• Title/Summary/Keyword: Mediated electron transfer

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Characteristics of Mediated Enzymatic Nitrate Reduction by Gallocyanine-Bound Nanoporous Electrode

  • Kim Seung-Hwan;Song Seung-Hoon;Yoo Young-Je
    • Journal of Microbiology and Biotechnology
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    • v.16 no.4
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    • pp.505-510
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    • 2006
  • A gallocyanine-bound nanoporous titanium dioxide electrode system was investigated to carry out a mediated enzyme reaction. Gallocyanine was bound either directly or through an aminopropylsilane linker to the film of nanoporous titanium dioxide and used as a mediator for nitrate reductase in the mediated enzymatic nitrate reduction. The electrode with the aminopropylsilane linker showed 20% higher efficiency of electron transfer at the same potential than that directly linked. The prepared electrodes showed $0.26{\mu}mol/h$ nitrate reduction at a $100mm^2$ surface of the electrode, and linear current response on nitrate ion concentration up to 1.0 mM, which is very useful as a biosensor of nitrate ion in water.

Selection of Mediators for Bioelectrochemical Nitrate Reduction

  • Kim Seung Hwan;Song Seung Hoon;Yoo Young Je
    • Biotechnology and Bioprocess Engineering:BBE
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    • v.10 no.1
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    • pp.47-51
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    • 2005
  • The bioelectrochemical reduction of nitrate in the presence of various mediators including methyl viologen and azure A was studied using a 3-electrode voltammetric system. The catalytic potential for the reduction of the mediators was observed in the reactor, which for methyl viologen and azure A were -0.74 V and -0.32 V, respectively, with respect to the potential of Ag/AgCl reference electrode. This potential was then applied to a working electrode to reduce each mediator for enzymatic nitrate reduction. Nitrite, the product of the reaction, was measured to observe the enzymatic nitrate reduction in the reaction media. Methyl viologen was observed as the most efficient mediator among those tested, while azure A showed the highest electron efficiency at the intrinsic reduction potential when the mediated enzyme reactions were carried out with the freely solubilized mediator. The electron transfer of azure A with respect to time was due to the adhesion of azure A to the hydrophilic surface during the reduction. In addition, the use of the adsorbed mediator on conductive activated carbon was proposed to inhibit the change in the electron transfer rate during the reaction by maintaining a constant mediator concentration and active surface area of the electrode. Azure A showed better than nitrite formation than methyl viologen when used with activated carbon.

Viologen-mediated Reductive Transformations of gem-Bromonitro Compounds and $\alpha$-Nitro Ketones by Sodium Dithionite

  • Kwanghee Koh Park;Won Kyou Joung;Sook Young Choi
    • Bulletin of the Korean Chemical Society
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    • v.14 no.4
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    • pp.461-465
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    • 1993
  • Reductive transformations of gem-bromonitro compounds and ${\alpha}$-nitro ketones were carried out conveniently with sodium dithionite by using dioctyl viologen as an electron-transfer catalyst in dichloromethane-water two-phase system:the bromine atom in gem-bromonitro compounds and the nitro group in ${\alpha}$-nitro ketones are replaced by hydrogen.

Methyl Viologen Mediated Oxygen Reduction in Ethanol Solvent: the Electrocatalytic Reactivity of the Radical Cation

  • Lin, Qianqi;Li, Qian;Batchelor-McAuley, Christopher;Compton, Richard G.
    • 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.

Enhancement of DNA-mediated Energy Transfer from Ethidium to meso-Tetrakis(N-methylpyridinium-4-yl)porphyrin by Ca2+ Ion

  • Kim, Jong-Moon;Park, Bo-Ra-Mi;Kim, Young-Rhan;Gong, Lindan;Jang, Myung-Duk;Kim, Seog-K.
    • Bulletin of the Korean Chemical Society
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    • v.33 no.4
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    • pp.1165-1169
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    • 2012
  • The fluorescence intensity of DNA-intercalated ethidium with [ethidium]/[DNA base] being 0.005 was quenched upon the binding of another intercalating ligand, meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP). Addition of $Ca^{2+}$ enhanced the quenching efficiency. The range of separations between donor and acceptor molecules, within which total quenching occurs, was calculated using a one-dimensional resonance energy transfer mechanism to be 9.5 base-pairs or $32.3{\AA}$ in the absence of $Ca^{2+}$ ions. The distance increased to 18.7 base-pairs or about $63.6{\AA}$ in the presence $100{\mu}M$ $Ca^{2+}$. Considering that (1) $Ca^{2+}$ had little effect on the binding modes of ethidium and TMPyP, which was investigated by reduced linear dichroism and (2) spectral overlap between the emission spectrum of ethidium and the absorption spectrum of TMPyP was maintained in the presence of $Ca^{2+}$, contributions from orientation factor and spectral overlap to $Ca^{2+}$-induced enhancement in DNA mediated energy transfer was limited. Although there is no direct evidence, electron transfer along the DNA stem may accompany the observed fluorescence quenching. In this respect, DNA bound $Ca^{2+}$ act as a partially conducting medium.

The Production of Tantalum Powder by MR and EMR Method (MR법 및 EMR법에 의한 탄탈륨 분말 제조)

  • Bae, In Seong;Park, Hyeoung Ho;Kim, Byung Il
    • Journal of the Korean Society for Heat Treatment
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    • v.15 no.1
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    • pp.16-20
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    • 2002
  • In conventional metallothermic reduction(MR) for obtaining tantalum powder in batch-type operation, it is difficult to control morphology and location of deposits because the reaction occurs by direct physical contact between reductants and feed materials. On the other hand, a electronically mediated reaction(EMR) is capable to overcome these difficulties through the reaction by electron transfer and have a merit of continuous process. In this study an MR and EMR method has been applied to the production of a tantalum powder by sodium reduction of $K_2TaF_7$. As the reduction temperature increases, the particle size and yield of tantalum powder obtained by MR and EMR method is increased.

