• Title/Summary/Keyword: Redox-active molecules

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Characterization of Electric Double-Layer Capacitor with 0.75M NaI and 0.5 M VOSO4 Electrolyte

  • Chun, Sang-Eun;Yoo, Seung Joon;Boettcher, Shannon W.
    • Journal of Electrochemical Science and Technology
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    • v.9 no.1
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    • pp.20-27
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    • 2018
  • We describe a redox-enhanced electric double-layer capacitor (EDLC) that turns the electrolyte in a conventional EDLC into an integral, active component for charge storage-charge is stored both through faradaic reactions with soluble redox-active molecules in the electrolyte, and through the double-layer capacitance in a porous carbon electrode. The mixed-redox electrolyte, composed of vanadium and iodides, was employed to achieve high power density. The electrochemical reaction in a supercapacitor with vanadium and iodide was studied to estimate the charge capacity and energy density of the redox supercapacitor. A redox supercapacitor with a mixed electrolyte composed of 0.75 M NaI and 0.5 M $VOSO_4$ was fabricated and studied. When charged to a potential of 1 V, faradaic charging processes were observed, in addition to the capacitive processes that increased the energy storage capabilities of the supercapacitor. The redox supercapacitor achieved a specific capacity of 13.44 mAh/g and an energy density of 3.81 Wh/kg in a simple Swagelok cell. A control EDLC with 1 M $H_2SO_4$ yielded 7.43 mAh/g and 2.85 Wh/kg. However, the relatively fast self-discharge in the redox-EDLC may be due to the shuttling of the redox couple between the polarized carbon electrodes.

Functional Diversity of Cysteine Residues in Proteins and Unique Features of Catalytic Redox-active Cysteines in Thiol Oxidoreductases

  • Fomenko, Dmitri E.;Marino, Stefano M.;Gladyshev, Vadim N.
    • Molecules and Cells
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    • v.26 no.3
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    • pp.228-235
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    • 2008
  • Thiol-dependent redox systems are involved in regulation of diverse biological processes, such as response to stress, signal transduction, and protein folding. The thiol-based redox control is provided by mechanistically similar, but structurally distinct families of enzymes known as thiol oxidoreductases. Many such enzymes have been characterized, but identities and functions of the entire sets of thiol oxidoreductases in organisms are not known. Extreme sequence and structural divergence makes identification of these proteins difficult. Thiol oxidoreductases contain a redox-active cysteine residue, or its functional analog selenocysteine, in their active sites. Here, we describe computational methods for in silico prediction of thiol oxidoreductases in nucleotide and protein sequence databases and identification of their redox-active cysteines. We discuss different functional categories of cysteine residues, describe methods for discrimination between catalytic and noncatalytic and between redox and non-redox cysteine residues and highlight unique properties of the redox-active cysteines based on evolutionary conservation, secondary and three-dimensional structures, and sporadic replacement of cysteines with catalytically superior selenocysteine residues.

Computational screening of electroactive indolequinone derivatives as high-performance active materials for aqueous redox flow batteries

  • Han, Young-Kyu;Jin, Chang-Soo
    • Current Applied Physics
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    • v.18 no.12
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    • pp.1507-1512
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    • 2018
  • The development of an organic-based aqueous redox flow battery (RFB) using quinone as an electroactive material has attracted great attention recently. This is because this battery is inexpensive, produces high energy density, and is environment friendly in stationary electrical energy storage applications. Herein, we investigate the redox potentials and solubilities of indole-5,6-quinone and indole-4,7-quinone derivatives in terms of the substituent effects of functional groups using theoretical calculations. Our results indicate that full-site substituted derivatives of indolequinone are more useful as active materials compared to single-site substituted derivatives. In particular, our calculations reveal that the substitution of $-PO_3H_2$ and $-SO_3H$ functional groups with multiple polar bonds is very effective in increasing the activity of the aqueous RFB. As a strategy to overcome the limitation that the aqueous solubility is intrinsically low because they are organic molecules, we suggest the substitution of functional groups with multiple polar bonds to the backbones of active organic materials. Among 180 indolequinone derivatives, 17 candidates that meet the redox potential standards ($${\leq_-}0.2V$$ or $${\geq_-}0.9V$$) and eight candidates with solubility exceeding 2 mol/L are identified. Three indolequinone derivatives that satisfy both conditions are finally presented as promising electroactive candidates for an aqueous RFB.

