• Bulletin of the Korean Chemical Society
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• 제27권3호
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• pp.381-385
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• 2006

The temperature dependence on the electron transfer rate constant $(k_{app})$ for hydroquinone redox center in $H_2Q(CH_2)_n$SH-SAMs (n = 1, 4, 6, 8, 10, and 12) on gold electrode was investigated to obtain reorganization energy $(\lambda)$ using Laviron’s formalism and Arrhenius plot of ln $[k_{app}/T^{1/2}]$ vs. T^{-1} based on the Marcus densityof-states model. All the symmetry factors measured for the SAMs were relatively close to unity and rarely varied to temperature change as expected. The electron tunneling constant $(\beta)$ determined from the dependence of the $k_{app}$ on the distance between the redox center and the electrode surface gives almost the same $\beta$ values which are quite insensitive to temperature change. Good linear relationship of Arrhenius plot for all $H_2Q(CH_2)_n$SH-SAMs on gold electrode was obtained in the temperature range from 273 to 328 K. The slopes n Arrhenius plot deduced that $\lambda$ of hydroquinone moiety is ca. 1.3-1.4 eV irrespectively of alkyl chain length of the electroactive SAM.

• 분석과학
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• 제9권3호
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• pp.292-301
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• 1996

산화환원반응 탐침제로, poly ether 꼬리가 결합된 Cobalt(II)bipyridine 착물을 합성 하였고, 이들 화합물의 느린 확산계수와 불균일 전자이동을 설명하였다. $Co(bpy(ppgm)_2)_{3^-}(ClO_4)_2$에 전해질 $LiClO_4$가 혼합된 neat 상태의 산화반응에 대한 확산계수는 $1.5{\times}10^{-15}cm^2/s$ 였다. 이 화합물들의 불균일 전자이동 속도상수들은 확산계수와 관련이 있었다. 확산계수의 감소에 따라 속도상수(k)의 감소가 일어났다. 강한 이온쌍을 형성하는 $ClO{_4}^-$의 화합물은 약한 이온 쌍을 형성하는 $CF_3COO^-$ 화합물보다 확산계수가 훨씬 작았다.

• Journal of Microbiology and Biotechnology
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• 제22권10호
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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.

• 전기화학회지
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• 제9권3호
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• pp.113-117
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• 2006

The electrochemical properties of the redox mediator, 2,2'-azinobis (3-ethylbenzothiazoline-6-sulfonate) ($ABTS^{2-}$) were studied using cyclic voltammetry. The measured potentials (${E^o}'$ vs SCE) of the two redox couples of ABTS are 0.45 V for $ABTS^{2-}/ABTS^{\cdot-}$ and 0.87 V for $ABTS^{\cdot-}/ABTS^0$. The rate constant for heterogeneous electron transfer and the diffusion coefficients for $ABTS^{2-}$ are $5x10^{-3}cm\;s^{-1}$ and $3.1x10^{-6}cm^2\;s^{-1}$, respectively. Our interest in $ABTS^{2-}$ stems from the fact that this molecule functions as a substrate to the copper oxidase, laccase, by providing the reducing equivalents necessary for the biocatalyzed reduction of dioxygen to water. Consequently, when laccase is tethered to an electrode surface or dissolved in solution, $ABTS^{2-}$ can be used to quantify enzyme activity electrochemically.