• Bulletin of the Korean Chemical Society
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• v.34 no.2
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• pp.475-481
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• 2013

By using ionic liquid 1-hexylpyridinium hexafluorophosphate ($HPPF_6$) based carbon ionic liquid electrode (CILE) as the substrate electrode, a $CoMoO_4$ nanorods and myoglobin (Mb) composite was casted on the surface of CILE with chitosan (CTS) as the film forming material to obtain the modified electrode (CTS/$CoMoO_4$-Mb/CILE). Spectroscopic results indicated that Mb retained its native structures without any conformational changes after mixed with $CoMoO_4$ nanorods and CTS. Electrochemical behaviors of Mb on the electrode were carefully investigated by cyclic voltammetry with a pair of well-defined redox peaks from the heme Fe(III)/Fe(II) redox center of Mb appeared, which indicated that direct electron transfer between Mb and CILE was realized. Electrochemical parameters such as the electron transfer number (n), charge transfer coefficient (${\alpha}$) and electron transfer rate constant ($k_s$) were estimated by cyclic voltammetry with the results as 1.09, 0.53 and 1.16 $s^{-1}$, respectively. The Mb modified electrode showed good electrocatalytic ability toward the reduction of trichloroacetic acid in the concentration range from 0.1 to 32.0 mmol $L^{-1}$ with the detection limit as 0.036 mmol $L^{-1}$ ($3{\sigma}$), and the reduction of $H_2O_2$ in the concentration range from 0.12 to 397.0 ${\mu}mol\;L^{-1}$ with the detection limit as 0.0426 ${\mu}mol\;L^{-1}$ ($3{\sigma}$).

• Bulletin of the Korean Chemical Society
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• v.15 no.10
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• pp.896-900
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• 1994

The pH-dependent reduction behavior of N-monosubstituted-4,4'-bipyridinium ions ($RBPY^+: R=methyl(C_1)$; benzyl; n-octyl; n-dodecyl) has been investigated by electrochemical and spectroelectrochemical techniques. At acidic condition, $RBPY^+$ is protonated and the protonated species are reduced by two consecutive one-electron processes. The $2e^-$ reduced species undergoes a chemical reaction with $H^+$. The second-order rate constant $(k_H)$ of the homogeneous chemical process is $(3.7{\pm}0.3){\times}10^3M^{-1}s^{-1}$ for the two electron reduction product of $C_1BPY^+$. At high pH, the electrode reduction of $RBPY^+$ is one-step $2e^-$ transfer process with concomitant addition of $H^+$, which is confirmed by cyclic voltammetric study using a microdisk electrode.

• Journal of the Korean Institute of Telematics and Electronics
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• v.24 no.4
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• pp.646-651
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• 1987

The photoconductive multilayer composed of glassy, porous, and fine-grained layers was fabdricated with Se and Sb2S3 by vacuum evaporation in order to be used as vidicon target. And its electrical, optical properties were investigatee. The fabrication conditions were as follow: the glassy layer was first deposited to have the thickness of 6500 \ulcornerat the deposition rate of 250\ulcornersec. High photosensitivity(\ulcorner=1) was obtained but its shortcoming was high dielectric constant. Therefore, the porous layer was added to lower dielectric constant and had 7500\ulcornerthick in the argon gas ambikent of 7x10-\ulcorner And the fine-grained layer was formed to prevent secondary electron emission and obtain good resolution. Its thickness was about 1700\ulcorner For the given vidicon target, the light transfer characteristic, that is, photosensitivity (\ulcorner) was measured to be 0.8 at the applied voltage of 25V. The spectral sensitivity was quite similar to that of the human eyes.

• Bulletin of the Korean Chemical Society
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• v.24 no.12
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• pp.1751-1756
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• 2003

An electrochemical study related to the electroreduction of 4-amino-6-methyl-3-thio-1,2,4-triazin-5-one(I), 6-methyl-3-thio-1,2,4-triazin-5-one(II), and 2,4-dimetoxy-6-methyl-1,3,5-triazine(III) in dimethylformamide at glassy carbon electrode has been performed. A variety of electrochemical techniques, such as differential pulse voltammetry (DPV), cyclic voltammetry (CV), chronoamperometry, and coulometry were employed to clarify the mechanism of the electrode process. The compounds I and II with thiol group exhibited similar redox behavior. Both displayed two cathodic peaks, whereas the third compound, III, without thiol group showed only one cathodic peak in the same potential range of the second peak of I and II. The results of this study suggest that in the first step the one electron reduction of thiol produced a disulfide derivative and in the second reduction step the azomethane in the triazine ring was reduced in two electron processes. A reduction mechanism for all three compounds is proposed on this basis. In addition, some numerical constants, such as diffusion constant, transfer coefficient, and rate constant of coupled chemical reaction in the first reduction peak were also reported.

• Journal of Electrochemical Science and Technology
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• v.4 no.2
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• pp.71-80
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• 2013

The study of methyl viologen ($MV^{2+}$) mediated oxygen reduction in electrolytic ethanol media possesses potential application in the electrochemical synthesis of hydrogen peroxide mainly due to the advantages of the much increased solubility of molecular oxygen ($O_2$) and high degree of reversibility of $MV^{2+/{\bullet}+}$ redox couple. The diffusion coefficients of both $MV^{2+}$ and $O_2$ were investigated via electrochemical techniques. For the first time, $MV^{2+}$ mediated $O_2$ reduction in electrolytic ethanol solution has been proved to be feasible on both boron-doped diamond and micro-carbon disc electrodes. The electrocatalytic response is demonstrated to be due to the radical cation, $MV^{{\bullet}+}$. The homogeneous electron transfer step is suggested to be the rate determining step with a rate constant of $(1{\pm}0.1){\times}10^5M^{-1}s^{-1}$. With the aid of a simulation program describing the EC' mechanism, by increasing the concentration ratio of $MV^{2+}$ to $O_2$ electrochemical catalysis can be switched from a partial to a 'total catalysis' regime.

