• Bulletin of the Korean Chemical Society
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• v.33 no.5
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• pp.1734-1740
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• 2012

Voltammetric characterization of hydrophilic anion transfer processes across a 66 microhole array interface between the water and polyvinylchloride-2-nitrophenyloctylether gel layer is demonstrated. Since the transfer of hydrophilic anions including $Br^-$, $NO_3{^-}$, $I^-$, $SCN^-$ and $ClO_4{^-}$ across the liquid/gel interface usually sets the potential window within a negative potential region, a highly hydrophobic organic electrolyte, tetraoctylammonium tetrakis(pentafluorophenyl)borate, providing a wider potential window was incorporated into the gel phase. The transfer reaction of perchlorate anions across the microhole-water/gel interface was first studied using cyclic voltammetry and differential pulse voltammetry. The full voltammetric response of perchlorate anion transfer was then used as a reference for evaluating the half-wave transfer potentials, the formal transfer potentials and the formal Gibbs transfer energies of more hydrophilic anions such as $Br^-$, $NO_3{^-}$, $I^-$, and $SCN^-$. The current response associated with the perchlorate anion transfer across the micro-water/gel interface versus the perchlorate concentration was also demonstrated for sensing applications.

• Journal of Electrochemical Science and Technology
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• v.9 no.2
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• pp.149-156
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• 2018

In this technical note, I report the analysis of electrochemical impedance data measured with potential sweeping. Even though the instruments for voltammetric impedance measurements have been developed for decades using different approaches, their applications are limited due to the lack of well-established protocols to easily analyze voltammetry data. To fill this gap, the singular point of the specific potential is considered that is only determined by the standard/formal potential and the transfer coefficient and is independent of the kinetics and experimental parameters (including revertability) of faradaic reactions. Taking the advantage of its inertness, I suggest an approach employing the singular point as a reference to obtain general electrochemical information. As all the concepts and methods are verified with numerical simulations, this technique is expected to be applied for complex reactions involving electrochemical and chemical reaction mechanisms.

• Applied Chemistry for Engineering
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• v.29 no.5
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• pp.581-588
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• 2018

In this article, electrochemical investigation of the transfer reaction of ionizable cefotiam (CTM), an antibiotic molecule across a polarized water/1,2-dichloroethane (water/1,2-DCE) interface was studied. Ion partition diagram providing the preferred charged form of CTM in either water or 1,2-DCE phase was established via the voltammetric evaluation of the transfer process of differently charged CTM species depending upon the pH variation of aqueous solutions. Thermodynamic information including the formal transfer potential and formal Gibbs transfer energy values in addition to important pharmacokinetics including partition coefficients of ionizable CTM were also evaluated. In particular, the current associated with the transfer of CTM present at pH 3.0 aqueous solution proportionally increased with respect to the CTM concentration which was further used for developing CTM sensitive ion sensor. In order to improve the portability and convenient usage, a single microhole interface fabricated in a supportive polyethylene terephthalate film was used of which hole was filled with a polyvinylchloride-2-nitrophenyloctylether (PVC-NPOE) gel replacing 1,2-DCE, a toxic organic solvent. A dynamic range of $1-10{\mu}M$ CTM was obtained.

• Bulletin of the Korean Chemical Society
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• v.32 no.3
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• pp.863-866
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• 2011

The electrode reaction of $Eu^{3+}$ in a LiCl-KCl eutectic melt has been re-examined using cyclic voltammetry (CV). In this work, for the first time, the kinetic details of a $Eu^{3+}/Eu^{2+}$ redox system have been completely elucidated, along with the thermodynamic property, through a curve fitting applied to experimental CV data, which were obtained in a wide scan rate range of 0.5 to 10 V/s. The simulated results showed an excellent fit to all experimental CV data simultaneously, even though the curve fittings were performed within a large dynamic range of initial transfer coefficient values, formal potentials, and standard rate constants. As a result, a proper formal potential, transfer coefficient, and standard rate constant for the $Eu^{3+}/Eu^{2+}$ redox system were successfully extracted using the CV curve fitting.

• Bulletin of the Korean Chemical Society
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• v.34 no.12
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• pp.3649-3653
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• 2013

As anode fabrication with different materials has been proven to be a successful alternative for enhancing power generation in the microbial fuel cells, a new approach to improved performance of MFCs with the use of menadione/carbon powder composite-modified carbon cloth anode has been explored in this study. Menadione has formal potential to easily accept electrons from the outer membrane cytochromes of electroactive bacteria that can directly interact with the solid surface. Surface bound menadione was able to maintain an electrical wiring with the trans-membrane electron transfer pathways to facilitate extracellular electron transfer to the electrode. In a single chamber air cathode MFC inoculated with aerobic sludge, maximum power density of $1250{\pm}35mWm^{-2}$ was achieved, which was 25% higher than that of an unmodified anode. The observed high power density and improved coulomb efficiency of 61% were ascribed to the efficient electron shuttling via the immobilized menadione.