Multi-Electron Donor Organic Molecules Containing Hydroquinone Methyl-Ether as Redox Active Units

  • Khandelwal, Manish;Hwang, In-Chul;Nair, Prakash Chandran R.;Lee, Jung-Woo
    • Bulletin of the Korean Chemical Society
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    • v.33 no.4
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    • pp.1190-1198
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    • 2012
  • Three hydroquinone dimethyl ether derivatives have been synthesized and characterized by X-ray diffraction. The electron donating properties were evaluated by using UV-vis spectroscopy, cyclic voltammetry and by ESR spectroscopy. The microcrystalline cation-radical salts of the three donor molecules were also isolated by using antimony pentachloride, a single electron Lewis acid oxidant.

Poly-3,4-dihydroxybenzaldehyde Modified with 3,4-dihydroxybenzoic acid for Improvement of Electrochemical Activities

  • Cha Seong-Keuck
    • Journal of the Korean Electrochemical Society
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    • v.7 no.4
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    • pp.167-172
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    • 2004
  • 3,4-dihydroxybenzaldehyde(3,4-DHB) was oxidatively el electropolymerized on glassy carbon (GC) electrodes to prepare CC/p-3,4-DHB type electrodes, which were subsequently modified with 3,4-dihydroxybenzoic acid(3,4-DHBA) using 0.05M HCI as a catalyst. The esterification reactions were performed between -OH sites on the polymeric film surface of the p-3,4-DHB and the -COOH sites within the 3,4-DHBA molecules in solution. These reactions had a rate constant value of $1.1\times10^{-1}\;s^{-1}$ for the esterification step as obtained from the first-order rate constant in the solution. The electrochemical responses of the GC/p-3,4-DHB-3,4-DHBA electrodes exert an influence upon the buffer solution, its pH and applied potential ranges. The redox process of the electrode was more easily controlled by charge transfer kinetics than that of the CC/p-3,4-DHB. The modified electrodes had redox active sites that were 10 times more active than those present before modification. The electrical admittance of the modified electrodes was also three times higher than that of the unmodified electrodes. After being annealed in ethanol for 20 hrs the electrodes brought about a 3.3 times greater change of water molecules in the redox reaction. The modified electrodes are stable in the potential range of 0.4 to 0.55V.

A Study on the Current-Voltage Characteristics of Self-Assembled Organic Molecules by using STM

  • Kim Seung-Un;Shin Hoon-Kyu;Kwon Young-Soo
    • KIEE International Transactions on Electrophysics and Applications
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    • v.5C no.3
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    • pp.115-118
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    • 2005
  • Currently, molecular devices are reported utilizing active self-assembled monolayers (SAMs) containing the nitro group as the active component, which has active redox centers [1]. SAMs are ordered molecular structures formed by the adsorption of an active surfactant on a solid surface. The molecules will be spontaneously oriented toward the substrate surface and form an energetically favorable ordered layer. During this process, the surface-active head group of the molecule chemically reacts with and chemisorbs onto the substrate In this paper, the electrical properties of the 4'4- di(ethynylphenyl)-2'-nitro-1-benzenethiolate was confirmed. This material is well known as a conducting molecule having possible application to molecular level negative differential resistance (NDR) device. To deposit the self-assembly monolayers onto the gold electrode, the prefabricated Au(1 l l) substrates were immersed into 0.5[mM/l] self-assembly molecule in THF solution. Then, the electrical properties and surface morphologies of 4' 4-di(ethynylphenyl)-2' -nitro-1-benzenethiolate were measured by using the ultra-high vacuum scanning tunneling microscopy (UHV-STM).

Electrical Characteristics of Self-Assembled Organic Thin Films Using Ultra-High Vacuum Scanning Tunneling Microscopy (UHV STM을 이용한 유기 초박막의 전기적 특성 연구)

  • Kim, Seung-Un;Shin, Hoon-Kyu;Kwon, Young-Soo
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2003.11a
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    • pp.108-111
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    • 2003
  • Currently, molecular devices are reported utilizing active self-assembled monolayers containing the nitro group as the active component, which has active redox centers[1]. We confirm the electrical properties of 4,4-di(ethynylphenyl)-2'-nitro-1-benzenethiolate. To deposit the SAM layer onto gold electrode, we transfer the prefabricated Au(111) substrates into a 1mM self-assembly molecules in THF solution. Au(111) substrates were prepared by ion beam sputtering method of gold onto the silicon wafer. As a result, we measured current-voltage curve using ultra high vacuum scanning tunneling microscopy (UHV STM), I-V curve also clearly shows several current peaks between the negative bias region (-0.3958V) and the positive bias region (0.4658V), respectively.

