• Title/Summary/Keyword: redox potential

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NMR Studies on Ferrocytochrome $C_3$ and its Interaction with Ferredoxin I

  • Kim, Andre;Park, Jang-Su
    • Journal of the Korean Magnetic Resonance Society
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    • v.3 no.1
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    • pp.12-26
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    • 1999
  • The 1H NMR signals of the heme methyl, propionate and related chemical groups of cytochrome C3 from Desulfovibrio vulgaris Miyazaki F (D.v. MF) were assigned by means of 1D NOE, 2D DQFCOSY and 2D TOCSY spectra. They were consistent with the assignments of the hemes with the highest and second-lowest redox potentials reported by Gayda et al. [Reference: 15]. The heme assignments were also supported by NOE between the methyl groups of these hemes and the side chain of Val-18, All the results contradicted the heme assignments for D.v. MF cytochrome C3 made on the basis of NMR [Reference: 11]. Based on these assignments, the interaction of cytochrome C3 with ferredoxin I was investigated by NMR. The major interaction site of cytochrome C3 was identified as the heme with the highest redox potential, which is surrounded by the highest density of positive charges. The stoichiometry and association constant were two cytochrome C3 molecules per monomer of ferredoxin I and 108 M-2 (at 53 mM ionic strength and $25^{\circ}C$), respectively.

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Regulation of Apoptosis by Nitrosative Stress

  • Kim, Ki-Mo;Kim, Peter K.M.;Kwon, Young-Guen;Bai, Se-Kyung;Nam, Woo-Dong;Kim, Young-Myeong
    • BMB Reports
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    • v.35 no.1
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    • pp.127-133
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    • 2002
  • Nitrosative stress can prevent or induce apoptosis. It occurs via S-nitrosylation by the interaction of nitric oxide (NO) with the biological thiols of proteins. Cellular redox potential and non-heme iron content determine S-nitrosylation. Apoptotic cell death is inhibited by S-nitrosylation of the redox-sensitive thiol in the catalytic site of caspase family proteases, which play an essential role in the apoptotic signal cascade. Nitrosative stress can also promote apoptosis by the activation of mitochondrial apoptotic pathways, such as the release of cytochrome c, an apoptosis-inducing factor, and endonuclease G from mitochondria, as well as the suppression of NF-${\kappa}B$ activity. In this article we reviewed the mechanisms whereby S-nitrosylation and nitrosative stress regulate the apoptotic signal cascade.

DNA Ligand - Redox Active Molecule Conjugates as an Electrochemical DNA Probe

  • Ihara, Toshihiro;Maruo, Voshiyuki;Uto, Yoshihiro;Takenaka, Shigeori;Takagi, Makoto
    • Analytical Science and Technology
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    • v.8 no.4
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    • pp.887-894
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    • 1995
  • Toward the development of universal, sensitive, and convenient method of DNA (or RNA) detection, two kinds of electrochemically active DNA ligands. acridine - viologen and oligonucleotide - ferrocene conjugate, were prepared. Thermodynamic and electrochemical study revealed that these probes bound strongly to DNA, and showed a typical cyclic voltammograms, indicating a potential for use as a reversible electrochemical labelling agent for DNA. Especially, using the electrochemically active oligonucleotide, we have been able to demonstrate the detection of DNA at femtomole levels by HPLC equipped with ordinary electrochemical detector (ECD). These results lead to the conclusion that the redox-active probes are very useful for the microanalysis of nucleic acid due to the stabilily of the complexes, high detection sensitivity, and wide applicability to the target structures (single- and double strands) and sequences.

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Elucidation of Electrode Reaction of EuCl3 in LiCl-KCl Eutectic Melts through CV Curve Analysis

  • Kim, Tack-Jin;Jung, Yong-Ju;Kim, Si-Hyung;Paek, Seung-Woo;Ahn, Do-Hee
    • 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.