• Journal of the Korean Vacuum Society
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• v.7 no.s1
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• pp.20-24
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• 1998

Photploymer films are widely used in printing and electronic industries, and their usage is expanding to encompass holography, data storage and data processing, optical waveguides and compact disks, etc. One of widely used photoplymerization initiator, 20chloro-hexaarylbiimidazole (o-Cl-HABI), is studied by laser flash photolysis in dichloromethane solution in the absence and presence of the visible light photosensitizing dye, 2, 5-bis[(2, 3, 6, 7 -tetrahydro- 1H, 5H -benzo [i, j,] quinolizin -1-yl) methylene]-cyclopenta-none, (JAW). In the presence of JAW, an increase in triarylimidazolyl radicals L.formation is observed in relative to the absence of JAW. The mechanism of this photosensitizing dissociation is concluded as the dissociation of the o-Cl-HABI radical anion formed by the electron transfer from excited singlet state of JAW to o-Cl-HABI. The observed formation of L.radicals exhibits a linear dependence on o-Cl-HABI concentration. The rate constant of electron transfer obtained from this dependence is equal to (1.0$\pm$0.2) x $10^9 M^{-1}s^{-1}$. No reaction between the excited triplet state of JAW and o-Cl-HABI is found.

• Korean Journal of Chemical Engineering
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• v.35 no.12
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• pp.2421-2429
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• 2018

Thiol-based self-assembled anchor linked to glucose oxidase (GOx) and gold nanoparticle (GNP) cluster is suggested to enhance the performance of glucose biosensor. By the adoption of thiol-based anchors, the activity of biocatalyst consisting of GOx, GNP, polyethyleneimine (PEI) and carbon nanotube (CNT) is improved because they play a crucial role in preventing the leaching out of GOx. They also promote electron collection and transfer, and this is due to a strong hydrophobic interaction between the active site of GOx and the aromatic ring of anchor, while the effect is optimized with the use of thiophenol anchor due to its simple configuration. Based on that, it is quantified that by the adoption of thiophenol as anchor, the current density of flavin adenine dinucleotide (FAD) redox reaction increases about 42%, electron transfer rate constant ($k_s$) is $9.1{\pm}0.1s^{-1}$ and the value is 26% higher than that of catalyst that does not use the anchor structure.

• Bulletin of the Korean Chemical Society
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• v.35 no.6
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• pp.1754-1758
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• 2014

The nucleophilic substitution reactions of bis(Y-aryl) chlorothiophosphates (1) with X-pyridines are investigated kinetically in acetonitrile at $35.0^{\circ}C$. The free energy relationships with both X and Y are biphasic concave upwards with a break point at X = 3-Ph and Y = H, respectively. The sign of cross-interaction constants (CICs; ${\rho}_{XY}$) is positive with all X and Y. Proposed mechanism is a stepwise process with a rate-limiting leaving group departure from the intermediate with all X and Y. The kinetic results of 1 are compared with those of Y-aryl phenyl chlorothiophosphates (2). In the case of Y = electron-withdrawing groups, the cross-interaction between Y and Y, due to additional substituent Y, is significant enough to change the sign of ${\rho}_{XY}$ from negative with 2 to positive with 1, indicative of the change of mechanism from a rate-limiting bond formation to bond breaking.

• Journal of Industrial and Engineering Chemistry
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• v.67
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• pp.486-496
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• 2018

Bimetallic Pd@Ni nanostructure exhibited enhanced co-catalytic activity for the selective hydrogenation of benzaldehyde compare to their monometallic counterparts. Impregnation of these mono/bimetallic nanostructures on mesoporous $TiO_2$ leads to several surface modifications. The bimetallic PNT-3 ($Pd_3@Ni_1/mTiO_2$) exhibited large surface area ($212m^2g^{-1}$), and low recombination rate of the charge carriers ($e^--h^+$). The hydrogenation reaction was analyzed under controlled experiments. It was observed that under UV-light irradiations and saturated hydrogen atmosphere the bimetallic PNT-3 photocatalyst display higher rate constant $k=5.31{\times}10^{-1}h^{-1}$ owing to reduction in the barrier height which leads to efficiently transfer of electron at bimetallic/$mTiO_2$ interface.

• Applied Chemistry for Engineering
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• v.28 no.5
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• pp.597-600
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• 2017

$(C_{10}H_8N_2H)_2Cr_2O_7$ was synthesized by reacting 4,4'-bipyridine and chromium (VI) trioxide. The structure of the product was characterized with FT-IR (infrared spectroscopy) and elemental analysis. The oxidation of benzyl alcohol using $(C_{10}H_8N_2H)_2Cr_2O_7$ in various solvents showed that the reactivity increased with the increase of the solvent dielectric constant, in the order of DMF (N,N'-dimethylformamide) > acetone > chloroform > cyclohexane. In the presence of DMF, an acidic catalyst such as $H_2SO_4$ $(C_{10}H_8N_2H)_2Cr_2O_7$ oxidized benzyl alcohol (H) and its derivatives ($p-OCH_3$, $m-CH_3$, $m-OCH_3$, m-Cl, $m-NO_2$). Electron donating substituents accelerated the reaction rate, whereas electron acceptor groups retarded the reaction rate. Hammett reaction constant (${\rho}$) was -0.70 (308 K). The observed experimental data were used to rationalize the hydride ion transfer in the rate determining step.