• 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.

• 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.

• 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.

• Carbon letters
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• v.28
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• pp.105-110
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• 2018

Owing to their scalability, flexible operation, and long cycle life, vanadium redox flow batteries (VRFBs) have gained immense attention over the past few years. However, the VRFBs suffer from significant polarization, which decreases their cell efficiency. The activation polarization occurring during vanadium redox reactions greatly affects the overall performance of VRFBs. Therefore, it is imperative to develop electrodes with numerous catalytic sites and a long cycle life. In this study, we synthesized heteroatom-rich carbon-based freestanding papers (H-CFPs) by a facile dispersion and filtration process. The H-CFPs exhibited high specific surface area (${\sim}820m^2g^{-1}$) along with a number of redox-active heteroatoms (such as oxygen and nitrogen) and showed high catalytic activity for vanadium redox reactions. The H-CFP electrodes showed excellent electrochemical performance. They showed low anodic and cathodic peak potential separation (${\Delta}E_p$) values of ~120 mV (positive electrolyte) and ~124 mV (negative electrolyte) in cyclic voltammetry conducted at a scan rate of $5mV\;s^{-1}$. Hence, the H-CFP-based VRFBs showed significantly reduced polarization.

• Journal of Surface Science and Engineering
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• v.52 no.3
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• pp.180-185
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• 2019

The demands to improve the performance of the vanadium redox flow battery have attracted an intense research on modifying the carbon-based electrode. In this study, the surface of graphite felt was reformed, using cobalt oxide. The cobalt oxide was implanted into graphite felt during hydrothermal and two step heat treatments. The cobalt was deposited by hydrothermal method and the two step heat treatments made lots of holes on the graphite felt surface which is called as porous surface. The porous surface acts as an electrochemically active site for the cathodic reaction of vanadium redox flow battery. The reformed electrode shows the electrochemically improved performance compared with the pristine electrode.

• BMB Reports
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• v.34 no.2
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• pp.139-143
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• 2001

Thioredoxin (Trx) is a redox protein possessing conserved sequence Cys-Gly-Pro-Cys in ail organisms. Trx acts as an electron donor of many proteins including thioredoxin peroxidase (TPx). Yeast Trx 2 has two redox active cysteine residues at positions 31 and 34. To investigate the redox activity of each cysteine, we generated mutants C31S, C34S, and C31S/C34S using site directed mutagenesis and examined the redox activity of Trx variants as an electron donor for yeast TPx enzymes. None of the three Cysmutated Trx proteins was active as a redox protein in the 5', 5'-dithiobis-(2-dinitrobenzoic acid) reduction under the condition of the presence of NADPH and thioredoxin reductase, and in the thioredoxin dependent peroxidase activity of yeast TPx II. C34S enhanced the glutamine synthetase protection activity of yeast TPx I, even though 100 times more protein was needed to exhibit the same activity to WT. The formation of a mixed disulfide intermediate between Trx and TPx II subunits was analyzed by SDS-PAGE. The mixed dieter form of TPx II was found only for C34S. These results suggest that Cys-31 more effectively acts as an electron donor for TPx enzymes.

• Korean Chemical Engineering Research
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• v.57 no.1
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• pp.17-21
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• 2019

The redox flow battery (RFB) is a large-capacity energy storage equipment, and the vanadium redox flow cell is a typical RFB, but VRFB is expensive. Iron-chrome RFBs are economical because they use low-cost active materials, but their low performance is an urgent problem. One of the reasons for the low performance is the crossover of the active materials. In this study, the sulfonated Poly (ether ether ketone) (sPEEK) membrane, which is a hydrocarbon membrane, was used instead of the fluorine membrane to reduce the crossover of the active materials. The chromium ion permeability of the sPEEK membrane was $1.8{\times}10^{-6}cm^2/min$, which was about 1/33 of that of the Nafion membrane. Thus, it was shown that the use of the sPEEK membrane instead of the fluorine membrane could solve the high active material crossover problem. The activation energy of iron diffusion through the sPEEK membrane was 24.9 kJ/mol, which was about 66% of Nafion membrane. And that the e-PTFE support in the polymer membrane reduces the active material crossover through Iron-Chrome Redox Flow Battery (ICRFB).

• Proceedings of the Korean Society of Toxicology Conference
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• 2001.05a
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• pp.84-88
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• 2001

Human Thioredoxin (TRX) with with redox-active dithiol (C-C-Y-C-) in the active site has been cloned as adult T cell leukemia derived factor produced by HTLV-I transformed cells. Thioredoxin (TRX) is one of the major components of the thiol-reducing system and plays multiple roles in cellular processes such as proliferation, apoptosis and gene expression.(omitted)

• BMB Reports
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• v.48 no.4
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• pp.200-208
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• 2015

The field of redox proteomics focuses to a large extent on analyzing cysteine oxidation in proteins under different experimental conditions and states of diseases. The identification and localization of oxidized cysteines within the cellular milieu is critical for understanding the redox regulation of proteins under physiological and pathophysiological conditions, and it will in turn provide important information that are potentially useful for the development of novel strategies in the treatment and prevention of diseases associated with oxidative stress. Antioxidant enzymes that catalyze oxidation/reduction processes are able to serve as redox biomarkers in various human diseases, and they are key regulators controlling the redox state of functional proteins. Redox regulators with antioxidant properties related to active mediators, cellular organelles, and the surrounding environments are all connected within a network and are involved in diseases related to redox imbalance including cancer, ischemia/reperfusion injury, neurodegenerative diseases, as well as normal aging. In this review, we will briefly look at the selected aspects of oxidative thiol modification in antioxidant enzymes and thiol oxidation in proteins affected by redox control of antioxidant enzymes and their relation to disease. [BMB Reports 2015; 48(4): 200-208]

• Applied Chemistry for Engineering
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• v.35 no.3
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• pp.255-259
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• 2024

In this study, an aqueous-based redox flow battery (RFB) was constructed using tungstosilic acid (TSA), which is a kind of polyoxometalate, as the negative electrode active material and iron chloride (FeCl3) as the positive electrode active material in a sulfuric acid (H₂SO₄) supporting electrolyte. As a result of the cell's performance, it exhibited capacity fading and low energy efficiency. To address these issues, malic acid (MA), an organic additive, was introduced to the positive electrode active material and then tested for electrochemical properties and single cell performance. The malic acid in the iron chloride aqueous solution is working as a chelate agent, and two carboxyl groups are effectively coordinated with iron ions. It was found that MA reduced the electrolyte resistance of the positive electrode active material, leading to chemical stabilization and an increase in capacity and energy efficiency.