Electrochemical Study of [Ni63-Se)2μ4-Se)3(dppf)3] Cluster and Its Catalytic Activity towards the Electrochemical Reduction of Carbon Dioxide

  • Park, Deog-Su;Jabbar, Md. Abdul;Park, Hyun;Lee, Hak-Myoung;Shin, Sung-Chul;Shim, Yoon-Bo
    • Bulletin of the Korean Chemical Society
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    • v.28 no.11
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    • pp.1996-2002
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    • 2007
  • The redox behavior of a [Ni6(μ3-Se)2(μ4-Se)3(Fe(η 5-C5H4P-Ph2)2)3] (= [Ni-Se-dppf], dppf = 1,1-bis(diphenylphosphino) ferrocene) cluster was studied using platinum (Pt) and glassy carbon electrodes (GCE) in nonaqueous media. The cluster showed electrochemical activity at the potential range between +1.6 and ?1.6 V. In the negative region (0 to ?1.6 V), the cluster exhibited two-step reductions. The first step was one-electron reversible, while the second step was a five-electron quasi-reversible process. On the other hand, in the positive region (0 to +1.6 V), the first step involved one-electron quasi-reversible process. The applicability of the cluster was found towards the electrocatalytic reduction of CO2 and was evaluated by experiments using rotating ring disc electrode (RRDE). RRDE experiments demonstrated that two electrons were involved in the electrocatalytic reduction of CO2 to CO at the Se-Ni-dppf-modified electrode.

Utilizing Natural and Engineered Peroxiredoxins As Intracellular Peroxide Reporters

  • Laer, Koen Van;Dick, Tobias P.
    • Molecules and Cells
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    • v.39 no.1
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    • pp.46-52
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    • 2016
  • It is increasingly apparent that nature evolved peroxiredoxins not only as $H_2O_2$ scavengers but also as highly sensitive $H_2O_2$ sensors and signal transducers. Here we ask whether the $H_2O_2$ sensing role of Prx can be exploited to develop probes that allow to monitor intracellular $H_2O_2$ levels with unprecedented sensitivity. Indeed, simple gel shift assays visualizing the oxidation of endogenous 2-Cys peroxiredoxins have already been used to detect subtle changes in intracellular $H_2O_2$ concentration. The challenge however is to create a genetically encoded probe that offers real-time measurements of $H_2O_2$ levels in intact cells via the Prx oxidation state. We discuss potential design strategies for Prx-based probes based on either the redoxsensitive fluorophore roGFP or the conformation-sensitive fluorophore cpYFP. Furthermore, we outline the structural and chemical complexities which need to be addressed when using Prx as a sensing moiety for $H_2O_2$ probes. We suggest experimental strategies to investigate the influence of these complexities on probe behavior. In doing so, we hope to stimulate the development of Prx-based probes which may spearhead the further study of cellular $H_2O_2$ homeostasis and Prx signaling.

Metabolic Engineering of Saccharomyces cerevisiae for Redox Balance of Xylose Fermentation

  • Kim, Soo Rin;Jin, Yong-Su
    • Current Research on Agriculture and Life Sciences
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    • v.32 no.4
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    • pp.199-202
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    • 2014
  • The bioconversion of cellulosic biomass hydrolyzates consisting mainly of glucose and xylose requires the use of engineered Saccharomyces cerevisiae expressing a heterologous xylose pathway. However, there is concern that a fungal xylose pathway consisting of NADPH-specific xylose reductase (XR) and $NAD^+$-specific xylitol dehydrogenase (XDH) may result in a cellular redox imbalance. However, the glycerol biosynthesis and glycerol degradation pathways of S. cerevisiae, termed here as the glycerol cycle, has the potential to balance the cofactor requirements for xylose metabolism, as it produces NADPH by consuming NADH at the expense of one mole of ATP. Therefore, this study tested if the glycerol cycle could improve the xylose metabolism of engineered S. cerevisiae by cofactor balancing, as predicted by an in-silico analysis using elementary flux mode (EFM). When the GPD1 gene, the first step of the glycerol cycle, was overexpressed in the XR/XDH-expressing S. cerevisiae, the glycerol production significantly increased, while the xylitol and ethanol yields became negligible. The reduced xylitol yield suggests that enough $NAD^+$ was supplied for XDH by the glycerol cycle. However, the GPD1 overexpression completely shifted the carbon flux from ethanol to glycerol. Thus, moderate expression of GPD1 may be necessary to achieve improved ethanol production through the cofactor balancing.

