ap)_4$ (ap=2-anilinopyridinate) were investigated with respect to dioxygen binding in $CH_2Cl_2$ containing 0.1 M tetrabutyl-ammonium perchlorate. $Rh_2(ap)_4$ binds dioxygen in nonaqueous media and forms a $Rh^{II}Rh^{III}$ superoxide complex, $Rh_2(ap)_4(O_2)$. This neutral species was isolated and is characterized by UV-visible and IR spectroscopy, mass spectrometry and cyclic voltammetry. It can be reduced by one electron at $E_{1/2}$ = -0.45 V vs. SCE in $CH_2Cl_2$ and gives ${[Rh_2(ap)_4(O_2)]}^-$ as demonstrated by the ESR spectrum of a frozen solution taken after controlled potential reduction. The superoxide ion in ${[Rh_2(ap)_4(O_2)]}^-$ is axially bound to one of the two rhodium ions, both of which are in a +2 oxidation state. $Rh_2(ap)_4(O_2)$ can also be stepwise oxidized in two one-electron transfer steps at $E_{1/2}$ = 0.21 V and 0.85 V vs. SCE in $CH_2Cl_2$ and gives ${[Rh_2(ap)_4(O_2)]}^+$ followed by ${[Rh_2(ap)_4(O_2)]}^{2+}$. ESR spectra demonstrate that the singly oxidized complex is best described as ${[Rh^{II}Rh^{III}(ap)_4(O_2)]}^+$ where the odd electron is delocalized on both of the two rhodium ions and the axial ligand is molecular oxygen.

• Nuclear Engineering and Technology
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• v.54 no.3
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• pp.965-974
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• 2022

Platinum anodes are widely used for metal oxides reduction in LiCl-Li₂O, however high-cost and low-corrosion resistance hinder their implementation. NiO-Li₂O ceramics is an alternative corrosion resistant anode material. Anode processes on platinum and NiO-Li₂O ceramics were studied in (80 mol.%) LiCl-(20mol.%)KCl and (80 mol.%)LiCl-(20 mol.%)KCl-Li₂O melts by cyclic voltammetry, potentiostatic and galvanostatic electrolysis. Experiments performed in the LiCl-KCl melt without Li₂O illustrate that a Pt anode dissolution causes the Pt²⁺ ions formation at 3.14 V and 550℃ and at 3.04 V and 650℃. A two-stage Pt oxidation was observed in the melts with the Li₂O at 2.40 ÷ 2.43 V, which resulted in the Li₂PtO₃ formation. Oxygen current efficiency of the Pt anode at 2.8 V and 650℃ reached about 96%. The anode process on the NiO-Li₂O electrode in the LiCl-KCl melt without Li₂O proceeds at the potentials more positive than 3.1 V and results in the electrochemical decomposition of ceramic electrode to NiO and O₂. Oxygen current efficiency on NiO-Li₂O is close to 100%. The NiO-Li₂O ceramic anode demonstrated good electrochemical characteristics during the galvanostatic electrolysis at 0.25 A/cm² for 35 h and may be successfully used for pyrochemical treating of spent nuclear fuel.

• Journal of Hydrogen and New Energy
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• v.26 no.2
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• pp.179-183
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• 2015

In this study, we propose a catalyst structure including enzyme and metal nano rod for glucose sensing. In the catalyst structure, glucose oxidase (GOx) and gold nano rod (GNR) are alternatingly immobilized on the surface of carbon nanotube (CNT), while poly(ethyleneimine) (PEI) is inserted in between the GOx and GNR to fortify their bonding and give them opposite polarization ($[GOx/GNR]_nPEI/CNT$). To investigate the impact of $[GOx/GNR]_nPEI/CNT$ on glucose sensing, some electrochemical measurements are carried out. Initially, their optimal layer is determined by using cyclic voltammogram and as a result of that, it is proved that $[GOx/GNR/PEI]_2/CNT$ is the best layer. Its glucose sensitivity is $13.315{\mu}AmM^{-1}cm^{-2}$. When it comes to the redox reaction mechanism of flavin adenine dinucleotide (FAD) within $[GOx/GNR/PEI]_2/CNT$, (i) oxygen plays a mediator role in moving electrons and protons generated by glucose oxidation reaction to those for the reduction reaction of FAD and (ii) glucose does not affect the redox reaction of FAD. It is also recognized that the $[GOx/GNR/PEI]_3/CNT$ is limited to the surface reaction and the reaction is quasi-reversible.

• Journal of the Korean Chemical Society
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• v.30 no.1
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• pp.19-26
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• 1986

A titanium oxide thin films were prepared by air oxidation and vapour oxidation and a $TiO_2$ single crystal was reduced by heating in an argon atmosphere. All the electrode characteristics of the Ti$O_{2-x}$, thin films are not different from those of slightly reduced single crystal rutile. In cyclic voltammogram of oxygen containing electrolyte solution at Ti$O_{2-x}$ electrodes, cathodic peaks were observed at between -0.8V and -1.0V vs. SCE. The cathodic current near 0V vs. SCE in saturated solution with nitrogen was observed to be greater than in saturated solution with air. The chronoamperogram was represented by the equation of i = $i_0e^{-kt}$, when the rate constant k was represented by the equation of k =$k_0{[H^+]}^nexp(A{\eta}+E_a/RT)$ The values of activation energy $E_a $were found to be 4.6~4.8kcal/mole in overpotential range of 0.035∼0.145 V and 1.6kcal/mole in overpotential range of 0.2∼0.5V. The values of n and A were found to be 0. 1 and 5.4~5.6/V in range of 0.035~0.145V, and in range of 0.2~0.5V, to be 0.04 and 1.3/V, respectively. This can be interpreted as an totally irreversible reduction of oxygen.