Photodamage to Double-stranded DNA by Xanthone Analogues Increases Exponentially with Their HOMO Energies

  • Hirakawa, Kazutaka;Yoshida, Mami;Oikawa, Shinji;Kawanishi, Shosuke
    • Journal of Photoscience
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    • v.9 no.2
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    • pp.488-490
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    • 2002
  • DNA photodamage mediated by photosensitizers are believed to play an important role in solar UVA carcinogenesis. We investigated the relationship between the DNA-damaging abilities of photoexcited xanthone analogues (as photosensitizers) and their highest occupied molecular orbital (HOMO) energies. DNA damage was examined using /sup 32/P-labeled DNA fragments obtained from the p53 tumor suppressor gene. These compounds induced DNA photodamage in a similar manner, and the extents of DNA damage were following order: xanthone> thioxanthone > acridone. Photoexcited xanthone caused nucleobase oxidation specifically at 5'-G of GG sequence in double-stranded DNA. An oxidative product of 2'-deoxyguanosine, 8-hydroxy-2'-deoxyguanosine (8-OHdG), was detected, and the amount was decreased by DNA denaturation. These findings suggest that photoexcited xanthone generates 8-OHdG at 5'-G of GG in double-stranded DNA through electron transfer. The calculated HOMO energies of these photosensitizers decreased in the following order: xanthone> thioxanthone > acridone. This study has demonstrated that DNA-damaging abilities of these photosensitizers increased exponentially with an increase in their HOMO energies.

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Electrical Recognition of Label-Free Oligonucleotides upon Streptavidin-Modified Electrode Surfaces

  • Park, Jong-Wan;Jung, Ho-Sub;Lee, Hea-Yeon;Kawai, Tomoji
    • Biotechnology and Bioprocess Engineering:BBE
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    • v.10 no.6
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    • pp.505-509
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    • 2005
  • For the purpose of developing a direct label-free electrochemical detection system, we have systematically investigated the electrochemical signatures of each step in the preparation procedure, from a bare gold electrode to the hybridization of label-free complementary DNA, for the streptavidin-modified electrode. For the purpose of this investigation, we obtained the following pertinent data; cyclic voltammogram measurements, electrochemical impedance spectra and square wave voltammogram measurements, in $Fe(CN)_6^{3-}/Fe(CN)_6^{4-}$ solution (which was utilized as the electron transfer redox mediator). The oligonucleotide molecules on the streptavidin-modified electrodes exhibited intrinsic redox activity in the ferrocyanide-mediated electrochemical measurements. Furthermore, the investigation of electrochemical electron transfer, according to the sequence of oligonucleotide molecules, was also undertaken. This work demonstrates that direct label-free oligonucleotide electrical recognition, based on biofunctional streptavidin-modified gold electrodes, could lead to the development of a new biosensor protocol for the expansion of rapid, cost-effective detection systems.

Coordination chemistry of mitochondrial copper metalloenzymes: exploring implications for copper dyshomeostasis in cell death

  • Daeun Shim;Jiyeon Han
    • BMB Reports
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    • v.56 no.11
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    • pp.575-583
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    • 2023
  • Mitochondria, fundamental cellular organelles that govern energy metabolism, hold a pivotal role in cellular vitality. While consuming dioxygen to produce adenosine triphosphate (ATP), the electron transfer process within mitochondria can engender the formation of reactive oxygen species that exert dual roles in endothelial homeostatic signaling and oxidative stress. In the context of the intricate electron transfer process, several metal ions that include copper, iron, zinc, and manganese serve as crucial cofactors in mitochondrial metalloenzymes to mediate the synthesis of ATP and antioxidant defense. In this mini review, we provide a comprehensive understanding of the coordination chemistry of mitochondrial cuproenzymes. In detail, cytochrome c oxidase (CcO) reduces dioxygen to water coupled with proton pumping to generate an electrochemical gradient, while superoxide dismutase 1 (SOD1) functions in detoxifying superoxide into hydrogen peroxide. With an emphasis on the catalytic reactions of the copper metalloenzymes and insights into their ligand environment, we also outline the metalation process of these enzymes throughout the copper trafficking system. The impairment of copper homeostasis can trigger mitochondrial dysfunction, and potentially lead to the development of copper-related disorders. We describe the current knowledge regarding copper-mediated toxicity mechanisms, thereby shedding light on prospective therapeutic strategies for pathologies intertwined with copper dyshomeostasis.

Development of Polymeric Layer for Enhancing The Adhesion of Nano-devices Fabricated by The Nanotransfer Molding Method

  • Lee, Gi-Seok;Seong, Myeong-Mo
    • Proceedings of the Korean Vacuum Society Conference
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    • 2013.02a
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    • pp.634-634
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    • 2013
  • Transfer molding methods have a problem that weak adhesion between nanostructures and substrates. It is important to make various nano scale applications, also the stability of nanostructure on substrate is related with device performance. We studied an effect of poly 4-vinylphenol (PVP) as the polymeric adhesion layer between organic nanowires and a Si substrate when the nanowires are transferred by liquid-bridge-mediated nanotransfer molding method (LB-nTM). Their structural stability was examined by optical microscopy, scanning electron microscopy as multiple transfer molding and washing process. Field-effect transistors were fabricated with organic semiconductor nanowires on a polymeric adhesion layer and their electrical properties showed no significant difference as the one without the adhesion layer. As a result, adhesion layer can be used in the washing process and making multi-layer nano-scale patterns.

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