Electrochemical Reaction and Short-Circuit Behavior between Lead Borate Glass Doped with Metal Filler and Ni-Cr Alloy Wire (금속 필러가 첨가된 Pb-B-O계 유리와 Ni-Cr 합금 와이어 간의 전기 화학적 반응과 단락 거동)

  • Choi, Jin Sam;Nakayama, Tadachika
    • Korean Journal of Materials Research
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    • v.31 no.8
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    • pp.471-479
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    • 2021
  • The electrochemical reaction between lead borate glass frit doped with Sn metal filler and Ni-Cr wire of a J-type resistor during a term of Joule heating is investigated. The fusing behavior in which the Ni-Cr wire is melted is not observed for the control group but measured for the Sn-doped specimen under 30 V and 500 mA. The Sn-doped lead borate glass frit shows a fusing property compared with other metal-doped specimens. Meanwhile, the redox reaction significantly contributes to the fusing behavior due to the release of free electrons of the metal toward the glass. The electrons derived from the glass, which used Joule heat to reach the melting point of Ni-Cr wire, increase with increasing corrosion rate at interface of metal/glass. Finally, the confidence interval is 95 ± 1.959 %, and the adjusted regression coefficient, R in the optimal linear graph, is 0.93, reflecting 93% of the data and providing great potential for fusible resistor applications.

A Treatment of Acid Mine Drainage Using the Rice Stalk and Cow Manure (볏짚 및 우분을 이용한 산성광산배수 정화)

  • 정영욱;민정식;이현주;권광수
    • Journal of the Korean Society of Groundwater Environment
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    • v.4 no.3
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    • pp.116-121
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    • 1997
  • Pilot wetland reactor systems to test acid mine drainage treatment efficiencies for metals were designed and operated at the Dalsung mine and surveyed the operating problems. pH and Eh (redox potential) were measured in situ and anayses of Cd, Pb, As, Zn, Cu, Fe, Al and Mn were carried out in the laboratory. Maximum metal removal efficiencies of the reactor containing the rice stalks, the cow manure and limestones were that Cu, Zn, Fe, Cd, Al, Mn and Pb were lowered by 98%, 100%, 99%, 100%, 97%, 61% and 100%, respectively and at that time the pH and Eh of the effluents from the reactor were 6 and about -300 mV. However, the redox potential was raised and removal of metal elements except aluminium was decreased with operation time. It suggests that the reduced condition is very important for the metal removal. During the operation, problems such as scaling in pipes and volume change of the substrate within the reactor occurred, which were preventing the flow of main drainage in pipes and reactor.

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Optimization of L-leucine Fermentation (L-leucine 발효의 최적화)

  • 신현철;하구선;조영제;전영중;김성준;이재홍
    • Microbiology and Biotechnology Letters
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    • v.20 no.6
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    • pp.677-680
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    • 1992
  • The effects of pH, temperature and oxygen transfer rate(OTR) on L-Ieucine fermentation were investigated employing Corynebacterium glutamicum CH 1516 in 71 fermentor. The optimum pH, temperature and OTR were determined to be 7.0, $30^{\circ}C$ and 0.21 kmole $O_2$/$m^3{\cdot}hr$, respectively. For the values of OTR lower than 0.19 kmole $O_2$/$m^3{\cdot}hr$ a significant amount of lactic acid was accumulated, while the packed cell volume(PCV) was rapidly increased at higher OTR values above 0.23 kmole $O_2$/$m^3{\cdot}hr$ and glutamic acid was produced to some extent. Scale-up studies for L-Ieucine fermentation which was carried out in 12001 pilot scale fermentor reaffirmed the results of 71 fermentation. The optimum redox potential value for L-Ieucine production was found to be -150 to -170 mY.

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