• Bulletin of the Korean Chemical Society
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• v.24 no.4
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• pp.437-440
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• 2003

In a mediator-aided microbial fuel cell, the choice of a proper mediator is one of the most important factors for the development of a better fuel cell system as it transfers electrons from bacteria to the electrode. The electrochemical behaviors within the lipid layer of two representative mediators, thionin and safranine O both of which exhibit reversible electron transfer reactions, were compared with the fuel cell efficiency. Thionin was found to be much more effective than safranine O though it has lower negative formal potential. Cyclic voltammetric and fluorescence spectroscopic analyses indicated that both mediators easily penetrated the lipid layer to pick up the electrons produced inside bacteria. While thionin could pass through the lipid layer, the gradual accumulation of safranine O was observed within the layer. This restricted dynamic behavior of safranine O led to the poor fuel cell operation despite its good negative formal potential.

• Applied Chemistry for Engineering
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• v.28 no.5
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• pp.506-512
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• 2017

The transfer reaction characteristics of tetracycline (TC) across a polarized water/1,2-dichloroethane (1,2-DCE) interface was studied via controlling both pH and ionic strength of the aqueous phase in conjunction with cyclic and differential pulse voltammetries. Formal transfer potential values of differently charged TC ionic species at the water/1,2-DCE interface were measured as a function of pH values of the aqueous solution, which led to establishing an ionic partition diagram for TC. As a result, we could identify which TC ionic species are more dominant in the aqueous or organic phase. Thermodynamic properties including the formal transfer potential, partition coefficient and Gibbs transfer energy of TC ionic species at the water/1,2-DCE interface were also estimated. In order to construct an electrochemical sensor for TC, a single microhole supported water/polyvinylchloride-2-nitrophenyloctylether (PVC-NPOE) gel interface was fabricated. A well-defined voltammetric response associated with the TC ion transfer process was achieved at pH 4.0 similar to that of using the water/1,2-DCE interface. Also the measured current increased proportionally with respect to the TC concentration. A $5{\mu}M$ of TC in pH 4.0 buffer solution with a dynamic range from $5{\mu}M$ to $30{\mu}M$ TC concentration could be analyzed when using differential pulse stripping voltammetry.

• Bulletin of the Korean Chemical Society
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• v.30 no.3
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• pp.582-588
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• 2009

Direct electron transfer of hemoglobin (Hb) in the chitosan (CTS) and $TiO_2$ nanoparticles (nano-$TiO_2$) composite films was achieved by using a room temperature ionic liquid of 1-butyl-3-methylimidazolium hexafluorophosphate ($BMIMPF_6$) modified carbon paste electrode (CILE) as the basal electrode. UV-Vis and FT-IR spectroscopy indicated that Hb in the film retained the native structure. Electrochemical investigation indicated that a pair of well-defined quasi-reversible redox peaks of Hb heme Fe(III)/Fe(II) was obtained with the formal potential located at -0.340 V (νs. SCE) in pH 7.0 phosphate buffer solution (PBS). The electrochemical parameters such as the electron transfer coefficient (α), the electron transfer number (n) and the standard electron transfer rate constant ($k_s$) were got as 0.422, 0.93 and 0.117 $s^{-1}$, respectively. The fabricated CTS/nano-$TiO_2$/Hb/CILE showed good electrocatalytic ability to the reduction of trichloroacetic acid (TCA) and hydrogen peroxide ($H_2O_2$), which exhibited a potential application in fabricating a new kind of third generation biosensor.

• Journal of Electrochemical Science and Technology
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• v.8 no.2
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• pp.96-100
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• 2017

Iridium(III) bis(2-phenylpyridinato-$N,C^{2^{\prime}}$)acetylacetonate ($(ppy)_2Ir(acac)$), a green dopant used in organic light-emitting devices (OLEDs), was subjected to electrochemical characterization to estimate its formal oxidation potential ($E^{o^{\prime}}$), HOMO energy level ($E_{HOMO}$), electron transfer rate constant ($k^{o^{\prime}}$), and diffusion coefficient ($D_o$). The employed combination of voltammetric methods, i.e., cyclic voltammetry (CV), chronocoulometry (CC), and the Nicholson method, provided meaningful insights into the electron transfer kinetics of $(ppy)_2Ir(acac)$, allowing the determination of $k^{o^{\prime}}$ and $D_o$. The quasi-reversible oxidation of $(ppy)_2Ir(acac)$ furnished information on $E^{o^{\prime}}$ and $E_{HOMO}$, allowing the latter parameter to be easily estimated by electrochemical methods without relying on expensive and complex ultraviolet photoemission spectroscopic (UPS) measurements.

• Polymer(Korea)
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• v.25 no.6
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• pp.782-788
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• 2001

The $[Ru(v-bpy)_3]^{2+}$ and vinylbenzoic acid (vba) were electrochemically copolymerized to afford electrodes modified with dopamine to study their properties such as electropolymerization rate, redox process, and electron transfer. The optimum mole ratio of the monomers was 5:2, which gave $1.84{ imes}10^{-2}s^{-1}$ of rate constant for first order reaction, while the ratio of the substances on the copolymeric film produced was 5:1.68. The formal potential produced from the hydroquinone=quinone+$2H^+2e^-$reaction at the electrode of GC/p- $[Ru(v-bpy)_3]^{2+}$/vba-dopamine was 0.17 V in phosphate buffer (pH=7.10). The electrocatalytic rate was $2.58{ imes}10^5cms^{-1}$;2.41 times faster than that of non-modified one. The mass change measured by EQCM was $3.28{ imes}10^3$$gmol^{-1}$ which is larger than that of non-modified one.