• Applied Chemistry for Engineering
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• v.35 no.4
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• pp.296-302
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• 2024

An ionic conjugated polymer-iron (III) chloride composite was prepared via in-situ quaternization polymerization of 2-ethynylpyridine (2EP) using iron (III) chloride. Various instrumental methods revealed that the chemical structure of the resulting conjugated polymer (P2EP)-iron (III) chloride composite has the conjugated backbone system having the designed pyridinium ferric chloride complexes. The polymerization mechanism was assumed to be that the activated triple bond of 2-ethynylpyridinium salt, formed at the first reaction step, is easily susceptible to the step-wise polymerization, followed by the same propagation step that contains the propagating macroanion and monomeric 2-ethynylpyridinium salts. The electro-optical and electrochemical properties of the P2EP-FeCl₃ composite were studied. In the UV-visible spectra of P2EP-FeCl₃ composite, the absorption maximum values were 480 nm and 533 nm, and the PL maximum value was 598 nm. The cyclic voltammograms of the P2EP-FeCl₃ composite exhibited irreversible electrochemical behavior between the oxidation and reduction peaks. The kinetics of the redox process of composites were found to be very close to a diffusion-controlled process from the plot of the oxidation current density versus the scan rate.

• Applied Chemistry for Engineering
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• v.21 no.1
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• pp.52-57
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• 2010

Although chemical sedimentation and ion exchange are usually applied to the treatment of heavy metal ions and radioactive cations, they have some serious disadvantages like a great consumption of chemicals, the disposal of valuable metals, and the secondary pollution of soil by the solid-waste. The advanced countries recently have studied the electrochemical ion exchange, combined electrochemical reduction and ion exchange, for the development of the alternative technique. This study has been performed to investigate the optimum condition for the preparation of the nickel hexacyanoferrate (NiHCNFe) which is an electrochemical ion exchanger. NiHCNFe film was deposited on the surface of nickel plate by chemical method or electrochemical method. The morphology and composition of NiHCNFe were observed by SEM and EDS, respectively. The peak current density of NiHCNFe was measured from the cyclic voltammograms of the continuous oxidation-reduction reaction in a parallel plane ion exchange electrode reactor. It was found that the chemical preparation method was better than the electrochemical method. The concentrated NiHCNFe was apparently deposited on nickel plate when dipping in the preparing solution for 118 h, especially. It also had a best durable performance as an ion exchange electrode.

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 2003.11a
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• pp.51-55
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• 2003

The thermal behavior of NiFe$_2$O$_4$ prepared by a solid-state reaction was investigated for H$_2$ generation by the thermochemical cycle. The reduction of NiFe$_2$O$_4$ started from 800 $^{\circ}C$, and the weight loss was 0.2-0.3 wt％ up to 1000 $^{\circ}C$. At this reaction, NiFe$_2$O$_4$ was reduced by release of oxygen bonded with the Fe$^3$ion in the B site of NiFe$_2$O$_4$. In the $H_2O$ decomposition reaction, H$_2$ was generated by oxidation of reduced NiFe$_2$O$_4$. The crystal structure of NiFe$_2$O$_4$ for redox reaction maintained spinel structure. Then, NiFe$_2$O$_4$ is excellent material in the thermochemical cyclic reaction due to release oxygen at low temperature for the reduction reaction and produce H$_2$ maintaining crystal structure for redox reaction.

• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.509-519
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• 1987

The tetradentate Schiff base ligand, 3,4-bis(salicylidene diimine) toluene, have been prepared by the reaction of salicylaldehyde with 3,4-diaminotoluene by Duff method. The Schiff base ligand reacts with Ni(II), Co(II), and Cu(II) ions to form new complexes, [Ni(o-BSDT)${\cdot}(H_2O)_2$], [Co(o-BSDT)${\cdot}(H_2O)$], and [Cu(o-BSDT)]. It seems that Ni(II) and Ni(II) complexes are hexacoordinated with the Schiff base ligand and two molecules of water, while the Cu(II) complexes are tetracoordinated with the Schiff base. The mole ratio of tetradentate Schiff base ligand to metals was found to be 1 : 1. The redox chemistry of these complexes was investigated by polarography and cyclic voltammetry with glassy carbon electrode in DMSO with 0.1M TEAP${\cdot}$[Ni(o-BSDT)${\cdot}(H_2O)_2$] hav EC reaction mechanisms which undergo a irreversible electron transfer followed by a fast chemical reaction. [Co(o-BSDT)${\cdot}(H_2O)_2$] undergoes a reduction of Co(II) to Co(I) and a oxidation of Co(II) to Co(III), and [Cu(o-BSDT)] undergoes a reduction of Cu(II) to Cu(I).