• Bulletin of the Korean Chemical Society
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• 제30권12호
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• pp.2875-2876
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• 2009

• Molecules and Cells
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• 제26권3호
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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.

• 한국수소및신에너지학회논문집
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• 제19권5호
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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.

• 전기화학회지
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• 제7권1호
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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.

• 전기화학회지
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• 제11권3호
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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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• 제31권3호
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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.

• 대한화학회지
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• 제34권5호
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• pp.490-497
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• 1990

1,4-dibora-2-cyclohexene 고리화합물 8을 합성하기 위한 두 가지 방법이 개발되었다. 방법 i)은 1,2-bis(dichloroaluminyl)ethane을 출발물질로 하는데 이 물질은 AlCl$_2$ 부분을 BCl$_2$로 치환시켜준다. 1,2-bis(dichloroaluminyl)ethane에 결합된 염소를 BI$_3$로 교환시켜 대응되는 요오드 화합물을 얻고 이 화합물을 alkynes와 반응시켜 헤테로고리화합물 8a, b를 많이 얻었다. 방법 ii)는 B$_2$Cl$_4$를 alkynes에 부가시켜 얻어지는 염소화합물에 BI$_3$를 치환시켜 bis(diiodoboryl)ethane유도체를 얻고 이 화합물에 alkynes와 산화환원반응을 하여줌으로 8c, d를 얻는다. 요오드 유도체인 8a는 pyridine 부가물인 9a를 생성하고 또 ether와 반응하여 ethoxy 유도체인 8e를 생성시킨다. 요오드 유도체의 dimethyl amino 치환제가 8f이다. 8a-d와 AlMe$_3$를 반응시켜 대응되는 methyl유도체인 8g-j를 얻고 이들 화합물은 THF속에서 칼륨과 반응시켜 불안정한 라디칼 음이온이 생성되고 여기서 ESR 결과가 측정된다. 8g-j의 전기화학적인 실험이 비가역적인 환원반응으로 나타났다. 8g-j화합물은 (C$_5$H$_5$)CO(C$_2$H$_4$)$_2$와 반응하여 중간체인 16개 VE(valence electron)를 갖는 착물 (C$_5$H$_5$)Co(8)이 얻어지는데 이 화합물은 다시 C-H 활성화에 의해 대응되는 붉은색의 1,4-diboracyclohexene 착물 10을 생성하게 된다. 착물 10h와 10j의 X-ray 구조가 결정되었다.