• Bulletin of the Korean Chemical Society
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• v.30 no.12
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• pp.2875-2876
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• 2009

• 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 Hydrogen and New Energy
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• v.19 no.5
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• pp.394-402
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• 2008

The Effects of Cu or Ni additives co-added with Ce/Zr mixed oxides to Fe-based oxide mediums were investigated for the purpose of the replacement of Rh, a precious metal additive, in terms of hydrogen storage(reduction by hydrogen) and release(water splitting). From the results of temperature programmed reduction(TPR), initial reduction rate of iron oxide in the mediums was greatly increased with the addition of Cu, similar to that of Rh. For isothermal redox reaction of 10 cycles, the total amounts of hydrogen evolved in water splitting steps for the mediums added with Cu or Ni were highly maintained at ca. 7 mmol/g-material, even though the oxidation rates were slightly lower than that for the medium added with Rh. This result suggests that the replacement of Rh to Cu or Ni is possible as a co-additive for Fe-based oxide mediums.

• Journal of the Korean Electrochemical Society
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• v.7 no.1
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• pp.26-31
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• 2004

The direct electrochemical studies of four laccases (plant and fungal laccases) have been investigated on a gold electrode functionalized with a new tether of 2.2'-dithiosalicylic aldehyde. Results from these studies indicate that the redox potential of the active site of plant laccase from Rhus vernificera is shifted to a more negative value(255 mV versus SCE) than that of fungal laccase from Pyricularia oryzae (480 mV versus SCE). Mechanistic studies indicate that the reduction of type-1 Cu precedes the reduction of type-2 and type-3 Cu ions when the electrode is poised initially at different potentials. Also a new tether, 2.2'-dithiosalicylic aldehyde, has been used to study the redox properties of two laccases (LCCI and Lccla) covalently attached to a gold electrode. An irreversible peak at 0.47V vs. SCE is observed in the cyclic voltammorams of LCCI. In contrast, the cyclic voltammograms of LCCIa contain a quasi-reversible peak at 0.18V vs. SCE and an irreversible peak at 0.50V vs. SCE. We find that the replacement of the eleven amino acids a the C-terminus with a single cysteine residue $(i.e., \;LCCI{\rightarrow}LCCIa)$ influences the rate of heterogeneous electron transfer between an electrode and the copper containing active sites $(K_{het}\;for\;LCCI=1.0\times10^{-2}\;s^{-1}\;and\;K_{het}\;for\;LCCI_a= 1.0\;times10^{-1}\;s^{-1}\'at\;0.18V\;versus\;SCE\;and\;4.0\times10^{-2}\;s^{-1}\;at\;0.50V\; versus\;SCE)$. These results show for the first time that the change of the primary structure of a protein via site-directed mutagenesis influences both the redox potentials of the copper ions in the active site and the rate of heterogeneous electron transfer.

• Journal of the Korean Electrochemical Society
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• v.11 no.3
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• pp.154-158
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• 2008

The synthesis of hollow ${Sb_93}{Pt_7}$ nanospheres smaller than 30 nm with a shell consisting of smaller nanoparticles, with an average particle size of ${\sim}$ 3 nm is reported. The formation of this alloy is driven by galvanic replacement reaction involving Sb nanoparticles and ${H_2}{PtCl_6} $ without need for any additional reductants. Further, the reaction proceeds selectively as long as the redox potential between two metals is favorable. The capacities of the hollow samples are 669 and 587mAh/g at rates of 1 and 7C, respectively, while those values for the nanoparticles are 647 and 480mAh/g at rates of 1, 7C, respectively. This result shows the significantly improved capacity retention of the hollow sample at higher C rates, indicating that high surface area of the hollow nanospheres makes the current density more effective than that for the solid counterpart.

• Journal of Ecology and Environment
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• v.31 no.3
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• pp.213-223
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• 2008

The increasing area of abandoned rice fields could provide new opportunities for wetland restoration in Asia. However, it is unknown how quickly or completely abandoned rice fields will recover from agricultural disturbances. We assessed water quality and plant community succession in abandoned rice fields with different hydrology in a mountain valley to understand the effects of hydrological regime on recovery. Water level, soil redox potential, water quality, plant composition, and primary production were measured. The sites, coded as D6, N13, and N16, had been recovering for 6, 13, and 16 years by 2006. N13 and N16 have been recovering naturally whereas D6 has been drained with a nearby dike and was tilled in 2001. The typical hydroperiods of D6, N13, and N16 were no surface water, permanently flooded, and seasonally flooded, respectively. The major change in vegetation structure of both D6 and N13 was the replacement of herbaceous species by woody species. Drawdown accelerated this change because Salix koreensis grew better in damp conditions than in flooded conditions. Phragmites japonica reduced plot-level plant species richness. The removal efficiency of $NH_4-N$, $NO_3-N$, and $PO_4-P$ from water varied seasonally, ranging between -78.8 to 44.3%, 0 to 97.5%, and -26.0 to 44.4%, respectively. In summary, abandoned rice fields quickly became suitable habitat for native wetland plant species and improved regional water quality. Variation among our sites indicates that it is likely possible to manage abandoned rice fields, mostly through controlling hydrology, to achieve site-specific restoration goals.

• Journal of the Korean Chemical Society
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• v.34 no.5
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• pp.490-497
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• 1990

Two synthetic routes for the 1,4-diboracyclohexene-2 ring 8 have been developed. Method i) starts with 1,2-bis(dichloroaluminyl)ethane, in which the AlCl$_2$ group is replaced by BCl$_2$. Exchange of the chlorine with BI$_3$ in 1,2-bis-(dichloroboryl)ethane yields the corresponding iodo compound, which reacts with the alkynes to heterocycles 8a, b in good yield. In method ii) B$_2$Cl$_4$ is added to alkenes, replacement of chlorine with BI$_3$ yields the bis(diiodoboryl)ethane derivatives which undergo redox reactions with alkynes to give 8c, d. The diiodo derivative 8a forms the pyridine adduct 9a, and reacts with ether to give the ethoxy derivative 8f. 8a-d react with AlMe$_3$ to yield the corresponding dimethyl derivatives 8g-j, which give unstable radical anions when treated with potassium in THF. The ESR parameters are reported. In electrochemical experiments irreversible reductions of 8g-j are observed. 8g-j react with (C$_5$H$_5$)Co(C$_2$H$_4$)$_2$ to give the intermediate 16 VE complexes (C$_5$H$_5$)Co(8), in which C-H activation occurs with formation of the corresponding red 1,4-diboracyclohexadiene complexes 10. The X-ray structure analyses of 10h and 10j are reported.