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Conducting Polymers with Functional Dopants and their Applications in Energy, Environmental Technology, and Nanotechnology

  • Kim, Sung Yeol;Song, Hyun-Kon
    • Clean Technology
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    • v.21 no.1
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    • pp.12-21
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    • 2015
  • Development of novel conducting polymers (CPs) is expected to facilitate the advancement of functional materials used for energy, environmental, and nanotechnology. Recent research efforts are focused on doping CPs with functional dopants to enhance their performance or add additional functions that are not inherent in CPs. This review surveys literatures about the doped CPs focusing on the roles of functional dopants, unlike other reviews focusing on the development of new conducting polymer backbones. The functional dopants presented in this review include redox active molecules, carbon nanomaterials, biopolymers, and chelating molecules. Depending on the dopants and their physicochemical properties, the doped CPs can be used for a variety of applications such as polymer batteries, membranes for waste water treatment, and chemical sensors. A major challenge of the CPs is presented and the ways to overcome the challenge is also suggested for the future development of stable, high performance CPs.

Current-Voltage Characteristics of Molecular Electronic Devices Using a Amino-Style Derivatives (Amino-style 유도체를 이용한 분자 전자 소자의 전류-전압 특성에 관한 연구)

  • Kim, So-Young;Koo, Ja-Ryong;Kim, Young-Kwan
    • Proceedings of the Korean Institute of Electrical and Electronic Material Engineers Conference
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    • 2004.07b
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    • pp.882-885
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    • 2004
  • Organic molecules have many properties that make them attractive for electronic applications. We have been examining the progress of memory cell by using molecular-scale switch to give an example of the application using both nanoscale components and Si-technology. In this study, molecular electronic devices were fabricated with amion style derivatives as redox-active component to compare to the devices using Zn-Porphyrin derivatives. This molecule is amphiphilic to allow monolayer formation by the Langmuir-Blodgett (LB) method, and then this LB monolayer is inserted between two metal electrodes. According to current-voltage (I-V) characteristics, it was found that the devices show remarkable hysteresis behavior and can be used as memory devices at ambient conditions, when aluminum oxide layer was existed on bottom electrode. Diode-like characteristics were measured only, when Pt layer was existed as bottom electrode. It was also found that this metal layer interacts with the organic molecules and acts as a protecting layer, when thin Ti layer was inserted between the organic molecular layer and the top Al electrode. These electrical properties of the devices may be applicable to active components for the memory and/or logic gates in the future.

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Cell Death and Stress Signaling in Glycogen Storage Disease Type I

  • Kim, So Youn;Bae, Yun Soo
    • Molecules and Cells
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    • v.28 no.3
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    • pp.139-148
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    • 2009
  • Cell death has been traditionally classified in apoptosis and necrosis. Apoptosis, known as programmed cell death, is an active form of cell death mechanism that is tightly regulated by multiple cellular signaling pathways and requires ATP for its appropriate process. Apoptotic death plays essential roles for successful development and maintenance of normal cellular homeostasis in mammalian. In contrast to apoptosis, necrosis is classically considered as a passive cell death process that occurs rather by accident in disastrous conditions, is not required for energy and eventually induces inflammation. Regardless of different characteristics between apoptosis and necrosis, it has been well defined that both are responsible for a wide range of human diseases. Glycogen storage disease type I (GSD-I) is a kind of human genetic disorders and is caused by the deficiency of a microsomal protein, glucose-6-phosphatase-${\alpha}$ ($G6Pase-{\alpha}$) or glucose-6-phosphate transporter (G6PT) responsible for glucose homeostasis, leading to GSD-Ia or GSD-Ib, respectively. This review summarizes cell deaths in GSD-I and mostly focuses on current knowledge of the neutrophil apoptosis in GSD-Ib based upon ER stress and redox signaling.